light metal systems. part 2: selected systems from al-cu-fe to al-fe-ti

XI

Landolt-BörnsteinNew Series IV/11A2

MSIT®

Introduction

Introduction

Data Covered

The series focuses on light metal ternary systems and includes phase equilibria of importance for alloydevelopment, processing or application, reporting on selected ternary systems of importance to industriallight alloy development and systems which gained otherwise scientific interest in the recent years.

General

The series provides consistent phase diagram descriptions for individual ternary systems. Therepresentation of the equilibria of ternary systems as a function of temperature results in spacial diagramswhose sections and projections are generally published in the literature. Phase equilibria are described interms of liquidus, solidus and solvus projections, isothermal and pseudobinary sections; data on invariantequilibria are generally given in the form of tables.

The world literature is thoroughly and systematically searched back to the year 1900. Then, thepublished data are critically evaluated by experts in materials science and reviewed. Conflicting informationis commented upon and errors and inconsistencies removed wherever possible. It considers those, and onlythose data, which are firmly established, comments on questionable findings and justifies re-interpretationsmade by the authors of the evaluation reports.

In general, the approach used to discuss the phase relationships is to consider changes in state and phasereactions which occur with decreasing temperature. This has influenced the terminology employed and isreflected in the tables and the reaction schemes presented.

The system reports present concise descriptions and hence do not repeat in the text facts which canclearly be read from the diagrams. For most purposes the use of the compendium is expected to be self-sufficient. However, a detailed bibliography of all cited references is given to enable original sources ofinformation to be studied if required.

Structure of a System Report

The constitutional description of an alloy system consists of text and a table/diagram section which areseparated by the bibliography referring to the original literature (see Fig. 1). The tables and diagrams carrythe essential constitutional information and are commented on in the text if necessary.

Where published data allow, the following sections are provided in each report:

Literature Data

The opening text reviews briefly the status of knowledge published on the system and outlines theexperimental methods that have been applied. Furthermore, attention may be drawn to questions which arestill open or to cases where conclusions from the evaluation work modified the published phase diagram.

Binary Systems

Where binary systems are accepted from standard compilations reference is made to these compilations.In other cases the accepted binary phase diagrams are reproduced for the convenience of the reader. Theselection of the binary systems used as a basis for the evaluation of the ternary system was at the discretionof the assessor.

XII


MSIT®

Introduction

Solid Phases

The tabular listing of solid phases incorporates knowledge of the phases which is necessary or helpfulfor understanding the text and diagrams. Throughout a system report a unique phase name and abbreviationis allocated to each phase.

Phases with the same formulae but different space lattices (e.g. allotropic transformation) aredistinguished by:

– small letters (h), high temperature modification (h2 > h1)(r), room temperature modification(1), low temperature modification (l1 > l2)

– Greek letters, e.g., , '– Roman numerals, e.g., (I) and (II) for different pressure modifications.In the table “Solid Phases” ternary phases are denoted by * and different phases are separated by

horizontal lines.

Heading

Literature Data

Binary Systems

Solid Phases

Pseudobinary Systems

Invariant Equilibria

Liquidus, Solidus, Solvus Surfaces

Isothermal Sections

Miscellaneous

Miscellaneous

Isothermal Sections




Solid Phases

Binary Systems

Text

References

Tables anddiagrams

Temperature-Composition Sections

Temperature-Composition Sections

Thermodynamics

Materials Properties and Applications

Thermodynamics

Materials Properties and Applications

Fig. 1: Structure of a system report

XIII


MSIT®

Introduction


Pseudobinary sections describe equilibria and can be read in the same way as binary diagrams. The notationused in pseudobinary systems is the same as that of vertical sections, which are reported under“Temperature-Composition Sections”.


The invariant equilibria of a system are listed in the table “Invariant Equilibria” and, where possible, aredescribed by a constitutional “Reaction Scheme” (Fig. 2).

The sequential numbering of invariant equilibria increases with decreasing temperature, one numberingfor all binaries together and one for the ternary system.

Equilibria notations are used to indicate the reactions by which phases will be– decomposed (e- and E-type reactions)– formed (p- and P-type reactions)– transformed (U-type reactions)For transition reactions the letter U (Übergangsreaktion) is used in order to reserve the letter T to denote

temperature. The letters d and D indicate degenerate equilibria which do not allow a distinction accordingto the above classes.


The phase equilibria are commonly shown in triangular coordinates which allow a reading of theconcentration of the constituents in at.%. In some cases mass% scaling is used for better data readability(see Figs. 3 and 4).

In the polythermal projection of the liquidus surface, monovariant liquidus grooves separate phaseregions of primary crystallization and, where available, isothermal lines contour the liquidus surface (seeFig. 3).

Isothermal Sections

Phase equilibria at constant temperatures are plotted in the form of isothermal sections (see Fig. 4).

Temperature – Composition Sections

Non-pseudobinary T-x sections (or vertical sections, isopleths, polythermal sections) show the phasefields where generally the tie lines are not in the same plane as the section. The notation employed for thelatter (see Fig. 5) is the same as that used for binary and pseudobinary phase diagrams.

Thermodynamics

Experimental ternary data are reported in some system reports and reference to thermodynamicmodelling is made.

Notes on Materials Properties and Applications

Noteworthy physical and chemical materials properties and application areas are briefly reported if theywere given in the original constitutional and phase diagram literature.

Miscellaneous

In this section noteworthy features are reported which are not described in preceding paragraphs. Theseinclude graphical data not covered by the general report format, such as lattice spacing – composition data,p-T-x diagrams, etc.

XIV


MSIT®

Introduction

Fig

ure

2:

T

ypic

al r

eact

ion s

chem

e

Ag-T

lT

l-B

iB

i-A

gA

g-T

l-B

i

(Tl)

(h)

(T

l)(r

),(A

g)

23

4d

1l

(A

g)

+ (

Bi)

26

1e 5

(Ag

) +

(T

l)(h

) +

Tl 3

Bi

L +

Tl 3

Bi

(A

g)

+ (

Tl)

(h)

28

9U

1

l (

Ag

)+(T

l)(h

)

29

1e 3

l (

Tl)

(h)+

Tl 3

Bi

30

3e 1

l (

Bi)

+T

l 2B

i 3

20

2e 7

l T

l 3B

i+T

l 2B

i 3

19

2e 8

(Tl)

(h)

Tl 3

Bi+

(Tl)

(r)

14

4e 9

L (

Ag

) +

Tl 3

Bi

29

4e 2

(max

)

L (

Ag

) +

(T

l)(h

)

28

9e 4

(min

)

L (

Ag

) +

Tl 2

Bi 3

20

7e 6

(max

)

(Ag

)+(B

i)+

Tl 2

Bi 3

L (

Ag)+

(Bi)

+T

l 2B

i 31

97

E1

(Ag

)+(T

l)(r

)+T

l 3B

i

(Tl)

(h)

Tl 3

Bi

+ (

Tl)

(r),

(Ag

)1

44

D1

(Ag

)+T

l 3B

i+T

l 2B

i 3

L (

Ag

)+T

l 3B

i+T

l 2B

i 31

88

E2

seco

nd b

inar

y

eute

ctic

rea

ctio

nfi

rst

bin

ary e

ute

ctic

rea

ctio

n

(hig

hes

t te

mper

ature

)te

rnar

y m

axim

um

reac

tion

tem

per

atu

re

of

26

1°C

mo

no

var

iant

equil

ibri

um

sta

ble

do

wn

to

lo

w

tem

per

ature

s

seco

nd

tern

ary

eute

ctic

reac

tion

equat

ion o

f eu

tect

oid

reac

tion a

t 144°C

XV


MSIT®

Introduction

20

40

60

80

20 40 60 80

20

40

60

80

A B

C Data / Grid: at.%

Axes: at.%

δ700

p1

500

400

400°C

γ

300

U e1

700

500

β(h)

400

300

E

300

α400

e2

500°C isotherm, temperature is usualy in °C

liquidus groove to decreasing temperatures

estimated 400°C isotherm

limit of known region

ternary invariantreaction

binary invariantreaction

primary γ-crystallization

20

40

60

80

20 40 60 80

20

40

60

80

Al B

C Data / Grid: mass%

Axes: mass%

L+γ

γ+β(h)

L+γ+β(h)

β(h)

L+β(h)

L

L+α

α

phase field notation

estimated phase boundary

tie line

three phase field (partially estimated)

experimental points(occasionally reported)

limit of known region

phase boundary

γ

Fig. 3: Hypothetical liquidus surface showing notation employed

Fig. 4: Hypothetical isothermal section showing notation employed

XVI


MSIT®

Introduction

References

The publications which form the bases of the assessments are listed in the following manner:[1974Hay] Hayashi, M., Azakami, T., Kamed, M., “Effects of Third Elements on the Activity of Lead

in Liquid Copper Base Alloys” (in Japanese), Nippon Kogyo Kaishi, 90, 51-56 (1974) (Experimental,Thermodyn., 16)

This paper, for example, whose title is given in English, is actually written in Japanese. It was publishedin 1974 on pages 51- 56, volume 90 of Nippon Kogyo Kaishi, the Journal of the Mining and MetallurgicalInstitute of Japan. It reports on experimental work that leads to thermodynamic data and it refers to 16 cross-references.

Additional conventions used in citing are:# to indicate the source of accepted phase diagrams* to indicate key papers that significantly contributed to the understanding of the system.Standard reference works given in the list “General References” are cited using their abbreviations and

are not included in the reference list of each individual system.

60 40 200

250

500

750

A 80.00B 0.00C 20.00

A 0.00B 80.00C 20.00Al, at.%

Tem

pera

ture

, °C

L

32.5%L+β(h)

β(r) - room temperature

β(r)

L+α+β(h)

α+β(h)

α

L+α

phase field notation

concentration ofabscissa element

alloy compositionin at.%

β(h)

modification

β(h) - high temperaturemodification188

temperature, °C

Fig. 5: Hypothetical vertical section showing notation employed

XVII


MSIT®

Introduction

General References

[C.A.] Chemical Abstarts - pathways to published research in the world's journal and patentliterature - http://www.cas.org/

[Curr.Cont.] Current Contents - bibliographic multidisciplinary current awareness Web resource - http://www.isinet.com/products/cap/ccc/

[E] Elliott, R.P., Constitution of Binary Alloys, First Supplement, McGraw-Hill, New York(1965)

[G] Gmelin Handbook of Inorganic Chemistry, 8th ed., Springer-Verlag, Berlin [H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York

(1958) [L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and

Technology (New Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P.,Kandler, H. and Stegherr, A., Structure Data of Elements and Intermetallic Phases (1971);Vol. 7, Pies, W. and Weiss, A., Crystal Structure of Inorganic Compounds, Part c, KeyElements: N, P, As, Sb, Bi, C (1979); Group 4: Macroscopic and Technical Properties of

Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic and Thermodynamic Data of

Binary Alloys, Subvol. a: Ac-Au ... Au-Zr (1991); Springer-Verlag, Berlin. [Mas] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, ASM, Metals Park, Ohio (1986) [Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International,

Metals Park, Ohio (1990) [P] Pearson, W.B., A Handbook of Lattice Spacings and Structures of Metals and Alloys,

Pergamon Press, New York, Vol. 1 (1958), Vol. 2 (1967) [S] Shunk, F.A., Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New York

(1969) [V-C] Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for

Intermetallic Phases, ASM, Metals Park, Ohio (1985) [V-C2] Villars, P. and Calvert, L.D., Pearson's Handbook of Crystallographic Data for

Intermetallic Phases, 2nd edition, ASM, Metals Park, Ohio (1991)

1


MSIT®

Al–Cu–Fe

Aluminium – Copper – Iron

Cui Ping Wang, Xing Jun Liu, Liming Zhang, Kiyohito Ishida

Literature Data

Critical evaluation of constitutional data in the Al-Cu-Fe system has been done by [1991Leg] covering the

then known literature. The present evaluation updates and amends this work within the same evaluation

program. The investigations on the phase equilibria in the Al-rich portion have been carried out by

[1924Fue, 1925Got, 1928Arc, 1928Gwy, 1932Yam, 1933Rol, 1934Fue, 1939Bra2, 1939Nis, 1940Fin,

1940Hun, 1940Shi, 1940Wie, 1941Bro, 1948Sha, 1950Phr, 1952Han, 1954Phi, 1984Ben, 1992Gay1,

1992Gay2, 1992Zak, 1993Fau1, 1993Fau2, 2000Yok1, 2000Yok2, 2000Yok3, 2001Ros], and two reviews

have been presented by [1961Phi] and [1976Mon]. The Cu-rich equilibria have been studied by [1938Nis,

1939Bra1, 1941Yut] and [1952Haw] and the Fe-rich equilibria by [1939Bra1]. The effect of small amount

of Fe on the phase equilibria in the Al-Cu alloys was reported by [2001Liu], and that of Cu on site

occupancy and diffusion behavior in the Al-Fe alloys was studied by [1997And, 2002Ban] and [1998Akd],

respectively. [1997Oht] determined the liquid/solid equilibria in the Cu-Fe side on the basis of

thermodynamic calculation and diffusion couple technique, and the extensive investigation of [1997Oht]

was continued by [1998Wan], in which solid/solid equilibria and an order-disorder transition of the bcc

phase are included. More recently, [2002Zha, 2003Zha1, 2003Zha2, 2003Zha3, 2003Zha4] carried out

detailed experimental investigations of the phase equilibria in the Al-rich portion around the icosahedral

quasicrystalline phase region on the basis of the techniques of differential thermal analysis, magnetothermal

analysis, scanning electron microscopy and X-ray diffraction. [2003Mie] presented a thermodynamic

assessment for the phase equilibria in the Cu-Fe side portion.

The different fields of crystallization are proposed by [1939Bra2] and [1971Pre], but in [1939Bra2] the

phase 1 is missing and in [1971Pre] the compositions given are not in good agreement with their published

diagram. General studies about the system have been proposed by [1935Bos, 1936Bra, 1940Bra, 1955Tur,

1956Spe, 1969LeM, 1972Miu, 1972Pro, 1973Kow, 1975Wac, 1978Pan1, 1981Bre] and [1987Str]. In

particular, in the past decade, enormous investigations on crystal structure and physical and mechanical

properties of icosahedral quasicrystalline phase have been performed by [1991Aud1, 1991Aud2, 1991Bes,

1991Che1, 1991Che2, 1991Fau, 1991Jan, 1991Men, 1991Lei, 1991Liu1, 1991Liu2, 1991Qui, 1991Wu,

1991Zha, 1992Che1, 1992Che2, 1992Eib, 1992Mat, 1992Nas, 1993Ban, 1993Bes, 1993Lee, 1993Men,

1993Was, 1994Bes, 1994Fre1, 1994Fre2, 1994Law, 1994Lef, 1995Div, 1996Qui, 1997Div, 1997Ham,

1997Pop, 1997Ros, 1997She, 1998Dun, 1998Ma, 2000Bou, 2000Dun, 2000Gre1, 2000Gre2, 2000Jon,

2000Nak, 2000Sha, 2000Ste, 2000Uch, 2001Bar, 2001Cai, 2001Gui, 2001Jon, 2001Sur, 2001Guo,

2002Hir, 2002Gre, 2002Kra, 2002Sha].

Binary Systems

The Al-Cu binary system was reviewed by [1985Mur], and has been adopted from [1994Mur] with

modification of [1998Liu], where it is found that earlier reported phase 0 does not exist, and the earlier

reported two-phase equilibrium ( 0+ 1) was determined as second order reaction 1- 0 in the composition

range of 62-68 at.% Cu. The Al-Fe and Cu-Fe binary systems have been accepted from [1993Kat] and

[2001Tur], respectively.

Solid Phases

Data on all solid phases are given in Table 1. The existence of a stable single icosahedral quasicrystalline

phase ( i) has been reported for the first time by [1987Tsa1] and [1987Tsa2] and later on by a series of

research groups [1988Bou, 1988Hir, 1988Ish, 1988Tsa, 1989Dev, 1989Don, 1989Eba]. The formation

range of the icosahedral phase found by [1987Tsa1] is close to the composition range of a ternary phase

discovered by [1939Bra2] and referred to as phase (about 20 to 26 at.% Cu and 12 to 13 at.% Fe) the

2


MSIT®

Al–Cu–Fe

structure of which was left unidentified. [1990Cal] has demonstrated that the phase is indeed the

icosahedral phase. Following [1990Fau1, 1991Fau], the composition range of the icosahedral phase is

around Fe12.5Cu25.5Al62. [1939Bra2, 1989Don, 1990Fau1, 2000Yok1, 2000Yok2] and [2003Zha1] agree

that the icosahedral i phase formation proceeds following a peritectic reaction.

There is also a general agreement that the Al-Cu-Fe icosahedral phase corresponds to an F type structure

which can be seen as an ordered F superstructure of the primitive six dimensional (6D) hypercubic lattice

[1988Ish, 1989Dev, 1989Eba] and exists as a single phase stable at 800°C. At lower temperatures (about

600°C) the structure strongly depends on the composition of the alloy. For compositions around

Fe12.5Cu25.5Al62 the icosahedral phase is perfect, without phasons and without any modification even after

annealing for 4 days at 500°C.

For compositions different but close to this domain, either a modulated structure appears [1991Aud1] or

even a transformation towards periodic phases (rhombohedral) [1990Den]. Further investigations of crystall

structure with an emphasis of phase transition and thermal stability of Al-Cu-Fe quasicrystalline in bulk and

layer states have been carried out by many groups on the basis of experiment and theory [1991Aud1,

1991Aud2, 1991Bes, 1991Che, 1991Dub, 1991Eib, 1991Fau, 1991Jan, 1991Lei, 1991Liu1, 1991Liu2,

1991Men, 1991Wu, 1991Zha, 1992Che1, 1992Che2, 1992Eib, 1992Hay, 1992Lu, 1992Mat, 1992Nas,

1993Ban, 1993Lee, 1993Men, 1993Nas, 1993Was, 1994Bes, 1994Fre1, 1994Fre2, 1994Law, 1994Lef,

1995Div, 1996Log, 1996Qui, 1997Div, 1997Ham, 1997Pop, 1997Ros, 1997She, 1998Dun, 1998Ma,

1999Rot, 2000Bou, 2000Dun, 2000Gre1, 2000Gre2, 2000Jon, 2000Nak, 2000Sha, 2000Ste, 2000Uch,

2001Cai, 2001Gui, 2001Guo, 2001Qia, 2002Gre, 2002Kra, 2002Sha].

Large grains with an average size of 0.2 mm were obtained by [1987Tsa2] and [1990Cal]. Further

replacement of Cu by Al in (Fe15Cu20-xAl65+x) alloys was said to reveal a three-phase structure of (Al)+

FeAl3+FeCu2Al7 [1988Tsa].

Pseudobinary Systems and Temperature – Composition Sections

The section Al3Fe-Al2Cu was reported by [1928Arc] as a pseudobinary system, however, this section is not

exactly pseudobinary [1928Arc, 1990Fau2]. Some pseudobinary phase diagrams along the composition

lines of the Cu35Al65 - Fe20Cu15Al65, Fe1.5Cu30Al68.5 - Fe1.5Cu40Al58.5, Fe3Cu30Al67 - Fe3Cu40Al57 and

Fe5Cu30Al65 - Fe5Cu40Al55 were determined by [2000Yok1, 2000Yok2], which show that the primary

crystal from the melt is the phase, and then i phase is formed by a peritectic reaction. [2000Yok1 and

2000Yok2] only focused on the two-phase (L+ i) region, and did not give detailed information. In addition,

it was found that some phase equilibria do not follow the phase equilibria rules.

More recently, [2003Zha2] reported a series of vertical phase diagrams, including the pseudobinary systems

along the Fe22.8Al77.2-Cu57.5Al42.5 (Fig. 1), Cu10Al90 - Fe20Cu30Al50 (Fig. 2), Cu37.5Al62.5 - Fe20Cu21Al59

(Fig. 3), Fe14.5Al85.5 - Fe3.5Cu50Al46.5 (Fig. 4) and the vertical section diagrams with 25 at.% Cu, 5 at.%

Fe, 7.5 at.% Fe, 10 at.% Fe, and 12 at.% Fe (Figs. 5-9). In the investigations of [2002Zha, 2003Zha2], the

phase equilibria of the i phase and other related phases are precisely described, and the icosahedral phase

is formed via a peritectic reaction (L+ + i) at 882°C, the shrinkage of the phase field with decreasing

temperature gives an indication of the compositional influence on the stability of the icosahedral phase.

[1939Bra1, 1939Bra2, 1971Pre] reported the existence of slightly distorted structures of the phase. In

Fig. 1 [2003Zha2] shows them as two phases, labeled as 1 and 2, based on of the results of [1939Bra1,

1939Bra2 and 1971Pre]. However, none of the authors [1939Bra1, 1939Bra2, 1971Pre, 2003Zha1,

2003Zha2, 2003Zha3] studied these structures in details.

[2003Zha2] did not distinguish between 1 and 2 except for the vertical section shown in Fig. 3, where

these two phases are distinguished. This is mainly concluded from their existence in the binary Al-Cu

system and supported by a few DTA and MTA measurements. According to this section a ternary reaction

corresponding to the 1 and 2 transition occurs at a temperature between ~595 and 565°C, involving liquid

phase. Below this temperature only 2 should exist. However, [2003Zha1, 2003Zha2, 2003Zha3] did not

consider this fact in the reaction scheme and in other vertical sections and used as notation in all figures.

Further investigations would be required to clarify phase equilibria involving different modifications of the

phase, as well as the 1 and 2 phases.

3


MSIT®

Al–Cu–Fe

It should be noted that the vertical sections presented here from [2003Zha2] are not always coherent with

the accepted binary systems.

[1998Wan] presented the calculated vertical section diagrams of 5, 10, and 15 mass% Al with a

consideration of the ordered structure of the bcc phase ( Fe), as shown in Figs. 10-12, which indicate that

the B2 ordered phase ( ) is not formed in the 5 mass% Al vertical sections. However, the metastable and

stable A2/B2 ordering reaction (( Fe)/ ) appears in the 10 and 15 mass% Al vertical sections,

respectively; and the miscibility gap of the B2 phase ( ) also appears in 15 mass% Al vertical section.


Two partial reaction schemes in the Cu-rich and Al-rich corners were proposed by [1938Nis] (Fig. 13), and

[1954Phi, 2003Zha3], respectively. In the Al-rich corner [2003Zha3] presented a detailed Scheil reaction

scheme including solid state reactions, where 13 four-phase equilibria, three three-phase eutectic equilibria,

four three-phase peritectic equilibria, and two three-phase eutectoid reactions are included (Fig. 14). In the

Cu-rich portion the invariant reactions related to the 0 phase are revised, as shown in Fig. 13, because

[1998Liu] reported that no 0 phase exists at high temperature in the Al-Cu system. The reaction at 1048°C,

given as L+T ( Fe)+Cu3Al by [1938Nis], where the phase T was considered to be a ternary compound, is

not compatible as a transition type reaction with the other equilibria, but should be a peritectic type

L+( Fe)+( Fe) Cu3Al.

The invariant reactions are listed in Table 2.

Liquidus Surface

Polythermal projections of the liquidus surface are proposed in Figs. 15 and 16 for the Cu- and Al- rich

corners, respectively. Figure 17 shows combined projection of liquidus surface with tie lines of the

four-phase equilibria based on the works of [1991Leg] and [2003Zha1]. The ternary phase 4, close to i,

is omitted in these figures. A partial liquidus surface diagram in the Al-rich portion and the formation

temperature of i phase is presented by [2000Yok1, 2000Yok2], which is in basic agreement with that

reported by [2003Zha1], who constructed the liquidus surface in the Al-rich portion, as shown in Fig. 16,

where 12 four-phase equilibria with the liquid phase exist.

Isothermal Sections

Figure 18 shows the Al-rich part of the isothermal section at room temperature obtained by [1991Fau] by

combining experimental results of [1990Cal] with previous literature data in the range of compositions

around the icosahedral i phase, in which 4 is not shown. Furthermore, [1992Gay1 and [1992Gay2]

determined the isothermal phase diagrams at temperatures from 550-800°C in the Al-rich region using

scanning electron microscopy and energy dispersive spectroscopy. This study indicates that the B2 ordered

phase ( ) has considerably greater solubility of Cu than previously reported, extending from AlFe to the

composition of about Fe5Cu45Al50. A schematic section at 680°C in the vicinity of the icosahedral region

was determined by [1993Gra] with a combination of the results of [1992Gay1, 1939Bra1]. The results of

[1993Gra] show that at 680°C, three crystalline phases surround the icosahedral region: the monoclinic

phase, the ordered simple cubic ( ) phase and ordered tetragonal 2 phase. [2001Ros] constructed the

isothermal section at 850°C. [1997Oht] has studied the solid/liquid equilibria in the Cu-Fe portion using

diffusion couple method. [1998Wan] performed the experimental determination and thermodynamic

calculation of the phase equilibria in the Cu-Fe side portion with a special attention for A2/B2 ordering

transition. There exists an order-disorder A2/B2 transition in this system, and a stable B2 phase ( ) is

formed over a wide range of compositions from the Al-Fe binary system to the Al-Cu binary system at

800-1000°C (Figs. 19-24). It is interesting to note that a miscibility gap of the bcc phase ( ) was divided

into A2+A2 (( Fe)+Cu3Al), A2+B2 (Cu3Al+ ) and B2+B2 (( (1)+ ( (2)) two-phase regions. [2003Zha3]

determined isothermal sections at 800, 700, 645, 620, 617, 600, 592 and 560°C using SEM/EDS methods

together with structural investigations, as shown in Figs. 25-32, in which the i icosahedral quasicrystalline

4


MSIT®

Al–Cu–Fe

phase was found to be in equilibrium with three phases (L, and ) at 800°C, four phases (L, , 2 and )

at 700°C, three phases ( 2, and ) at 645°C, four phases ( 2, two , 3 and ) at 620°C, and four phases

( 2, , 3 and ) below 560°C.

Thermodynamics

[1993Saa1, 1993Saa2] reported the enthalpy of formation of the i, 2, and phases using differential

thermal analysis. It is shown that the heat formation of the 2 and i phases are of the same order of

magnitude, although the value of 2 is slightly higher than that of the i phase. [1994Was] theoretically

constructed the free energy function for quasicrystalline phase to investigate the phase transition.

[1992Wan] determined specific heat of phason-strained quasicrystals, and [1997Las] reported the

low-temperature specific heat (0.1<T<10K) of several quasicrystals, and [1999Wan] measured the heat

capacities of two Fe12.5Cu25Al62.5 samples containing icosahedral quasicrystals and B2 structure,

respectively, by means of a high-precision automatic adiabatic calorimeter over the temperature range of

75-385 K. [1999Hol] measured the melting entropy by differential thermal analysis, and pointed out that

the entropy of mixing plays an important role in the stabilization of the quasicrystalline phase. The

thermodynamic assessments of the Al-Cu-Fe system have been performed by [1997Oht, 1998Wan,

2003Mie] within the framework of the CALPHAD method. [1997Oht] calculated the liquid/solid phase

equilibria in the Cu-Fe side portion using regular solution model for the liquid, fcc ( Fe) and bcc phases.

[1998Wan] extended the work of [1997Oht] to make a thermodynamic assessment of the Al-Cu-Fe ternary

system, in which the thermodynamic assessments of Al-Fe [1998Ohn], Al-Cu [1998Liu] and Cu-Fe

[1995Che] binary systems are adopted, and two-sublattice model is used to describe the free energy of the

bcc ( ) phase in order to describe the A2/B2 ordering reaction. In [1998Wan] thermodynamic assessment

is focused on the phase equilibria at Cu-Fe side, and a prediction of the phase equilibria in Al-rich portion

is given, and the ternary compounds are not included. Recently, a thermodynamic description of the phase

equilibria at the Cu-Fe side was made by [2003Mie], where the ordering of the bcc phase was not

considered.


Considerable investigations were focused on the electronic transport properties of quasicrystals [1990Kle,

1992Chi, 1993Dre, 1992Lin, 1992Poo, 1994Tra, 1995Tra, 1999Bra, 1999Rot, 2000Bel1, 2000Bel2,

2000Bil, 2000Bra1, 2000Bra2, 2000Gre1, 2000Gre2, 2000Hab, 2000Lan1, 2000Mad, 2000Miz, 2000Pre,

2000Rap, 2000Smo, 2000Zha]. Other properties such as mechanical properties [2000Wan, 2000Tre,

2000Wu2, 2002Dub], corrosion behavior [2000Rue], oxidation behavior [2000Weh], creep behavior

[2000Gia] were studied. The magnetic behavior of Cu-rich Al-Cu-Fe alloys in the solid and liquid states has

been discussed and reviewed by [1975Wac, 1978Pan1] and [1978Pan2]. The magnetic properties of

mechanically alloyed nanocrystalline phase was also reported by [1999Tor] and [2001Kim] and the

tribological properties of sintered bulk icosahedral samples were studied by [2000Bru].

Recently, some investigations have been performed on the technological application of quasicrystals by

means of coatings and composites, and a review was reported by [2000Dub]. [2000Fle] and [2000Lan2,

2002Fik] have studied the quasicrystalline coatings by plasma spraying process. [2000Lee1] and [2000Blo]

developed composite materials for metal/quasicrystal and polymer/quasicrystal, by means of gas-atomized

process, respectively.

Miscellaneous

The icosahedral quasicrystalline phase was found to coexist in rapidly quenched Fe15Cu20Al65 alloys with

a crystalline bcc-Mg32(Al,Zn)49 type phase [1988Che]. The effect of iron on the precipitation hardening of

Al-Cu-Fe alloys has been studied by means of hardness tests, dilatation, electrical resistivity and yield

strength measurements [1940Fin] and by X-ray powder diffraction analysis [1940Hun]; due to the

formation of ternary constituents, iron was found to remove Cu from Al-base alloys and thus to effectively

suppress the ageing of Al-Cu alloys [1940Fin] and [1940Hun]. [1972Pro] examined the iron effect (up to

5


MSIT®

Al–Cu–Fe

12% Fe) on the transformation of the supersaturated Cu3Al phase. A solution of 0.5% aqueous hydrofluoric

acid was shown to be a useful universal etchant to reveal the microstructure of iron containing Al-base

alloys [1973Kow]. The influence of silicon on the phase equilibria and formability of the icosahedral

quascrystalline phase have been studied in the quaternary Al-Cu-Fe-Si system by DTA, X-ray and

microstructural analysis [1986Gul, 1987Che, 1987Zak, 2000Lee2].

Some investigations on phase formation of icosahedral phase were carried out by mechanical alloying

process [2000Sri, 2001Bar, 2001Muk, 2002Bar, 2002Tch]. Solidification behavior of quasicrystal phase

was studied by [1994Hol, 1996Zha, 1996Gru, 1998Hol, 1998Vol, 2002Yok]. Laser sputtering technique

was used to study the surface of quasicrystal [2002Mel] and to synthesis Al-base icosahedral

quasicrystalline powder [2000Nic]. The melting behavior of Bi and Pb nanoparticles embedded in Al-Cu-Fe

icosahedral matrix by rapid solidification were reported by [2001Sin, 2000Sin]. A study on the effect of

pressure on Al-Cu-Fe icosahedral phase was performed by [1999Pon]. [2000Bu] investigated the reaction

between Al-Cu-Fe quasicrystal phase and nitrogen oxides at high temperature, and indicated that the

quasicrystalline Al-Cu-Fe powder has a high capacity for the decomposition of nitrogen oxides at high

temperature. [2000Wu1] and [2000Wu2] investigated the surface microstructure of surface deformed areas

of Al-Cu-Fe icosahedral quasicrystal using electron microscopy.

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Al–Cu–Fe

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8


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Al–Cu–Fe

[1987Zak] Zakharov, A.M., Guldin, J.T., Arnold, A.A., “Effect of Si on Phase Equilibria in Alloys of

the Al-Cu-Fe System with 40% Cu and 0-10% Fe” (in Russian), Izv. Vyss. Uchebn. Zaved.,

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[1988Tsa] Tsai, A.P., Inoue, A., Masumoto, T., “New Quasicrystals in Al65Cu20M15 (M = Cr, Mn or

Fe) Systems Prepared by Rapid Solidification”, J. Mater. Sci. Lett., 7, 322-326 (1988)


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Growth of Al-Cu-Fe Quasicrystals”, J. Mater. Sci. Lett., 8, 827-830 (1989) (Equi. Diagram,

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[1989Eba] Ebalard, S., Spaepen, F., “The Body-Centered-Cubic-Type Icosahedral Reciprocal Lattice

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Pseudo-Icosahedral Symmetry”, J. Phys. (France), 51, 651-660 (1990) (Crys. Structure,

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[1990Fau1] Faudot, F., Quivy, A., Calvayrac, Y., Gratias, D., Harmelin, M., “About the Al-Cu-Fe

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Stockholm, 1990 (Equi. Diagram, Experimental, Crys. Structure, 14)

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Phases, Marseille, March 1990, 123-124 (Equi. Diagram, #, 4)

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[1991Aud1] Audier, M., Brechet, Y., de Boissieu, M., Guyot, P., Janot, C., Dubois, J.M., “Perfect and

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(1991) (Crys. Structure, Experimental, 29)

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Al–Cu–Fe

[1991Aud2] Audier, M., “Reversible Icosahedral-Rhombohedral Transition via a Modulated Icosahedral

State”, Int. Workshop Methods Struct. Anal. of Modulated Struct. and Quasicrystals

Lekeitio-Bilbao, Spain, 555-571 (1991) (Crys. Structure, Experimental, 29)

[1991Bes] Bessiere, M., Lefebvre, S., Quivy, A., Devaud-Rzepski, J., Calvayrac, Y., “High Resolution

Bragg Peak Profiles of Al62.3Cu25.3Fe12.4 Icosahedral Alloy: A New Type of

Morphological Transformation”, Int. Workshop Methods Struct. Anal. of Modulated Struct.

and Quasicrystals Lekeitio-Bilbao, Spain, 587-592 (1991) (Crys. Structure, Experimental,

Phys. Prop., 9)

[1991Che] Chen, L., Chen, X., “A Study of a Stable Aluminum-Copper-Iron Quasicrystal in Solid and

Liquid State”, Phys. Status Solidi B, 169(1), 15-21 (1992) (Equi. Diagram, Experimental, 9)

[1991Che1] Cheng, Y.F., Hui, M.J., Li, F.H., “An Intermediate State between the Decagonal and

Monoclinic Phases in an Al-Cu-Fe Alloy”, Philos. Mag. Lett., 64(3), 129-132 (1991) (Crys.


[1991Che2] Cheng, Y.F., Hui, M.J., Li, F.H., “A New Commensurate Phase and its Ralated

Incommensurate Phase in Al-Cu-Fe Alloy”, Philos. Mag. Lett., 63(1), 49-55 (1991) (Crys.


[1991Dub] Dubois, J.M., Dong, C., Janot, C., de Boissieu, M., Audier, M., “The Reversible

Crystal-Quasicrystal Transitions in Icosahedral Aluminum-Copper-Iron Alloys”, Phase

Transitions, 32(1-4), 3-28 (1991) (Crys. Structure, Experimental, 34)

[1991Eib] Eibschutz, M., Lines, M.E., Chen, H.S., Thiel, F.A., “Structure Difference Between i and T

Phases of Al-Cu-Co and Al-Cu-Fe Observed by Moessbauer Effect”, Phys. Rev. B, 46(1),

491-495 (1992) (Experimental, Moessbauer, Review, 27)

[1991Fau] Faudot, F., Quivy, A., Calvayrac, Y., Gratias, D., Harmelin, M., “About the Al-Cu-Fe

Icosahedral Phase Formation”, Mater. Sci. Eng. A, 133, 383-387 (1991) (Equi. Diagram,

Experimental, 14)

[1991Jan] Janot, C., Audier, M., de Boissieu, M., Dubois, J.M., “Al-Cu-Fe Quasi-Crystals:

Low-Temperature Unstability via a Modulation Mechanism”, Europhys. Lett., 14(4),

355-360 (1991) (Equi. Diagram, Experimental, 27)

[1991Leg] Legendre, B., Harmelin, M., “Aluminium – Copper – Iron”, MSIT Ternary Evaluation

Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International

Services GmbH, Stuttgart; Document ID: 10.14601.1.20, (1991) (Crys. Structure, Equi.

Diagram, Assessment, 71)

[1991Lei] Lei, T., Henley, Ch.L., “Equilibrium Faceting Shape of Quasicrystals at Low Temperatures:

Cluster Model”, Philos. Mag. B, 63(3), 677-685 (1991) (Calculation, Crys. Structure, 33)

[1991Liu1] Liu, W., Köster, U., “Decomposition of Icosahedral Quasicrystals in Al-Cu-Fe Alloys” (in

German), Z. Metallkd., 82(10), 790-798 (1991) (Crys. Structure, Equi. Diagram,

Experimental, 29)

[1991Liu2] Liu, W., Köster, U., Müller, F., Rosenberg, M., “Quasicrystalline and Crystalline Phases in

Aluminum-Copper-Iron-Chromium (Al65Cu20(Fe,Cr)15) Alloys”, Phys. Status Solidi A,

132(1), 17-34 (1992) (Crys. Structure, Experimental, 29)

[1991Men] Menguy, N., Audier, M., “Stability and Instability of the Different Phases in the

Rhombohedral-Icosahedral Transition of an Al-Fe-Cu Alloy”, Int. Workshop Methods

Struct. Anal. of Modulated Struct. and Quasicrystals Lekeitio-Bilbao, 572-586 (1991)


[1991Qui] Quilichini, M., Hennion, B., Heger, G., Lefebvre, S., Quivy, A., “Inelastic Neutron

Scattering by Quasicrystals”, Int. Workshop Methods Struct. Anal. of Modulated Struct. and

Quasicrystals, Lekeitio-Bilbao, Spain, 600-606 (1991) (Experimental, Thermodyn., 9)

[1991Wu] Wu, L., Xiao, J., Chen, Z., “A TEM Study of Crystalline Phases in the Rapidly Solidified

Al65Cu20Fe15 Alloys”, J. Cent.-South Inst. Min. Metall. (China), 22(1), 60-64 (1991) (Crys.


10


MSIT®

Al–Cu–Fe

[1991Zha] Zhang, Z., Li, N.C., Urban, K., “A Quasicrystalline Transition State in an Annealed

Al65Cu20Fe15 Alloy”, J. Mater. Res., 6(2), 366-370 (1991) (Crys. Structure, Experimental,

17)

[1992Che1] Cheng, Y.F., Li, F.H., “An Attempt to Describe One-Dimensional Incommensurate

Composite Structure as Phason-Defected One-Dimensional Quasiperiodic Structure”, Acta

Crystallogr., Sect. A: Found. Crystallogr., 48, 796-804 (1992) (Calculation, Crys.

Structure, Theory, 17)

[1992Che2] Chen, Z., Jiang, X., Wang, Y., Zhou, D., “The Constitution of Multicomponent

Quasicrystalline Alloys”, J. Mater. Sci. Lett., 11(22), 1493-1495 (1992) (Crys. Structure,

Experimental, 5)

[1992Chi] Chien, C.L., Lu, M., “Three States of Al65Cu20Fe15: Amorphous, Crystalline, and

Quasicrystalline”, Phys. Rev. B, 45(22), 12793-12796 (1992) (Crys. Structure,

Experimental, 22)

[1992Eib] Eibschutz, M., Lines, M.E., Chen, H.S., Thiel, F.A., “Structure Difference Between i and T

Phases of Al-Cu-Co and Al-Cu-Fe Observed by Moessbauer Effect”, Phys. Rev. B, 46(1),

491-495 (1992) (Experimental, Moessbauer, Review, 27)

[1992Gay1] Gayle, F.W., Sharpiro, A.J., Biancaniello, F.S., Boettinger, W.J., “The Al-Cu-Fe Phase

Diagram: 0-25 at.% Iron and 50-75 at.% Aluminum - Equilibria Involving the Icosahedral

Phase”, Metall. Trans. A, 23A(9), 2409-2417 (1992) (Abstract, Equi. Diagram,

Experimental, 21)

[1992Gay2] Gayle, F.W., “Phase Equilibria at 550°C in the Al-Cu-Fe System: 50 to 70 at.% Al, 0 to 9

at.% Fe”, J. Phase Equilib., 13(6), 619-622 (1992) (Crys. Structure, Experimental, 12)

[1992Hay] Hayzelden, C., Spaepen, F., “Kinetics of the Icosahedral-to-Approximant Transformation

in Aluminum-Copper-Iron”, Mater. Res. Soc. Symp. Proc., 205, 183-188 (1992) (Crys.

Structure, Kinetics, Experimental)

[1992Lin] Lin, S.T., Jiang, I. M., Cheng, H.Y., Chen, Y.C., Chou, L.S., “Electric and Magnetic

Properties of Al65Cu20(Fe(1-x)Mnx)15 Quasicrystals with x = 0.0, 0.2, 0.4, and 0.6”, J. Phys.:

Condens. Matter, 4(3), 735-746 (1992) (Crys. Structure, Electr. Prop., Equi. Diagram,

Experimental, Magn. Prop., 31)

[1992Lu] Lu, M., Chien, C.L., “Aluminum-Copper-Iron (Al65Cu20Fe15) in Amorphous, Crystalline

and Quasicrystalline States”, Hyperfine Interact., 71(1-4), 1525-15299 (1992) (Crys.

Structure, Experimental)

[1992Mat] Matsubara, E., Waseda, Y., “Structural Study of Icosahedral Al65Cu20Tm15 Alloys

(Tm=Fe, Ru and Os) by Anomalous X-ray Scattering Method”, Met. Abstr. Light Metals

and Alloys, 25, 174 (1992) (Crys. Structure, Experimental, 0)

[1992Nas] Nasu, S., Miglierini, M., Ishihara, K.N., Shingu, P.H., “Transformation from Icosahedral

Quasicrystalline to Amorphous Structure in Al65Cu20Fe15”, J. Phys. Soc. Jpn., 61(10),


[1992Poo] Poon, S.J., “Electronic Properties of Quasicrystals an Experimental Review”, Adv. Phys.,

41(4), 303-363 (1992) (Crys. Structure, Experimental, Phys. Prop., Review, 223)

[1992Wan] Wang, K. Scheidt, C., Garoche, P., Calvayrac, Y., “Specific-Heat Measurements of

Phason-Strained Quasicrystalline Aluminum-Iron-Copper (AlFeCu)”, J. Phys. I, 2(8),

1553-1557 (1992) (Crys. Structure, Experimental)

[1992Zak] Zakharov, A.M., Guldin, I.T., Arnold, A.A., Matsenko, Yu.A., “Phase Equilibria in

Multicomponent Aluminum Systems with Copper, Iron, Silicon, Manganese and

Titanium”, Metalloved. Obrab. Tsvetn. Splavov: To 90 Anniversary of Academician A.A.

Bochvar Birthday. RAN. Inst. Metall. M, 6-17 (1992) (Equi. Diagram, Experimental, 14)

[1993Ban] Bancel, P.A., “Phason-Induced Transformations of Icosahedral Al-Cu-Fe”, Philos. Mag.

Lett., 67(1), 43-49 (1993) (Crys. Structure, Equi. Diagram, Experimental, 10)

[1993Bes] Bessiere, M., Lefebvre, S., Lee, H., Colella, R., Motsch, T., Denoyer, F., “Feasibility of

Phase Determination in Quasicrystals and Microcrystals by Means of Multiple Bragg

Scattering”, Z. Kristallogr., 209, 390-394 (1994) (Crys. Structure, Experimental, 14)

11


MSIT®

Al–Cu–Fe

[1993Dre] Drews, A.R., Rubinstein, M.,Stauss, G.H., Bennett, L.H., Swartzendruber, L.J., “NMR,

Magnetism and Mossbauer Effect in Icosahedral Al63Cu24.5Fe12.5 - a Thermodynamically

Stable Quasi-Periodic Alloy”, J. Alloys Compd., 190, 189-195 (1993) (Experimental,

Moessbauer, Thermodyn., Magn. Prop., 15)

[1993Fau1] Faudot, F., Harmelin, M., “The Al-Cu-Fe Phase Diagram: Liquidus Surface and Equilibria

Involving the Quasicrystalline Icosahedral Phase and its Approximants”, Calorim. Therm.

Anal., 24, 121-124 (1993) (Crys. Structure, Experimental , Equi. Diagram)

[1993Fau2] Faudot F., “Phase Diagram Al-Cu-Fe. Al-Rich Region and Region of Icosahedral Phases”,

Annal. Chim. Sci. Mat.(France), 18(7), 445-456 (1993) (Equi. Diagram, Experimental, 31)

[1993Gra] Gratias, D., Calvayrac, Y., Devaud-Rzepski, J., Faudot, F., Harmelin, M., Quivy, A.,

Bancel, P.A., “The Phase Diagram and Structures Of the Ternary Al-Cu-Fe System in the

Vicinity of the Icosahedral Region”, J. Non-Cryst. Solids, 153-154, 482-488 (1993) (Crys.

Structure, Equi. Diagram, Review, 18)

[1993Kat] Kattner, U.R., Burton, B.P., “Aluminum-Iron”, in “Phase Diagrams of Binary Iron Alloys”,

ASM, Metals Park, OH, 12-28 (1993) (Crys. Structure, Equi. Diagram, Review, Magn.

Prop., Thermodyn., 99)

[1993Lee] Lee, B.H., Colella, R., “Phase Determination of X-Ray Reflection in a Quasicrystal” , Acta

Crystallogr., A49, 600-605 (1993) (Crys. Structure, Experimental, 15)

[1993Men] Menguy, N., de Boissieu, M., Guyot, P., Audier, M., Elkaim, E., Lauriat, J.P., “Single

Crystal X-Ray Study of a Modulated Icosahedral AlCuFe Phase”, J. Phys. I, 3, 1953-1968

(1993) (Calculation, Crys. Structure, Experimental, 33)

[1993Nas] Nasu, S., Miglierini, M., Ishihara, K.N., Shingu, P.H., “Transformation from Icosahedral

Quasicrystalline to Amorphous Structure in Al65Cu20Fe15”, Met. Abstr. Light Metals and

Alloys, 26, 155 (1993) (Crys. Structure, Experimental, 0)

[1993Saa1] Saadi, N., Harmelin, M., Faudot, F., Legendre, B., “Enthalpy of Formation of the

Al0.63Co0.25Fe0.12 Icosahedral Phase”, J. Non-Cryst. Solids, 153-154, 500-503 (1993)

(Equi. Diagram, Experimental, Thermodyn., 14)

[1993Saa2] Saadi, N., Harmelin, M., Legendre, B., “Determination of the Formation Enthalpy of

Crystalline and Quasicrystalline Phases of the Al-Cu-Fe System by Solution Calorimetry”,

J. Chim. Phys., 90(2), 355-366 (1993) (Crys. Structure, Experimental, Thermodyn., 21)

[1993Was] Waseda, A., Araki, K., Kimura, K., Ino, H., “Quasicrystals and Approximants in the

Al-Co-(Fe, Ru) and Al-Pd-Mn Systems”, J. Non-Cryst. Solids, 153-154, 635-639 (1993)

(Crys. Structure, Equi. Diagram, Experimental, 19)

[1994Bes] Bessiere, M., Lefebvre, S., Lee, H., Colella, R., Motsch, T., Denoyer, F., “Feasibility of

Phase Determination in Quasicrystals and Microcrystals by Means of Multiple Bragg

Scattering”, Z. Kristallogr., 209, 390-394 (1994) (Crys. Structure, Experimental, 14)

[1994Fre1] Freiburg, C., Grushko, B., Melchers, M., Reichert, W., “Structure of (Al,Cu)13Fe4 with

Cu-Contents of 0, 2 and 4 at. percent”, Mater. Sci. Forum, 166-169, 455-460 (1994)

(Experimental, Crys. Structure, 7)

[1994Fre2] Freiburg C., Grushko B., “An Al13Fe4 Phase in the Al-Cu-Fe Alloy System.”, J. Alloys

Compd., 210, 149-152 (1994) (Crys. Structure, Experimental, 18)

[1994Hol] Holland-Moritz, D., Herlach, D.M., Grushko, B., Urban, K., “Phase Selection in

Undercooled Melts of Al-Cu-Co And Al-Cu-Fe Quasi-Crystal-Forming Alloys”, Mater.

Sci. Eng. A, 181(1-2), 766-770 (1994) (Equi. Diagram, Experimental, Kinetics, Mechan.

Prop., 19)

[1994Law] Lawther, D.W., Dunlap, R.A., “Positron-Annihilation Study of Equilibrium Defects in

Al-Cu-Fe Face-Centered-Icosahedral Quasicrystals”, Phys. Rev. B, 49(5), 3183-3189

(1994) (Crys. Structure, Experimental, Phys. Prop., Thermal Conduct., 65)

[1994Lef] Lefebvre, S., Bessiere, M., Calvayrac, Y., Itie, J.P., Polian, J.P., Sadoc, A., “Icosahedral and

Approximant Structures of AlCuFe Phases: A Study by Diffraction at High Pressure”,

Mater. Sci. Forum, 166-169, 449-454 (1994) (Crys. Structure, Experimental, 11)

12


MSIT®

Al–Cu–Fe

[1994Mur] Murray, J.L., “Al-Cu (Aluminium-Copper)”, in “Phase Diagrams of Binary Copper

Alloys”, Subramanian, P.R., Chakrabati, D.J., Laughlin D.E., (Eds.), ASM International,

Materials Park, OH, 18-42 (1994) (Equi. Diagram, Crys. Structure, Thermodyn., Review,

226)

[1994Tra] Trambly de Laissardiere, G.; Fujiwara, T., “Electronic Structure and Conductivity in a

Model Approximant of the Icosahedral Quasicrystal Al-Cu-Fe”, Phys. Rev. B, 50(9),

5999-6005 (1994) (Calculation, Crys. Structure, Phys. Prop., 34)

[1994Was] Waseda, A., Kimura, K., Ino, H., “Free Energy Analysis for the Phase Transition Of

Quasicrystals and Phase Diagram Of The Al-Cu-Fe System”, Mater. Sci. Eng. A, 181/

182(1-2), 762-765 (1994) (Calculation, Equi. Diagram, Experimental, Thermodyn., 11)

[1995Che] Chen, Q., Jin, Z., “The Fe-Cu System: A Thermodynamic Evaluation”, Metall. Mater.

Trans. A, 26A, 417-426 (1995) (Calculation, Thermodyn., Assessment, Equi. Diagram, 55)

[1995Div] Divinski, S.V., Larikov, L.N., “Modulated Quasicrystal Structure”, Philos. Mag. Lett.,

72(5), 345-351 (1995) (Calculation, Theory, 27)

[1995Tra] Trambly de Laissardiere, G., Nguyen Manh, D., Magaud, L., Julien, J.P., Cyrot-Lackmann,

F., Mayou, D., “Electronic Structure and Hybridization Effects in Hume-Rothery Alloys

Containing Transition Elements”, Phys. Rev. B, 52(11), 7920-7933 (1995) (Calculation,

Crys. Structure, Electr. Prop., 64)

[1996Gru] Grushko, B., Wittenberg, R., Holland-Moritz, D., “Solidification of Al-Cu-Fe Alloys

Forming Icosahedral Phase”, J. Mater. Res., 11(9), 2177-2185 (1996) (Experimental, 31)

[1996Log] Lograsso, T.A., Delaney, D.W., “Preparation of Large Single Grains of the Quasicrystalline

Icosahedral Al-Cu-Fe Phase”, J. Mater. Res., 11(9), 2125-2127 (1996) (Crys. Structure,

Experimental, 12)

[1996Qui] Quiquandon, M., Quivi, A., Devaud, J., Faudot, F., Lefebvre, S., Bessiere, M., Calvayrac,

Y., “Quasicrystal and Approximat Structures in the Al-Cu-Fe System”, J. Phys.: Condensed

Matter, 8(15), 2487-2512 (1996) (Crys. Structure, Equi. Diagram, Experimental, 29)

[1996Zha] Zhang F.X., Wang W.K., “Phase Formation Behavior in Undercooled

Quasicrystal-Forming Al-Cu-Fe Alloy Melts”, Mater. Sci. Eng. A, 205, 214-220 (1996)


[1997And] Anderson, I.M., “Alchemi Study of Site Distributins of 3d-Transition Metals in B2-Ordered

Iron Aluminides”, Acta Mater., 45(9), 3897-3909 (1997) (Calculation, Crys. Structure,

Experimental, Theory, 26)

[1997Div] Divakar, R., Sundararaman, D., Raghunathan, V.S., “Al-Cu-Fe Quasicrystals: Stability and

Microstructure”, Prog. Cryst. Growth Charact., 34, 263-269 (1997) (Crys. Structure,

Experimental, 18)

[1997Ham] Hamada, E., Oshima, N., Suzuki, T., Sato, K., Kanazawa, I., Nakata, M., Takeuchi, S.,

“Positron Annihilation Studies of Icosahedral AlCuRu and AlCuFe Alloys”, Mater. Sci.

Forum, 255-257, 451-453 (1997) (Experimental, Crys. Structure, 16)

[1997Las] Lasjaunias, J.C., Calvayrac, Y., Yang, H., “Investigation of Elementary Excitation in

AlCuFe Quasicrystals by Means of Low-Temperature Specific Heat”, J. Phys. I, 7, 959-976

(1997) (Electr. Prop., Equi. Diagram, Experimental, Thermodyn., 48)

[1997Oht] Ohtani, H., Suda, H., Ishida, K., “Solid/Liquid Equilibria in Fe-Cu Based Ternary Systems”,

ISIJ Int., 37(3), 207-216 (1997) (Calculation, Equi. Diagram, Experimental, Review,

Thermodyn., 47)

[1997Pop] Popescu, R., Macovei, D., Manciu, M., Zavaliche, F., Fratiloiu, D., Jianu, A., Devenyi, A.,

Manaila, R., Xie, R., Hu, T., Orton, B.R., Cernik, R.J., Tang, C.C., “The Au-Substituted

Al-Cu-Fe Icosahedral Phase: Evidence for Bond Hybridization”, J. Phys.: Condens. Matter,


[1997Ros] Rosas, G., Perez, R., “Crystalline and Quasicrystalline Phases in AlCuFe and AlCuFeCr

Alloys”, J. Mater. Sci., 32, 2403-2409 (1997) (Equi. Diagram, Experimental, 12)

13


MSIT®

Al–Cu–Fe

[1997She] Shen, Z., Pinhero, P.J., Lograsso, T.A., Delaney, D.W., Jenks, C.J., Thiel, P.A., “The

Five-Fold Surface of Quasicrystalline AlCuFe: Preparation and Characterization with

LEED and AES”, Surf. Sci., 385, L923-L929 (1997) (Crys. Structure, Experimental, 39)

[1998Akd] Akdeniz, M.V., Mekhrabon, A.O., “The Effect of Substitutional Impurities on the Evolution

of Fe-Al Diffusion Layer”, Acta Mater., 46(4), 1185-1192 (1998) (Calculation,

Thermodyn., 55)

[1998Dun] Duneau, M., Audier, M., “Structural Characteristics of Pentagonal Al-Fe-Cu Phases”,

Philos. Mag. A, 77(3), 675-688 (1998) (Crys. Structure, Experimental, 9)

[1998Hol] Holland-Moritz, D., Schroers, J., Herlach, D.M., Grushko, B., Urban, K., “Undercooling

and Solidification Behaviour of Melts of the Quasicrystal-Forming Alloys Al-Cu-Fe and

Al-Cu-Co”, Acta Mater., 46, 1601-1615 (1998) (Equi. Diagram, Experimental, 44)

[1998Liu] Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria in the Cu-Rich Portion of

the Cu-Al Binary System”, J. Alloys Compd., 264, 201-208 (1998) (Equil. Diagram,

Experimental, 25)

[1998Ma] Ma, X.L., Rüdiger, A., Liebertz, H.; Köster, U.; Liu, W., “A New Structural Variant of

-Al3O4 and its Orientation Relationship with the Cubic -Al4Cu9”, Scr. Mater., 39(6),


[1998Ohn] Ohnuma, I., Ikeda, O., Kainuma, K., Sundman, B., Ishida, K., ”Phase Separation Induced

by Interaction between Chemical and Magnetic Ordering in BCC Phase in Fe-Al Binary

System”, CALPHAD XXVII, Beijing, P.R.China, 17-22 May, 1998, 4, (1998) (Thermodyn.,

Calculation, Assessment)

[1998Vol] Voltz, C., Bletry, J., Audier, M., “Drop Tube Solidification of Al-Cu-Fe Quasicrystalline

Phase”, Philos. Mag. A, 77(6), 1351-1366 (1998) (Crys. Structure, Equi. Diagram,

Experimental, 28)

[1998Wan] Wang, C.P., Liu, X.J., Ohnuma, I., Kainuma, R., Hao, S.M., Ishida, K., “Ordering and Phase

Separation of the BCC Phase in the Fe-Cu-Al System”, Z. Metallkd., 89(12), 828-835

(1998) (Crys. Structure, Equi. Diagram, Experimental, Thermodyn., #, *, 18)

[1999Bra] Brand, R.A., Pelloth, J., Hippert, F., Calvayrac, Y., “Correlations in the Electronic

Properties of AlCuFe Quasicrystals and High-Order Approximants: Fe’(57) Moessbauer,

and Al’(27) and Cu’(65) Nuclear Magnetic Resonance Studies”, J. Phys.: Condens. Matter,

11, 7523-7543 (1999) (Crys. Structure, Experimental, Moessbauer, Review, 51)

[1999Hol] Hollamd-Moritz, D., Lu, I.-R., Wilde, G., Schroers, J., Grushko, B., “Melting Entropy of

Al-Based Quasicrystals”, J. Non-Cryst. Solids, 250-252, 829-832 (1999) (Experimental,

Thermodyn., 17)

[1999Pon] Ponkratz, U., Nicula, R., Jianu, A., Burkel, E., “Quasicrystals Under Pressure: a

Comparison Between Ti-Zr-Ni and Al-Cu-Fe Icosahedral Phases”, J. Non-Cryst. Solids,

250-252, 844-848 (1999) (Crys. Structure, Experimental, 20)

[1999Rot] Roth, C., Schwabe, G., Knöfler, R., Zavaliche, F., Madel, O., Haberkern, R., Häussler, P.,

“A Detailed Comparison Between the Amorphous and the Quasicrystalline State of

Al-Cu-Fe”, J. Non-Cryst. Solids, 250-252, 869-873 (1999) (Equi. Diagram, Experimental,

12)

[1999Tor] Toro, J.A., Torre, L.M.A., Riveiro, J.M., “Spin-Glass-Like Behavior in Mechanically

Alloyed Nanocrystalline Fe-Al-Cu”, Phys. Rev. B, 60(18), 12918-12923 (1999) (Crys.

Structure, Experimental, Magn. Prop., 27)

[1999Wan] Wang, L., Tan, Z.C., Zhang, J.B., Meng, S.H., Zhang, L.M., Zhou, Q.G., Dong, C., “Heat

Capacities of Al62.5Cu25Fe12.5 Quasicrystals and B2 Related Crystals”, Thermochim. Acta,

331, 21-25 (1999) (Crys. Structure, Experimental, Thermodyn., 9)

[2000Bel1] Belin-Ferre, E., Dubois, J-M., Fournee, V., Brunet, P., Sordelet, D.J., Zhang, L.M., “About

the Al 3p Density of States in Al-Cu-Fe Compounds and its Relation to the Compound

Stability and Apparent Surface Energy of Quasicrystals”, Mater. Sci. Eng. A, 294-296,


14


MSIT®

Al–Cu–Fe

[2000Bel2] Belin-Ferre, E., Fournee, V., Dubois, J.M., “Al 3p Occupied States in Al-Cu-Fe

Intermetallics and Enhanced Stability of the Icosahedral Quasicrystal”, J. Phys.: Condens.

Matter, 12, 8159-8177 (2000) (Crys. Structure, Equi. Diagram, Experimental, 32)

[2000Bil] Bilusic, A., Smontara, A., Lasjaunias, J.C., Ivkov, J., Calvauras, Y., “Thermal and

Thermoelectric Properties of Icosahedral Al62Cu25.5Fe12.5 Quasicrystal”, Mater. Sci. Eng.

A, 294-296, 711-714 (2000) (Crys. Structure, Experimental, Phys. Prop., 21)

[2000Blo] Bloom, P.D., Baikerikar, K.G., Otaigbe, J.U., Sheares, V.V., “Development of Novel

Polymer/Quasicrystal Composite Materials”, Mater. Sci. Eng. A, 294-296, 156-159 (2000)

(Crys. Structure, Experimental, Mechan. Prop., Phys. Prop., 10)

[2000Bou] Boudard, M., Letoublon, A., Boissieu, M., Ishimasa, T., Mori, M., Elkaim, E., Lauriat, J.P.,

“Phase Transition and Diffuse Scattering Studies in the Al-Cu-Fe Ternary System”, Mater.

Sci. Eng. A, 294-296, 217-220 (2000) (Crys. Structure, Experimental, 19)

[2000Bra1] Brand, R.A., Voss, J., Calvayrac, Y., “Phason-Dynamics Studied by Quasielastic

Moessbauer Scattering in i-Al-Cu-Fe Quasicrystals”, Mater. Sci. Eng. A, 294-296, 666-669

(2000) (Calculation, Crys. Structure, Experimental, Moessbauer, 27)

[2000Bra2] Brand, R.A., Coddens, G., Chumakov, A.I., Dianoux, A.J., Calvayrac, Y., “The Phonon

Density of States in the Archetypical Icosahedral Quasicrystal Al62Cu25.5Fe12.5”, Mater.

Sci. Eng. A, 294-296, 662-665 (2000) (Calculation, Crys. Structure, Experimental, 17)

[2000Bru] Brunet, P., Zhang, L.M., Sordelet, D.J., Besser, M.; Dubois, J-M., “Comparative Study of

Microstructural and Tribological Properties of Sintered, Bulk Icosahedral Samples”, Mater.

Sci. Eng. A, 294-296, 74-78 (2000) (Crys. Structure, Experimental, Phys. Prop., 6)

[2000Bu] Bu, J., Rhee, H.-K., Shen, Y.Z., Shin, K.S., “Decomposition of NO on the Surface of

Al-Cu-Fe Quasicrystal at High Temperature”, J. Mater. Sci. Lett., 20, 1165-1167 (2000)


[2000Dub] Dubois, J-M., “New Prospects from Potential Applications of Quasicrystalline Materials”,

Mater. Sci. Eng. A, 294-296, 4-9 (2000) (Crys. Structure, Experimental, Phys. Prop.,

Review, 38)

[2000Dun] Duneau, M., “Covering Clusters in the Katz-Gratias Model of Icosahedral Quasicrystals”,

Mater. Sci. Eng. A, 294-296, 192-198 (2000) (Calculation, Crys. Structure, Experimental,

34)

[2000Fle] Fleury, E., Lee, S.M., Kim, W.T., Kim, D.H., “Effect of Air Plasma Spraying Parameters

on the Al-Cu-Fe Quasicrystalline Coating Layer”, J. Non-Cryst. Solids, 278, 194-204

(2000) (Crys. Structure, Experimental, Phys. Prop., 28)

[2000Gia] Giacometti, E.; Baluc, N.; Bonneville, J., “Creep Behavior of Icosahedral Al-Cu-Fe”,

Mater. Sci. Eng. A, 294-296, 777-780 (2000) (Crys. Structure, Experimental, 18)

[2000Gre1] Grenet, T., Giroud, F., Loubet, C., Joulaud, J.L., Capitan, M., “Real Time Study of the

Quasicrystal Formation in Annealed Al-Cu-Fe Metallic Multilayers”, Mater. Sci. Eng. A,


[2000Gre2] Grenet, T., Giroud, F., “Observation of 2D Quantum Interference Effect in Quasicrystalline

i-Al-Cu-Fe Thin Films”, Mater. Sci. Eng. A, 294-296, 576-579 (2000) (Crys. Structure,

Electr. Prop., Experimental, 10)

[2000Hab] Haberkern, R., Khedhri, K., Madel, C., Haussler, P., “Electronic Transport Properties of

Quasicrystalline Thin Films”, Mater. Sci. Eng. A, 294-296, 475-480 (2000) (Crys. Structure,

Experimental, Phys. Prop., 18)

[2000Jon] Jono, M., Matsuo, Y., Ishii, Y., “A Phason Strain in an Al-Cu-Fe Icosahedral Quasicrystal”,

Mater. Sci. Eng. A, 294-296, 680-684 (2000) (Crys. Structure, Experimental, 8)

[2000Lan1] Landauro, C.V., Solbrig, H., “Temperature Dependence of the Electronic Transport in

Al-Cu-Fe Phases”, Mater. Sci. Eng. A, 294-296, 600-603 (2000) (Calculation, Crys.

Structure, 20)

[2000Lan2] Lang, C.I., Sordelet, D.J., Besser, M.F., Shechtman, D., Biancaniello, F.S., Gonzales, E.J.,

“Quasicrystalline Coatings: Thermal Evolution of Structure and Properties”, J. Mater. Res.,

15(9), 1894-1904 (2000) (Equi. Diagram, Experimental, Mechan. Prop., Phys. Prop., 41)

15


MSIT®

Al–Cu–Fe

[2000Lee1] Lee, S.M., Jung, J.H., Fleury, E., Kim, W.T., Kim, D.H., “Metal Matrix Composites

Reinforced by Gas-Atomised Al-Cu-Fe Powders”, Mater. Sci. Eng. A, 294-296, 99-103

(2000) (Calculation, Crys. Structure, Experimental, Mechan. Prop., 9)

[2000Lee2] Lee, S.M., Kim, B.H., Kim, S.H., Fleury, E., Kim, W.T., Kim, D.H., “Effect of Si Addition

on the Formability of the Icosahedral Quasicrystalline Phase in an Al65Cu20Fe15 Alloy”,

Mater. Sci. Eng. A, 294-296, 93-98 (2000) (Crys. Structure, Experimental, Mechan. Prop.,

11)

[2000Mad] Madel, C., Schwalbe, G., Haberkern, R., Haussler, P., “Hume-Rothery Effect in Amorphous

and Quasicrystalline Al-Cu-Fe”, Mater. Sci. Eng. A, 294-296, 535-538 (2000) (Crys.

Structure, Experimental, Phys. Prop., 11)

[2000Miz] Mizutani, U., “Electron Transport Mechanism in the Pseudogar System: Quasicrystals,

Approximants and Amorphous Alloys”, Mater. Sci. Eng. A, 294-296, 464-469 (2000) (Crys.


[2000Nak] Nakano, H., Sato, Y., Matsuo, S., Ishimasa, T., “Development of 3D Visualization System

for the Study of Physical Properties of Quasicrystals”, Mater. Sci. Eng. A, 294-296, 542-547

(2000) (Crys. Structure, Experimental, Phys. Prop., 29)

[2000Nic] Nicula, R., Jianu, A., Grigoriu, C., Barfels, T., Burkel, E., “Laser Ablation Synthesis of

Al-Based Icosahedral Powders”, Mater. Sci. Eng. A, 294-296, 86-89 (2000) (Crys.

Structure, Experimental, Mechan. Prop., 12)

[2000Pre] Prekul, A.F., Kuzmin, N.Yu., Shchegolikhina, N.J., “Thermal Activation of Carriers and

Characteristic Features of the Electronic Structure of Quasicrystalline Systems”, Mater. Sci.

Eng. A, 294-296, 527-530 (2000) (Crys. Structure, Experimental, Phys. Prop., 7)

[2000Rap] Rapp, O., “Electronic Transport Properties of Quasicrystals: the Unique Case of the

Magnetoresistance”, Mater. Sci. Eng. A, 294-296, 458-463 (2000) (Crys. Structure,

Experimental, Magn. Prop., Phys. Prop., 24)

[2000Rue] Rüdiger, A., Köster, U., “Corrosion Behavior of Al-Cu-Fe Quasicrystals”, Mater. Sci. Eng.

A, 294-296, 890-893 (2000) (Crys. Structure, Experimental, 5)

[2000Sin] Singh, A., Tsai, A.P., “The Nature of Lead-Quasicrystal Interfaces and its Effect on the

Melting Behavior of Lead Nanoparticles Embedded in Quasicrystalline Matrices”, Mater.


[2000Sha] Shalaeva, E.V., Prekul, A.F., “Structural State of -Solid Solution in Quenched

Quasicrystal-Forming Alloys of Al61Cu26Fe13”, Phys. Status Solidi A, 180, 411-425 (2000)


[2000Smo] Smontara, A., Lasjaunias, J.C., Paulsen, C., Bilusic, A., Calvayras, Y., “Low-Temperature

Thermal Conductivity of Icosahedral Al63Cu25Fe12 and Al62Cu25.5Fe12.5 Quasicrystals”,

Mater. Sci. Eng. A, 294-296, 706-710 (2000) (Crys. Structure, Experimental, Phys. Prop.,

Thermal Conduct., 14)

[2000Sri] Srinivas, V., Barua, P., Murty, B.S., “On Icosahedral Phase Formation in Mechanically

Alloyed Al70Cu20Fe10”, Mater. Sci. Eng. A, 294-296, 65-67 (2000) (Crys. Structure,

Experimental, 11)

[2000Ste] Steurer, W., “The Quasicrystal-to-Crystal Transformation. I. Geometrical Principles”,

Z. Kristallogr., 215, 323-334 (2000) (Calculation, Crys. Structure, 44)

[2000Tre] Trefilov, V.I., Mil’man, Yu.V., Lotsko, D.V., Belous, A.N., Cgugunova, S.I., Timofeeva,

I.I., Bykov, A.I., “Studies of Mechanical Properties of Quasicrystalline Al-Cu-Fe Phase by

the Indentation Technique”, Dokl. Phys., 45(8), 363-366 (2000) (Experimental, Mechan.

Prop., 15)

[2000Uch] Uchiyama, H., Takahashi, Y., Sato, K., Kanazawa, I., Kimura, K., Komori, F., Suzuki, R.,

Ohdaira, T., Tamura, R., Takeuchi, S., “Stable Quasicrystals Studied by Means of the Slow

Positron Beam”, Nucl. Instrum. Methods Phys. Res. / B, B171, 245-250 (2000) (Crys.


16


MSIT®

Al–Cu–Fe

[2000Wan] Wang, R., Yang, W., Gui, J., Urban, K., “Dislocation Mechanism of High-Temperature

Plastic Deformation of Al-Cu-Fe and Al-Pd-Mn Icosahedral Quasicrystals”, Mater. Sci.

Eng. A, 294-296, 742-747 (2000) (Crys. Structure, Experimental, 18)

[2000Weh] Wehner, B.I., Köster, U., Rudiger, A., Pieper, A., Sordelet, D.J., “Oxidation of Al-Cu-Fe

and Al-Pd-Mn Quasicrystals”, Mater. Sci. Eng. A, 294-296, 830-833 (2000) (Crys.


[2000Wu1] Wu, J.S., Brien, V., Brunet, P., Dong, C., Dubois, J.M., “Scratch-Induced Surface

Microstructures on the Deformed Surface of Al-Cu-Fe Icosahedral Quasicrystals”, Mater.


[2000Wu2] Wu, J.S., Brien, V., Brunet, P., Dong, C., Dubois, J.M., “Electron Microscopy Study of

Scatch-Induced Surface Microstructures in an Al-Cu-Fe Icosahedral Quasicrystal”, Philos.

Mag. A, 80(7), 1645-1655 (2000) (Crys. Structure, Experimental, 51)

[2000Yok1] Yokoyama, Y., Note, R., Fukaura, K., Sunada, H., Hiraga, K., Inoue, A., “Growth of a

Single Al64Cu23Fe13 Icosahedral Quasicrystal Using the Czochralski Method and

Annealing Removal of Strains”, Mater. Trans. , JIM, 41(11), 1583-1588 (2000) (Equi.

Diagram, Experimental, 14)

[2000Yok2] Yokoyama, Y., Fukaura, K., Sunada, H., “Preparation of Large Grained Al64Cu23Fe13

Icosahedral Quasicrystal Directly From the Melt”, Mater. Trans., JIM, 41(1), 668-674


[2000Yok3] Yokoyama, Y., Fukaura, K., Sunada, H., Note, R., Hiraga, K., Inoue, A., “Production of

Single Al64Cu23Fe13 Icosahedral Quasicrystal with the Czochralski Method”, Mater. Sci.

Eng. A, 294-296, 68-73 (2000) (Equi. Diagram, Experimental, 11)

[2000Zha] Zhang, L.M., Brunet, P., Zhang, H.C., Dong, C., Dubois, J.M., “Influence of Valence

Electron Concentration over the Friction Behaviors of Quasicrystal and B2-Type

Approximants in Al-Cu-Fe Ternary System”, Tribol. Lett., 8, 233-236 (2000) (Equi.

Diagram, Experimental, Mechan. Prop., 11)

[2001Bar] Barua, P., Murty, B.S., Srinivas, V., “Mechanical Alloying of Al-Cu-Fe Elemental

Powders”, Mater. Sci. Eng. A, 304-306, 863-866 (2001) (Equi. Diagram, Experimental, 13)

[2001Cai] Cai, T., Shi, F., Shen, Z., Gierer, M., Goldman, A.I., Kramer, M.J., Jenks, C.J., Lograsso,

T.A., Delaney, D.W., Thiel, P.A., van Hove, M.A., “Structural Aspect of the Fivefold

Quasicrystalline Al-Cu-Fe Surface from STM and Dynamical LEED Studies”, Surf. Sci.,


[2001Jon] Jono, M., Matsuo, Y., Yamamoto, K., Ishii, Y., “X-Ray Diffraction Study of a Phason Strain

in an Al-Cu-Fe Icosahedral Quasicrystal”, Philos. Mag. A, 8(11), 2577-2590 (2001) (Crys.


[2001Liu] Liu, X.J., Wang, C.P., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Stability Among the

(A1), (A2), and (D83) Phases in the Cu-Al-X System”, J. Phase Equilib., 22, 431-438


[2001Gui] Gui, J., Wang, J., Wang, R., Wang, D., Liu, J., Chen, F., “On Some Discrepancies in the

Literature about the Formation of Icosahedral Quasi-Crystal in Al-Cu-Fe Alloys”, J. Mater.

Res., 16(14), 1037-1046 (2001) (Crys. Structure, Experimental, 24)

[2001Guo] Guo, J.Q., Tsai, A.P., “Single-Crystal Growth of the Al-Cu-Fe Icosahedral Quasicrystal

from the Ternary Melt”, J. Mater. Res., 16(11), 3038-3041 (2001) (Crys. Structure, Equi.


[2001Kim] Kim, H-G., Muyng, W-N., Sumiyama, K., Suzuki, K., “Formation of a Nanocrystalline

Phase by Chemical Leaching of Rod-Milled Al0,6(Fe50Cu50) Alloy”, J. Alloys Compd., 322,

214-219 (2001) (Crys. Structure, Experimental, Phys. Prop., 17)

[2001Muk] Mukhopadhyay, N.K., “An Investigation on the Transformation of the Icosahedral Phase in

the Al-Fe-Cu System During Mechanical Milling and Subsequent Annealing”, Philos. Mag.

A, 82(16), 2979-2993 (2002) (Crys. Structure, Experimental, 31)

17


MSIT®

Al–Cu–Fe

[2001Ros] Rosas, G., Perez, R., “On the Relationships Between Isothermal Phase Diagrams and

Quasicrystalline Phase Transformations in AlCuFe Alloys”, Mater. Sci. Eng. A, 298, 79-83


[2001Qia] Qiang, J.-B., Wang, D.-H., Bao, C.-M., Wang, Y.-M., Xu, W.-P., Song, M.-L., Dong, Ch.,

“Formation Rule for Al-Based Ternary Quasi-Crystals: Example of Al-Ni-Fe Decagonal

Phase”, J. Mater. Res., 16(9), 2653-2660 (2001) (Crys. Structure, Equi. Diagram,

Experimental, 31)

[2001Sin] Singh, A., Tsai, A.P., “Melting Behaviour of Bismuth Nanoparticles Embedded in

Al-Cu-Fe Quasicrystalline Matrix”, Scr. Mater., 44(8-9), 2005-2008 (2001) (Equi.

Diagram, Experimental, Thermodyn., 16)

[2001Sur] Suryanarayana, C., “Mechanical Alloying and Milling”, Prog. Mater. Sci., 46(1-2), 1-184

(2001) (Crys. Structure, Equi. Diagram, Experimental, Kinetics, Review, Thermodyn., 932)

[2001Tur] Turchanin, M.A., Agraval, P.G., “Thermodynamics of Liquid Alloys, and Stable and

Metastable Phase Equilibria in the Copper-Iron System”, Powder Metall. Met. Ceram., 40

(7-8), 337-353 (2001), translated from Poroshk. Metall. (Kiev), (7-8), 34-53 (2001)

(Thermodyn., Experimental, Assessment, Equi. Diagram, 56)

[2002Ban] BanerJee, R., Amancherla, S., Banerjee, S., Fraser, H.L., “Modeling of Site Occupancies in

B2 FeAl And NiAl Alloys with Ternary Additions”, Acta Mater., 50, 633-641 (2002)

(Calculation, Equi. Diagram, Experimental, 21)

[2002Bar] Barua, P., Murty, B.S., Mathur, B.K., Srinivas, V., “Icosahedral Phase Formation Domain

in Al-Cu-Fe System by Mechanical Alloying”, J. Mater. Res., 17(3), 653-659 (2002) (Crys.


[2002Dub] Dub, S., Novikov, N., Milman, Yu., “The Transition from Elastic to Plastic Behavior in an

Al-Cu-Fe Quasicrystal Studied by Cyclic Nanoindentation”, Philos. Mag. A, 82(10),


[2002Fik] Fikar, J., Schaller, R., Guilbaud, N., Baluc, N., “Mechanical Spectroscopy of Icosahedral

Al-Cu-Fe Quasicrystals Metal-Based Composites”, Def. Diffus. Forum, 203-205, 289-292

(2002) (Experimental, Phys. Prop., 7)

[2002Gre] Grenet, T., Giroud, F., “Formation of Icosahedral Al-Cu-Fe Quasicrystal in Annealed

Metallic Multilayers”, Philos. Mag. A, 82(16), 2909-2922 (2002) (Crys. Structure,

Experimental, 30)

[2002Gul] Gulay, L.D., Harbrecht, B., “The Crystal Structures of the 1 and 2 Phases in the Al-Cu

System”, in “Crystal Chemistry of Intermetallic Compounds”, Abstr. VIII Int. Conf. Lviv,

P139, 73 (2002) (Crys. Structure, Experimental, 5)

[2002Hir] Hiraga, K., “The Structure of Quasicrystals Studied by Atomic-Scale Observations of

Transmission Electron Microscopy”, Adv. Imag. Electr. Phys., 122, 1-86 (2002)

(Assessment, Crys. Structure, 99)

[2002Kra] Kraposhin, V.S., Talis, A.L., Dubois, J.M., “Structural Realization of the Polytope

Approach for the Geometrical Description of the Transition of a Quasicrystal into a

Crystalline Phase”, J. Phys.: Condens. Matter, 14, 8987-8996 (2002) (Crys. Structure,

Experimental, 20)

[2002Mel] Mele, A., Liu, H., Russo, R.E., Mao, X., Giardini, A., Satta, M., “Inductively Coupled

Plasma Mass Spectrometric Study of Laser Sputtering from the Surface of an Al-Cu-Fe

Alloy and Quasicrystal”, Appl. Surf. Sci., 186, 322-328 (2002) (Crys. Structure,

Thermodyn., 19)

[2002Sha] Shalaeva, E.V., “On Mutual Transformation of Icosahedral Phase and -Solid Solution with

Participation of Ordered -Like Displasements in Quenched Alloys of Al61Cu26Fe13”, J.

Alloys Compd., 342, 134-138 (2002) (Crys. Structure, Experimental, 9)

[2002Tch] Tcherdyntsev, V.V., Kaloshkin, S.D., Salimon, A.I., Tomilin, I.A., Korsunsky, A.M.,

“Quasicrystalline Phase Formation by Heating a Mechanically Alloyed Al65Cu23Fe12

Powder Mixture”, J. Non-Cryst. Solids, 312-314, 522-526 (2002) (Crys. Structure,

Experimental, 19)

18


MSIT®

Al–Cu–Fe

[2002Yok] Yokoyama, Y., Matsuo, Y., Yamamoto, K., Hiraga, K., “Growth Condition and X-Ray

Analysis of Single Al64Cu23Fe13 Icosahedral Quasicrystal by the Czochralski Method”,

Mater. Trans., JIM, 43(4), 762-765 (2002) (Crys. Structure, Experimental, 13)

[2002Zha] Zhang, L.M., Lück, R, “Phase Equilibria of the Icosahedral Al-Cu-Fe Phase”, J. Alloys

Compd., 342, 53-56 (2002) (Equi. Diagram, Experimental, #, *, 11)

[2003Zha1] Zhang, L.M., Lück, R., “Phase Diagram of the Al-Cu-Fe Quasicrystal-Forming Alloy

System. I. Liquidus Surface and Phase Equilibria with Liquid”, Z. Metallkd., 94(2), 91-97

(2003) (Crys. Structure, Equi. Diagram, Experimental, Magn. Prop., #, *, 25)


System. II. Isopleths”, Z. Metallkd., 94(2), 98-107 (2003) (Equi. Diagram, Experimental, #,

*, 11)


System. III. Isothermal Sections”, Z. Metallkd., 94(2), 108-115 (2003) (Equi. Diagram,



System. IV. Formation and Stability of the -Al10Cu10Fe1 Phase”, Z. Metallkd., 94(3),

341-344 (2003) (Equi. Diagram, Experimental, Magn. Prop., 12)

[2003Mie] Miettinen, J., “Thermodynamic Description of the Cu-Al-Fe System at the Cu-Fe Side”,

Calphad, 27(1), 91-102 (2003) (Equi. Diagram, Thermodyn., #, *, 19)

Table 1: Crystallographic Data of Solid Phases

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

<660.45

cF4

Fm3m

Cu

a = 404.88 pure Al [V-C2]

(Cu)

<1084.87

cF4

Fm3m

Cu

a = 361.48 pure Cu [V-C2]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 366.60

a = 364.67

[V-C2]

[Mas2]

( Fe)

1538-1394

( Fe)

< 912

cI2

Im3m

W

a = 293.78

a = 293.15

a = 286.65

[V-C2]

[Mas2]

[V-C2], extensive joint solubility of Al

and Cu

Cu3Al

1049-559

cI2

Im3m

W

a = 294.6 [V-C2]

70.6 to 82 at.% Cu [Mas2]

, CuAl2<591

tI12

I4/mcm

Al2Cu

a = 606.3

c = 487.2

[V-C2]

31.9 to 33 at.% Cu [Mas2]

1, CuAl(h) 1)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

[V-C2, Mas2, 1985Mur]

49.8 to 52.4 at.% Cu [Mas2]

Pearson symbol: [1931Pre]

19


MSIT®

Al–Cu–Fe

2, CuAl(r) 1)

<560

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

[V-C2]

49.8 to 52.3 at.% Cu [Mas2]

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 59.8 at.% Cu [Mas2]

structure: [2002Gul]

2, Cu11.5Al9(r)

<570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

[V-C2]

55.2 to 56.3 at.% Cu [Mas2, 1994Mur]


1, CuxAl100-x

958-848

Cubic?

cP8

Pm3m

CsCl

[V-C2]

59.4 to 62.1 at.% Cu [Mas2]

[1998Wan]

2, Cu2-xAl

850-560

hP6

P63/mmc

InNi2

a = 414.6

c = 506.3

[V-C2]

55.0 to 61.1 at.% Cu [Mas2]

NiAs type in [Mas2, 1994Mur]

, Cu1-xAlx<686

hR*

R3m

a = 1226

c = 1511

0.381 x 0.407 [Mas2, 1985Mur]

59.3 to 61.9 at.% Cu [Mas2]

at x = 38.9 [V-C]

0, Cu100-xAlx1037-800

CI52

I43m

Cu5Zn8

- 59.8 to 69 at.% Cu [1998Liu]

1, Cu9Al4<890

CP52

P43m

Cu9Al4

a = 870.68

62 to 68.5 at.% Cu [Mas2, 1998Liu]

[V-C2] from single crystal

2, CuxAl100-x

<363

TiAl3long period

superlattice

a = 366.8

c = 368.0

76.5 to 78 at.% Cu [Mas2]

at 76.4 at.% Cu

(subcell only)

, FexCuyAlz

Fe4Al13

<1160

mC102

C2/m

Fe4Al13

a = 1548.9

b = 808.31

c = 1247.6

= 107.72°

0.22 < x < 0.31 [2003Zha1]

0 < y < 6

0.78 < z < 0.72

at x = 0.24

y = 0

z = 0.76 [V-C2]

Fe2Al5<1171

oC56

P63/mmc

Al5Co2

a = 767.5

b = 640.3

c = 420.3

[1953Sch]

for 72.0 at.% Al

70 to 73 at.% Al [1993Kat]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

20


MSIT®

Al–Cu–Fe

1)1 and 2 phases are not distinquished in [2003Zha1, 2003Zha2, 2003Zha3], notation is used in the diagrams

Table 2: Invariant Equilibria

, FeAl2<1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

[1973Cor], [V-C]

66 to 66.9 at.% Al [1993Kat]

at 66.9 at.% Al [V-C2]

, Al3Fe2

1232-1102

cI16

a = 598.0

~58 to ~65 at.% Al [1993Kat]

at 61 at.% Al [V-C], [1988Ray]

, (FexCuyAlz)

FeAl

< 1310

cP8

Pm3m

CsCl

a = 290.9

0 < x < 1,

0 < y < 1,

~0.23 < z 0.70

ordered bcc [V-C2]

23.3 to ~55 at.% Al [1993Kat]

1, Fe3Al

<552.5

cF16

Fm3m

BiF3

a = 579.23 [V-C]

23 to 34 at.% Al [1993Kat]

* 1, Al23CuFe4 oC28

Cmcm

Al6Mn

a = 643.43

b = 746.04

c = 877.69

[1961Bla]

exp=3.62 Mgm-3

* 2, FeCu2Al7 tP40

P4/mnc

Al7Cu2Fe

a = 633.6

c = 1487.0

[1956Bow], [1958Bro]

exp= 4.30 Mgm-3

* 3, FeCu10Al10 hP5

P3m1

-Ni2Al3

- [1939Bra2]

* i, ~Fe12.5Cu25.5Al62 - - icosahedral face centered

6D hypercubic unit [1989Dev],

[1989Eba], [1990Cal], [1990Fau2]

* 4, Fe15Cu20Al65 cI62

Mg32(Al,Zn)49

a = 1407 [1988Che], sample was heterogeneous

( 4+ i)

Reaction T [°C] Type Phase Composition (at.%)

Al Cu Fe

L + + ( Fe) Cu3Al 1048 P1 L 17.1 80.0 2.9

L + ( Fe) (Cu) + Cu3Al 1046 U1 L 17.0 81.0 2.0

L + Cu3Al 0 + 1015 U2 L 35.5 59.3 6.0

L + + i 882 P2 L 58.6 35.4 5.2

L + 2 ~750 p1max L 68.7 28.7 2.6

L + i + 2 ~740 U3 L 65.7 31.9 2.4

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

21


MSIT®

Al–Cu–Fe

L + i + 2 ~695 U4 L 61.3 36.7 2.0

3 + i 640 esol.1max - - - -

3 + 2 ~630 esol.2max - - - -

L + 1 626 p2max L 90.2 8.4 1.4

L + 2 + ~622 U5 L 61.5 37.7 0.8

L + 1 + 2 622 U6 L 87.45 11.70 0.85

L + 1 + (Al) 620 U7 L

(Al)

94.4

99.35

4.90

0.63

0.70

0.02

+ 2 3 + ~618 Usol.1

2

48.8

44.7

49.0

55.0

2.2

0.3

+ i 3 + 2 ~616 Usol.2

i

52.5

61.9

44.0

28.3

3.5

9.8

L + 2 + ~595 U8 L 62.2 36.9 0.9

L + 1 2 + (Al) 590 U9 L

(Al)

89.80

99.88

9.65

0.12

0.55

0.001

L 2 + 588 e1max L 68.2 31.0 0.8

2 + + 3 ~580 Esol.1 52.0 44.5 3.5

L 2 + + ~565 E1 L 66.4 32.9 0.9

Cu3Al (Cu) + + 1 564 Esol.2 Cu3Al 24.2 75.3 0.5

L (Al) + 2 + 542 E2 L

(Al)

82.83

99.77

17.03

0.23

0.14

0.0006


Al Cu Fe

20 40500

750

1000

Fe 22.80Cu 0.00Al 77.20

Fe 0.00Cu 57.50Al 42.50Cu, at.%

Tem

pera

ture

, °C

P2,882

L

L+β

L+λ1

L+λ2

L+λ1+λ2

λ2 λ2+τi

(Al)+λ1

τi

τi+λ2+β

(Al)+λ1+λ2(Al)+λ2

L+λ2+τiL+τi+β

L+λ2+β

L+τi

β

τ3+ε2

β+ε2ε2

τi+β+τ3

τi+τ2+τ3

τ2+τ3 τ3

β+τ3

τi+τ3

τ3+ητ2+τ3+η

τ2+τ3+ββ+τ3+η

~630

580

616

L

L+ε1

L+ε2

ε2+δ1

ζ2+δ1

Fig. 1: Al-Cu-Fe.

Vertical section along

the composition line

between Fe22.8Al77.2

and Cu57.5Al42.5

22


MSIT®

Al–Cu–Fe

20500

600

700

800

900

1000

1100

1200

Fe 20.00Cu 30.00Al 50.00

Fe 0.00Cu 10.00Al 90.00Cu, at.%

Tem

pera

ture

, °C

P2,882

U6,622

E2,542

L

L+λ

τi+β

λ+τi+β

L+β

L+λ+β

λ+τi

L+λ+τi

τi+τ2

τ2

L+λ+τ2

λ+τ2

L+τ1+τ2

L+(Al)+τ2

(Al)+θ+τ2

L+τ2

(Al)+θL+(Al)+θL+(Al)

L+τ1

L+λ+τ1

p1

τi

β

max

Fig. 2: Al-Cu-Fe.



between

Fe20Cu30Al50 and

Cu10Al90

10500

600

700

800

900

1000

1100

1200

Fe 0.00Cu 37.50Al 62.50

Fe 20.00Cu 21.00Al 59.00Fe, at.%

Tem

pera

ture

, °C

P2,882

Usol2

L

L+β

λ+β

τi+λ+βτi+β

L+λ+βL+λ

L+τi L+τi+

β

L+τi+τ2

L+τ2+β

L+τ2+η1U8,595

E1,565

τ2+η+τ3

τi+τ3+τ2τi+τ3τi+τ3+β

τ2+τi+βU4,695

L+τ2

θ+η2

L+η1+θL+η1

L+λ+τi

τ2+βesol1

τ2+η2+θ

max

L+η2+θL+τ2+η2

Fig. 3: Al-Cu-Fe



between

Fe20Cu21Al59 and

Cu37.5Al62.5

23


MSIT®

Al–Cu–Fe

10 20 30 40500

600

700

800

900

1000

1100

Fe 14.50Cu 0.00Al 85.50

Fe 3.50Cu 50.00Al 46.50Cu, at.%

Tem

pera

ture

, °C

P2,882

L+λ+β

L+β

L

L+λ

L+β+τi

L+λ+τi

L+τi

β

τi+βτ2+τi+β

τ2+τ3

τ2+η+τ3

τ2+τ3+β

τi+τ2+τ3

β+ε2

β+τ3

τ3+ε2

β+τ3+ητ3+ητ3

Esol1,580

Usol2,616

U4,695

U3,740

(Al)+τ1+τ2

L+τ1+τ2

L+λ+τ2

λ+τ2

τ2

τi+τ2

L+λ+τ1

(Al)+λ(Al)+λ+τ1

L+λ+(Al)

L+(Al)+τ1

L+τ1

(Al)+τ1

U9,590

U6,622

p1

τi+τ3+βp2

τi+τ2+L

Usol1U7,620

max

max

10500

600

700

800

900

1000

1100

1200

Fe 20.00Cu 25.00Al 55.00

Fe 0.00Cu 25.00Al 75.00Fe, at.%

Tem

pera

ture

, °C

LL+β

β

λ+β

L+λ+β

L+λ

L+τi

λ+τi

λ+τi+β

L+τ2

L+λ+τ2

L+τ2+θ

(Al)+θ+τ2E2,542

L+τi+τ2

L+τ2τ2+τi

E1

τ2+τi+τ3 θ+τ2

τ2+τi

τ2+η+τ3

e1U8,595

τi

L+λ+τi

U 3,740

U4,695

P2,882

β+

η+

τ2+τ3 τ2+θτ2+η

(Al)+θL+(Al)+θL+θ

β+

Esol1

Usol2

maxp1

max

Fig. 4: Al-Cu-Fe.



between Fe14.5Al85.5

and Fe3.5Cu50Al46.5

Fig. 5: Al-Cu-Fe.

Vertical section at

25 at.% Cu

24


MSIT®

Al–Cu–Fe

10 20 30 40500

750

1000

Fe 7.50Cu 0.00Al 92.50

Fe 7.50Cu 50.00Al 42.50Cu, at.%

Tem

pera

ture

, °C

L+β

β

L

L+λ

L+τ2

L+λ+τ2

L+τ1+τ2

L+(Al)+λL+λ+τ1

p2

L+τ1L+(Al)+τ1

(Al)+τ1+τ2

(Al)+τ1 (Al)+τ2

E2

(Al)+θ+τ2

τ2+θ

L+τ2+θ

L+(Al)+τ2

(Al)+τ1+λ τ2+θ

τ2+η τ2+τ3

τ2+τ3+η

Esol1

τ2+τ3+β

Usol2

τi+τ2+βτi+τ3+β

τi+τ3τi+τ2+τ3

τi+β

L+τi+βL+τi

U3

L+τi+λ

p1max

P2,882

U4,695L+τi+τ2

U6

U9

L+τ2+η

E1

L+τ2+βτ2+β

U8

η+(Al)+λ

L+λ+β

max

U7

10 20 30 40500

750

1000

Fe 5.00Cu 0.00Al 95.00

Fe 5.00Cu 50.00Al 45.00Cu, at.%

Tem

pera

ture

, °C

L

L+β

L+λ+β

L+τi+β

β

τi+β

τ3

τ2+τ3+τiτ2+η+τ3

τ2+τ3τ2+η

(Al)+τ1+τ2

(Al)+τ1

L+(Al)+τ1

L+τ1

L+τ1+τ2

L+λ+τ1L+(Al)+λ

(Al)+λ+τ1

(Al)+λL+(Al)+τ2

(Al)+τ2

E2 (Al)+τ2+θ

L+τ2+θ

τ2+θ+η

L+τ2+ηE1

U8,595

τ2+β+τ3

L+τ2+β

L+λ+τi

L+λ+τ2

L+λ

L+τ2

U9

U6

e1

τ2+βτ3+τi+β

β+τ3

τi+β+τ2

U2,695U3L+τi+τ2

p1

P2,882

p2

Esol1,580

L+τi

τ2+θ

U 7

τi+τ3

Usol2max

max

max

Fig. 7: Al-Cu-Fe.

Vertical section at

7.5 at.% Fe

Fig. 6: Al-Cu-Fe.

Vertical section at

5 at.% Fe

25


MSIT®

Al–Cu–Fe

10 20 30500

600

700

800

900

1000

1100

1200

Fe 10.00Cu 0.00Al 90.00

Fe 10.00Cu 40.00Al 50.00Cu, at.%

Tem

pera

ture

, °C

L

L+βL+λ+β

L+τi+β

L+τi

L+λ+τ i

U3,740

U4,695

L+τi+τ2

τi+τ2+β

τ1+β

τi+τ3+β

τi+τ3

τi+τ1+τ3

τi+τ2

τ2

τ2+λ

L+τ1+τ2

L+λ+τ2

U6,622

U9,590L+τ1(Al)+λ+τ1

L+λ+(Al)L+τ1+λ

p2

p1

L+(Al)+τ1

(Al)+τ1+τ2

(Al)+τ1

β

P2,882

L+λ

U7

(Al)+λ

max

max

Usol2

10 20 30500

600

700

800

900

1000

1100

1200

Fe 12.00Cu 0.00Al 88.00

Fe 12.00Cu 40.00Al 48.00Cu, at.%

Tem

pera

ture

, °C

L+β

L+λ+β

L

L+λ

L+(Al)+λL+λ+τ1

p2

L+λ+τ2

U6,622

λ+τ2λ+τ1+τ2

L+(Al)+τ1

(Al)+τ1+τ2

(Al)+τ1

(Al)+τ1+λ

p1

P2,882

L+τi+β

L+λ+τ

i

L+τi

τi+β

β

τi+τ2

τi

λ+τ2+τi

U3,740

L+τ1

L+τ1+τ2

U9,590

(Al)+λ

τ2+τ1

U7,620

max

max

Fig. 8: Al-Cu-Fe.

Vertical section at

10 at.% Fe

Fig. 9: Al-Cu-Fe.

Vertical section at

12 at.% Fe

26


MSIT®

Al–Cu–Fe

20 40 60 80

750

1000

1250

1500

Fe 90.18Cu 0.00Al 9.82

Fe 0.00Cu 88.97Al 11.03Cu, at.%

Tem

pera

ture

, °C

(Cu)

(αδFe)

L+(αδFe)

(αδFe)+(Cu)

L

20 40 60

750

1000

1250

1500

Fe 81.30Cu 0.00Al 18.70

Fe 0.00Cu 79.26Al 20.74Cu, at.%

Tem

pera

ture

, °C

L

(αδFe)+L(αδFe)

(αδFe)+(Cu)

Cu3Al

(αδFe)+Cu3Al+(Cu)

Fig. 10: Al-Cu-Fe.

Calculated vertical

section at 5 mass% Al

Fig. 11: Al-Cu-Fe.

Calculated vertical

section at

10 mass% Al

27


MSIT®

Al–Cu–Fe

20 40 60

750

1000

1250

1500

Fe 73.24Cu 0.00Al 26.76

Fe 0.00Cu 70.64Al 29.36Cu, at.%

Tem

pera

ture

, °C

L

(αδFe)+L(αδFe)

β(1)

Cu3Al

β(2)

β(1)+(Cu)β(2)+γ1

Tc

β(1)+β(2)

Fig. 13: Al-Cu-Fe. Partial reaction scheme for the Cu corner

Cu-Fe

l + (δFe) (γFe)

1487 p1

Al-Cu-Fe

L+(αδFe)+(γFe) Cu3Al1048 P

1

Al-Cu

l + Cu3Al γ

0

1037 p3

l + (γFe) (Cu)

1095 p2

l (Cu) + Cu3Al

1032 e1

Cu3Al (Cu)+γ

1+(αδFe)564 E

sol2

L+Cu3Al γ

0+(αδFe)1015 U

2

L+(γFe) (Cu)+Cu3Al1046 U

1

L+Cu3Al+(αδFe)

L + (γFe) +Cu3Al (αδFe) + (γFe) +Cu

3Al

(γFe)+(Cu)+Cu3Al

Cu3Al+γ

0+(αδFe)

(Cu) + γ1 + (αδFe)

L + γ0 + (αδFe)

Fig. 12: Al-Cu-Fe.

Calculated vertical

section at

15 mass% Al

28


MSIT®

Al–Cu–Fe

Fig

. 14:

A

l-C

u-F

e.

Par

tial

reac

tion s

chem

e fo

r th

e A

l co

rner

Al-

Fe

Al-

Cu

-Fe

Al-

Cu

L +

λτ 1

62

6p2max

l (

Al)

+ λ

65

5e 2

L +

β +

λτ i

88

2P2

l +

ε2

η6

24

p4

L +

λτ 2

75

0p1

max

Lτ 2

+ η

+ θ

56

5E1

L +

βτ 2

+ η

59

5U8

L +

ε2

β +

η6

22

U5

L +

τi

β +

τ2

69

5U4

L+

λτ i

+ τ2

74

0U3

lθ

+ (

Al)

54

8e 3

l +

ηθ

59

1p5

Lτ 2

+ θ

58

8e 1

max

L +

λτ 1

+ τ2

62

2U6

L +

λτ 1

+ (

Al)

62

0U7

L +

τ1

τ 2+

(A

l)5

90

U9

L(A

l) +

τ2+

θ5

42

E2

l +

(A

l) +

λL

+λ+

τ 1

L+

τ 2+

λ

L+λ

+τ2

L+

λ+τ i

β+λ+

τ i

L+

τ 2+

τ iλ+

τ 2+

τ i

τ 2+λ

+τ1

L +

(A

l) +

τ1

(Al)

+λ+

τ 1

(Al)

+τ 2

+τ1

L+

(Al)

+τ 2

L+

θ+(A

l)

L+

θ+τ 2

(Al)

+τ 2

+θ

L+

ε 2+η

τ i+τ 2

+β

L+

ε 2+β

L+

β+η

β+ε 2

+η

L+

τ 2+

η

L+

θ+η

η+τ 2

+θ

?

βτ 3

+ τi

64

0e sol1max

βτ 3

+ ε2

63

0e sol2max

β +

ε2

τ 3+

η6

18

Usol1

β +

τi

τ 2 +

τ3

61

6Usol2

τ i+β+

τ 3τ i+

β+τ 3 β+

τ 3+

ε 2β+

τ 3+

ε 2

βτ 2

+ η

+τ 3

58

0Esol1

L+

θ+τ 2

β+τ 2

+ηβ+

τ 2+

τ 3τ 2

+τ i+

τ 3

τ 3+

ε 2+

η

L+

τ 2+

τ 1

L+

β+τ i

L+

τ 2+

β

η+τ 3

+τ 2

L+

λ+τ 1

β+η+

τ 3

L+

β+λ

29


MSIT®

Al–Cu–Fe

10

20

30

40

60 70 80 90

10

20

30

40

Fe 45.00Cu 55.00Al 0.00

Cu

Fe 0.00Cu 55.00Al 45.00 Data / Grid: at.%

Axes: at.%

p2

e1

p3

U2

U1

(Cu)

Cu3Al

γ0

(αδFe)

(γFe)

P1

10

20

30

40

10 20 30 40

60

70

80

90

Fe 50.00Cu 0.00Al 50.00

Fe 0.00Cu 50.00Al 50.00

Al Data / Grid: at.%

Axes: at.%

λ

β

Fe2Al5

τ i

U4

U8

E1

P2

E2

U6

p 2

U7

e2

1100

10501000

950900

800750

700

U9

e3

τ2

θ

p5

p4

η

ε2

(Al)

τ1

U5

U3

e1

maxp1

max

max

Fig. 15: Al-Cu-Fe.

Partial liquidus

surface projection of

the Cu corner

Fig. 16: Al-Cu-Fe.

Liquidus surface

projection and

contour lines for the

Al-rich portion

30


MSIT®

Al–Cu–Fe

10

20

30

40

10 20 30 40

60

70

80

90

Fe 50.00Cu 0.00Al 50.00

Fe 0.00Cu 50.00Al 50.00


Axes: at.%

λ

τ1

τ2

τ i

p5

e3E2

U6

U9

U7

e2 (Al)

p1max

e1max

Fe2Al5

p4

U5

U4

U8

E1

P2

τ i

β

U3

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

δ1

ζ2

η2

θ

β

τ1

τ2

τ i

τ3

λFe2Al5

(Al)

Fig. 17: Al-Cu-Fe.

Liquidus surface

projection and

invariant planes

Fig. 18: Al-Cu-Fe.

Al-rich part of the

isothermal section at

room temperature

31


MSIT®

Al–Cu–Fe

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

β+Cu3Al

β(1)+β(2)

β

(αδFe)

(αδFe)+(Cu)

λFe2Al5

ζ

L

(Cu)

β+(Cu)Cu3Al

γ1

ε2

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

β

Cu3Al

(αδFe)

β(1)+β(2)

β+Cu3Al

(αδFe)+(Cu)

λFe2Al5

ζ

L

(Cu)

Fig. 19: Al-Cu-Fe.

Calculated

isothermal section at

800°C

Fig. 20: Al-Cu-Fe.

Calculated isothermal

section at 900°C

32


MSIT®

Al–Cu–Fe

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

λFe2Al5

ζ

(αδFe)

β β(1)+β(2)

β+Cu3Al

(αδFe)+Cu3Al

(αδFe)+(Cu)

L

(Cu)

(γFe)

Cu3Al

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

L

β

λFe2Al5

ζ

β+L

(αδFe)

(αδFe)+L

(γFe)

Fig. 21: Al-Cu-Fe.


section at 1000°C

Fig. 22: Al-Cu-Fe.


section at 1100°C

33


MSIT®

Al–Cu–Fe

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

β

(αδFe)

L

β+L

(αδFe)+L

ε

(γFe)

20

40

60

80

20 40 60 80

20

40

60

80

Fe Cu


Axes: at.%

(αδFe)

L

(γFe)

(αδFe)+L

Fig. 23: Al-Cu-Fe.


section at 1200°C

Fig. 24: Al-Cu-Fe.


section at 1300°C

34


MSIT®

Al–Cu–Fe

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Fe 60.00Cu 0.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

Fe2Al5+β

λ+βλ+Fe

2 Al5 +β

λ+Fe2Al5 λ λ+L

λ+τ i+L

β+L

β

β+τi +λ

β+τ i

β+τi +L

β+ε2+L

ε2

β+ε2

L+ε2

L

τ i L+τ i

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Fe 60.00Cu 0.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

λ

L

L+λ

β

τ2

τ i

ε2

L+λ+τ2

λ+τ2

L+τ2

λ+τi +β

λ+β

λ+β+Fe2 Al

5 L+τ i

L+τ i+βτ i+β

β+ε2

L+β+ε2

L+ε2

L+β

Fig. 25: Al-Cu-Fe.

Isothermal section in

the Al-rich portion at

800°C

Fig. 26: Al-Cu-Fe.



700°C

35


MSIT®

Al–Cu–Fe

10

20

30

30 40 50

50

60

70

Fe 40.00Cu 20.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

β

τ3β+τ3

β+ε2

L+β+ε2

ε2

L+τ2

L

L+β

L+ε2τ i+β

τ i+λ

λ+τ i+β

λ+β

τ iτ2 +β+L

τ2

τ2+λ+τ i

10

20

30

30 40 50

50

60

70

Fe 40.00Cu 20.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

λ+β

λ+τ i+β

τ i+β

τ i+λτ i

τ2+L

L+τ2 +β

β+ε2

β+τ3+ε2

ε2

η+ε2

β+η+ε2β+τ3

L+η+ββ

τ3β

L

η

L+η

τ i+β+τ3

τ2

τ i+λ+β

Fig. 28: Al-Cu-Fe.



620°C

Fig. 27: Al-Cu-Fe.



645°C

36


MSIT®

Al–Cu–Fe

10

20

30

30 40 50

50

60

70

Fe 40.00Cu 20.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

λ+β

τ i+λ+β

τ i+β

β+ε2ε2

η+ε2

β

τ3

τ2+L

L

L+β+η

τ3+ε2

τ i+λ

τ iL+τ

2 +β

β

τ2

η

τ i+β+λ

10

20

30

30 40 50

50

60

70

Fe 40.00Cu 20.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

τ i+λ+β

β

τ3

L+τ2 +β

L+β+η

τ i

L

τ2

η

β+τ iβ+λ

L+τ2

β+ε2

ε2

λ+τ i+τ2

λ+τ i

β

τ3+ε2

Fig. 29: Al-Cu-Fe.



617°C

Fig. 30: Al-Cu-Fe.



600°C

37


MSIT®

Al–Cu–Fe

10

20

30

30 40 50

50

60

70

Fe 40.00Cu 20.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

L

η

ε2

τ3

β

τ2

τ i

τ i+λ+β

L+τ2 +η

τ i+β

L+τ2

λ+τ i+τ2

β+ε2

βλ+β

τ3+ε2

10

20

30

30 40 50

50

60

70

Fe 40.00Cu 20.00Al 40.00

Fe 0.00Cu 60.00Al 40.00


Axes: at.%

λ+β

λ+τ i+β

τ i+β

τ i

λ+τ i

τ2+θ+η

L+θ+τ2

ε2

β+ε2

τ2 +τ

3 +η

η+τ3+ε2

β

τ3

L

τ2

η

θ

τ3 +ε

2

λ+τ i+τ2

Fig. 31: Al-Cu-Fe.

Isothermal section

diagram in the Al-rich

portion at 592°C

Fig. 32: Al-Cu-Fe.



560°C

38


MSIT®

Al–Cu–Gd

Aluminium – Copper – Gadolinium

Paola Riani, Pierre Perrot

Literature Data

First critical evaluation of the Al-Cu-Gd data was made within the MSIT Ternary Evaluation Program by

[1991Ran] incorporating literature data up to 1988. The present assessment continues the work of

[1991Ran] and considers all information published up to 2002, which leads to amended descriptions of the

reliably known phase equilibria.

As for the phase equilibria, isothermal section at 500 and 600°C have been studied by [1988Pre] and

[2001Gum], respectively. [1988Pre] prepared 76 alloys by arc melting the constituent metals under argon

and annealing at 500°C for not less than 400 hours and quenching. [2001Gum] synthesized 38 ternary

samples by arc melting under purified Ar atmosphere of the components of purities of 99.5 mass% Gd,

99.95 mass% Cu and Al. All alloys prepared were heat treated at 600 and 500°C in evacuated silica

ampoules for 1000 h and then quenched in cold water. Generally X-ray powder diffraction techniques were

used for phase analysis, determination of solubility, etc.

Other contributions to the phase relationships result from the determining the mutual solubility of GdAl2and GdCu2. [1973Hid] annealed samples for two weeks at 800°C; using X-ray diffraction they established

the solubility limit of GdCu2 in GdAl2 to be at 20 at.% over-all Cu concentration. [1974Oes] studied the

homogeneity ranges of GdCu2 and GdAl2 by substituting Cu by Al and Al by Cu, respectively, on samples

prepared by induction melting and quenching. The limits reported are: Cu in GdCu2 can be replaced by Al

up to about 1 at.%, Al in GdAl2 can be replaced by Cu up to about 10 at.%. Between these two binary

compounds, at the composition GdCuAl, the sample has the Fe2P type structure [1968Dwi, 1973Oes,

1975Bus, 1988Pre]. This compound has no significant homogeneity range on the line GdAl2 to GdCu2. The

high pressure modification of GdCuAl and its structure were reported by [1987Tsv1, 1987Tsv2]. Other

ternary compounds were found or confirmed: GdCu4Al8 by [1976Bus] and [1979Fel], GdCu6Al6 by

[1980Fel] and [1981Fel], GdCu4Al by [1978Tak], Gd2Cu7Al10 by [1982Pre], and Gd2Cu6Al11 by

[1978Pop]. [1986Bor] determined the temperature dependence of the lattice parameters of the binary

compound Gd(Cu1-xAlx)2 for temperatures below 150 K with x values up to 0.07.

Binary Systems

The binary systems Al-Gd from [2002Bod], Al-Cu from [2003Gro] and Cu-Gd from [1988Sub, 1994Sub]

are used as boundary systems.

Solid Phases

The solubility of Al in the compound GdCu2 is not more than 3 at.% according to [1988Pre] which is in

good agreement with the value of [1974Oes], whereas different values have been reported for the solubility

of Cu in GdAl2: negligible according to [1988Pre] and [2001Gum], and 10 at.% Cu [1974Oes] or 20 at.%

Cu [1973Hid] and [1994Mag]. Notice however that in the figure reported by [2001Gum] and shown here

an extension of the GdAl2 phase up to about 5 at.% is presented.

The following remarks may be noteworthy for the different ternary phases.

For GdCuAl3 the crystal structure described as BaAl4 by [1988Pre] and assumed to be BaNiSn3 type by

[1994Mul], was not confirmed by [2001Gum]; however the compound Gd3Cu2.1Al8.9 with a close

composition and the related oI28 La3Al11 type structure, was found.

Magnetic properties of GdT4Al8 and GdT6Al6 (T = Cr, Mn, Cu) and crystallographic site occupation were

described by [2001Duo]. The phases GdCu4Al8 and GdCu6Al6 have the same structure (ThMn12 type) and

probably belong to the same solid solution range, although the investigators did not mention this point.

39


MSIT®

Al–Cu–Gd

For the ternary alloys the phase with the ideal BaCd11 type structure has been described for GdCu7.8Al3.2,

with Gd in 4a, Cu in 8d and (Cu+Al) in 4b and 32i by [2001Gum]; an orthorhombic variant of this structure

was observed for GdCu6.6Al4.4 [2001Gum] with similar values of the co-ordination numbers.

For the Gd2(Cu,Al)17 compound the crystal structure was described by [1982Pre, 1988Pre, 2001Gum] as

pertaining to the Th2Zn17 type, corresponding to Gd in 6c, Cu in 9d and a mixed occupation (Cu + Al) in

the other sites. For the Gd2Cu7Al10 compound [1982Pre] a homogeneity range was described by [1988Pre]

and [2001Gum] respectively by the formula Gd2Cu6.7-8.0Al9.0-10.3 and Gd2Cu9.4-6.7Al7.6-10.3.

According to [1978Pop] the structure Th2Ni17 type was observed in the Gd system at ~Gd2Cu6Al11; this

phase however was not confirmed by [1988Pre] and [2001Gum].

The alloy GdCu4Al, which was reported as a ternary compound [1978Tak], is included in the ternary

homogeneity range of the binary compound Gd(Cu1-xAlx)5 with 0 x 0.6 derived from GdCu5, to which

a limit of solubility for Al up to 50 at.%, with the formula of GdCu2Al3 was assigned [1988Pre]. Details on

crystal structures of the solid phases are reported in Table 1.

Isothermal Sections

Based on crystallographic data Kuz’ma and co-authors published equilibria in two subsequent papers,

[1988Pre], [2001Gum]. The isothermal sections at 500 and 600°C published in both papers are

incompatible, however the applied changes are not commented and no indication is given how the equilibria

have been concluded. The problem arising from the two papers may be summarized as follows: the phase

previously indicated by [1988Pre] as GdCuAl3 (BaAl4 type) was not found by [2001Gum] (neither at 500°C

nor at 600°C); a composition 5,Gd3Cu2.1Al8.9 was instead proposed for a phase with the structure La3Al11

type. The new phase 6,GdCu0.9Al2.1 (PuNi3 type) was identified by [2001Gum]. For the phase with

unknown structure previously indicated by [1988Pre] as GdCu5Al4, the composition 2,GdCu7.8Al3.2

(BaCd11 type) was proposed by [2001Gum]. The phase indicated as ~GdCu11Al8 in the English version of

[1988Pre], but cited by [2001Gum] as Gd2Cu11Al8, referring to the same publication of [1988Pre], but to

the Russian version, is described as 3,GdCu6.6Al4.4 (Tb(Cu0.58Al0.42)11 type) by [2001Gum]. In the earlier

published 500°C isothermal section by [1988Pre] the 2, 3 phases were not characterized in their structure

and the annealing times were much shorter than in the later published work of [2001Gum] in which structure

and composition ranges of the phases have been refined. In [2001Gum] the authors claim to have found at

both temperatures, 500 and 600°C, the same phases but do not give an isothermal section at 500°C. The

present evaluation accepted the phases and phase compositions as published in [2001Gum] and amended

with considerable reservation the 500°C section accordingly. This revealed that the refined compositions of

2, 3 and 5 can not exist in an equilibrium configurations as shown earlier by [1988Pre]. Therefore the

equilibria at 500°C had to be modified, too, to show a possible configuration. See the isothermal section at

500°C, Fig. 1.

There is some disagreement between the accepted binary Al-Cu system [2003Gro] and the Al-Cu phases

shown in the diagrams by [1988Pre] and [2001Gum]. In the 600°C section by [2001Gum] no indication is

given of the liquid phase in the Al-rich region. The 2 phase should possibly be 1, instead of the phase

should have been observed. The phase sequence along the Al-Cu edge at 600°C reported in [2001Gum]

would be in better agreement with the accepted binary Al-Cu system with a temperature of ~ 550°C instead

of 600°C, except for the phase. Fig. 2 shows the partial isothermal section at 600°C after [2001Gum]

corrected to eliminate the above inconsistencies.

The present evaluation supersedes the slightly different evaluation made in the MSIT Evaluation Program

by [1991Ran].


[2001Duo] studied the magnetic properties of GdCu4Al8 and GdCu6Al6 by means of standard

magnetization and susceptibility measurements, magnetization measurements in high fields up to 35 T and

measurements of specific heat; moreover they analyzed the data in terms of a simple mean-field

two-sublattice model and found that the coupling between Gd moments is fairly weak and leads to

antiferromagnetic ordering at rather low temperatures.

40


MSIT®

Al–Cu–Gd

Magnetic and electrical properties of the GdCu5-xAlx (x = 0 to 2) alloys have been described by [1998Tun]:

all the alloys were of the CaCu5 type; to avoid the cubic AuBe5 type, splat cooling was applied to

GdCu5-xAlx alloys with x = 0 and 0.1; for 0.5 x 2.0 it was found that the AuBe5 type structure does not

exist and these compounds melt congruently to form the hexagonal CaCu5 type structure.

[1994Mul] investigated the magnetic properties and the 155Gd Mössbauer spectra of GdCuAl3 which was

found to order anti-ferromagnetic at low temperatures.

[1998Jav] studied the magnetic properties of the RCuAl (R = Y, Ce to Sm, Gd to Tm and Lu) intermetallic

compounds by means of susceptibility, magnetization and specific heat measurements and observed a

magnetic ordering at low temperatures in most of these materials: PrCuAl and NdCuAl showed an

antiferromagnetic behavior while in the heavy rare-earth compounds (R=Gd-Er) a ferromagnetic coupling

was found.

The magnetization, electrical resistivity and AC susceptibility measurements, carried out by [2000Jar],

provide evidence for a ferromagnetic type of order-disorder transition at 83 K in GdCuAl; a second

transition at 23 K was also found.

References

[1931Pre] Preston, G.D., “An X-ray Investigation of some Copper-Aluminium Alloys”, Phials. Mag.,


[1968Dwi] Dwight, A.E., Müller, M.H., Conner, R.A.Jr., Downey, J.W., Knott, H., “Ternary

Compounds with the Fe2P-Type Structure”, Trans. Met. Soc. AIME, 242, 2075-2080 (1968)


[1973Hid] Hidaka, M., Sakai, M., Hosokawa, H., Sakurai, J., “The Paramagnetic Curie Temperature

of the Alloys Gd(Al1-xCux)2 and Gd(Al1-xNix)2”, J. Phys. Soc. Japan, 35, 452-455 (1973)


[1973Oes] Oesterreicher, H., “Structural and Magnetic Studies on Rare Earth Compounds RNiAl and

RCuAl”, J. Less-Common Met., 30, 225-236 (1973) (Crys. Structure, Experimental, 21)

[1974Oes] Oesterreicher, H., “Constitution of Aluminum Base Rare Earth Alloys RT2-RAl2 (R = Pr,

Gd, Er; T = Mn, Fe, Co, Ni, Cu)”, Inorg. Chem., 13, 2807-2811 (1974) (Crys. Structure,

Equi. Diagram, Experimental, 30)

[1975Bus] Buschow, K.H.J., “Note on the Magnetic Properties of Some Fe2P-Type Rare-Earth

Intermetallic Compounds”, J. Less-Common Met., 39, 185-188 (1975) (Crys. Structure,

Experimental, 1)

[1976Bus] Buschow, K.H.J., van Vucht, J.H.N., van den Hoogenhof, W.W., “Note on the Crystal

Structure of the Ternary Rare Earth - 3d Transition Metal Compounds of the Type RT4Al8”,

J. Less-Common Met., 50, 145-150 (1976) (Crys. Structure, Experimental, 2)

[1978Pop] Pop, I., Coldea, M., Wallace, W.E., “NMR and Magnetic Susceptibility of Gd2Cu6Al11 and

Gd2Co6Al11 Intermetallic Compounds”, J. Solid State Chem., 26, 115-121 (1978) (Crys.


[1978Tak] Takeshita, T., Malik, S.K., Wallace, W.E., “Crystal Structure of RCu4Ag and RCu4Al (R =

Rare Earth) Intermetallic Compounds”, J. Solid State Chem., 23, 225-229 (1978) (Crys.


[1979Fel] Felner, I., Nowik, I., “Magnetism and Hyperfine Interactions of 57Fe, 151Eu, 155Gd, 161Dy,166Er and 170Yb in RM4Al8 Compounds (R=Rare Earth or Y, M=Cr, Mn, Fe, Cu)”., J. Phys.

Chem. Solids, 40, 1035-1044 (1979) (Crys. Structure, Experimental, 8)

[1980Fel] Felner, I., “Crystal Structure of Ternary Rare Earth - 3d Transition Metal Compounds of the

RT6Al6 Type”, J. Less-Common Met., 72, 241-249 (1980) (Crys. Structure, Experimental,

10)

[1981Fel] Felner, I., Seh, M., Rakavy, M., Nowik, I., “Magnetic Order and Hyperfine Interactions in

RFe6Al6 (R = Rare Earth)”, J. Phys. Chem. Solids, 42, 369-377 (1981) (Crys. Structure,

Experimental, 6)

41


MSIT®

Al–Cu–Gd

[1982Pre] Prevarskiy, A.P., Kuz'ma, Yu.B., “New Compounds with Th2Sn17 Type Structure in

REM-Al-Cu Systems”, Russ. Metall., 6, 155-156 (1982) (Crys. Structure, Experimental, 5)

[1985Mur] Murray, J.L., “The Aluminum-Copper System”, Int. Met. Rev., 30(5), 211-233 (1985) (Equi

Diagram, Crys. Structure, Review, 230)

[1986Bor] Borombaev, M.K., Levitin, R.Z., Markosyan, A.S., Smetana, Z., Sneginev, V.V., Svoboda,

P., “Magnetic and Crystallographic Properties of Gd(Cu1-xNix)2 and Gd(Cu1-xAlx)2

Intermetallic Compounds”, Phys. Status Solidi, 97, 501-509 (1986) (Crys. Structure,


[1987Tsv1] Tsvyashchenko, A.V., Fomicheva, L.N., “High-Pressure Synthesis and Structural Studies of

Rare Earth (R) Compounds RCuAl”, J. Less-Common Met., 134(2), L13-L15 (1987) (Crys.


[1987Tsv2] Tsvyashchenko, A.V., Fomicheva, L.N., “New Polymorphic Modifications of the

Compounds RTAl (R = r.e.m., T = Cu, Ni)”, Inorg. Mater., 23, 1024-1027 (1987), translated

from Izv. Akad. Nauk SSSR, Neorg. Mater., 23(7), 1148-1152 (1987) (Crys. Structure,

Experimental, 15)

[1988Gsc] Gschneidner, Jr K.A., Calderwood, F.W., “The Al-Gd (Aluminum-Gadolinium) System”,

Bull. Alloy Phase Diagrams, 9, 680-683 (1988) (Equi. Diagram, Review, 41)

[1988Pre] Prevarskii A.P., Kuz'ma, Yu.B., “X-Ray Structural Investigation of the System Gd-Cu-Al”,

Russ. Metall., (1), 205-207 (1988), translated from Izv. Akad. Nauk SSSR, Met., (1), 207-209

(1988) (Crys. Structure, Equi. Diagram, Experimental, 6)

[1988Sub] Subramanian, P.R., Laughlin, D.E., “The Cu-Gd (Copper-Gadolinium) System”, Bull. Alloy

Phase Diagrams, 9, 347-354 (1988) (Equi. Diagram, Review, 34)

[1989Mee] Meetsma, A., de Boer, J.L., van Smaalen, S., “Refinement of the Crystal Structure of

Tetragonal Al2Cu”, J. Solid State Chem., 83(2), 370-372 (1989) (Crys. Structure,

Experimental, 17)

[1991Ell] Ellner, M., Kolatschek, K., Predel, B., “On the Partial Atomic Volume and the Partial Molar

Enthalpy of Aluminium some Phases with Cu and Cu3Al Structures”, J Less-Common

Metals, 170, 171-184 (1991) (Crys. Structure, Experimental, 57)

[1991Ran] Ran, Q., “Aluminium - Copper - Gadolinium”, MSIT Ternary Evaluation Program, in MSIT

Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH,

Stuttgart; Document ID: 10.12786.1.20 (1991) (Crys. Structure, Equi. Diagram,

Assessment, 23)

[1994Mag] Magnitskaya, M., Chelkowska, G., Borstel, G., Neumann, M., Ufer, H.,

“ElectronicStructure of Gd-Based Laves Phase Alloys”, Phys. Rev. B, 49, 1113-1119 (1994)

(Calculation, Magn. Prop., Crys. Structure, 25)

[1994Mul] Mulder, F.M., Thiel R.C., Buschow, K.H.J., “155Gd Mössbauer Effect in Several

BaNiSn3-Type Compounds”, J. Alloys Compd., 216, 95-98 (1994) (Crys. Structure, Magn.

Prop., Moessbauer, 9)

[1994Mur] Murray, J.L., “Al-Cu (Aluminum-Copper)” in “Phase Diagrams of Binary Copper Alloys”,

Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM International Materials

Park, OH, Vol. 10, 18-42, (1994) (Equi. Diagram, Review, 226)

[1994Sub] Subramanian P.R., Laughlin, D.E., “The Cu-Gd (Copper-Gadolinium) System” in “Phase

Diagrams of Binary Copper Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E.

(Eds.), ASM International, Materials Park, OH, Vol. 10, 185-190 (1994) (Equi. Diagram,

Review, 33 )

[1996Goe] Gödecke, T., Sommer, F., “Solidification Behaviour of the Al2Cu Phase”, Z. Metallkd.,

87(7), 581-586 (1996) (Equi. Diagram, Crys. Structure, 8)

[1998Jav] Javorský, P., Havela, L., Sechovský, V., Michor, H., Jurek, K., “Magnetic Behaviour of

RCuAl Compounds”, J. Alloys Compd., 264, 38-42 (1998) (Experimental, Magn. Prop.,

Crys. Structure, 15)

42


MSIT®

Al–Cu–Gd

[1998Liu] Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria in the Cu-rich Portion of

the Cu-Al Binary System”, J. Alloys Compd., 264(1-2), 201-208 (1998) (Equi. Diagram,


[1998Tun] Tung, L.D., Buschow, K.H.J., Franse, J.J.M., Brommer, P.E., Duijn, H.G.M., Brück, E.,

Thuy, N.P., “Magnetic and Electrical Properties of the Pseudo-Binary GdCu5-xAlxCompounds”, J. Alloys Compd., 269, 17-24 (1998) (Crys. Structure, Electr. Prop.,


[2000Jar] Jarosz, J., Talik, E., Mydlarz, T., Kusz, J., Boehm, H., Winiarski, A., “Crystallographic,

Electronic Structure and Magnetic Properties of the GdTAl; T = Co, Ni and Cu Ternary

Compounds”, J. Magn. Magn. Mater., 208, 169-180 (2000) (Crys. Structure, Experimental,

Magn. Prop., 23)

[2000Sac] Saccone, A., Cardinale, A.M., Delfino S., Ferro R., “Gd-Al and Dy-Al Systems: Phase

Equilibria in the 0 to 66.7 at.% Al Composition Range”, Z. Metallkd., 91(1), 17-23 (2000)

(Experimental, Equi. Diagram, Crys. Structure, 12)

[2001Duo] Duong, N.P., Klaasse, J.C.P., Brück, E., de Boer, F.R., Buschow, K.H.J., “Magnetic

Properties of GdT4Al8 and GdT6Al6 Compounds (T = Cr, Mn, Cu)”, J. Alloys Compd., 315,


[2001Gum] Gumeniuk, R.V., Stel’makhovych, B.M., Kuz’ma, Yu.B., “The Gd-Cu-Al System”, J.

Alloys Compd., 329, 182-188 (2001) (Crys. Structure, Equi. Diagram, Experimental, 27)

[2002Bod] Bodak, O., “Al-Gd (Aluminium-Gadolinium)”, MSIT Binary Evaluation Program, in MSIT



Assessment, 15)


System”, Abstr. VIII Int. Conf. ”Crystal Chemistry of Intermetallic Compounds”,

September 2002, Lviv, P139, 73 (2002) (Crys. Structure, Experimental, 5)

[2003Gro] Gröbner, J., “Al-Cu (Aluminium - Copper)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart; to be published, (2003) (Crys. Structure, Equi. Diagram, Assessment, 68)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

(Cu)

< 1084.62

Cu1-xAlx

cF4

Fm3m

Cu

a = 361.46

a = 361.52

a = 365.36

at 25°C [Mas2], 0 to 19.7 at.% Al [Mas2]

0 to 0.1 at.% Ce at 876°C [1994Sub]

[1991Ell], x = 0, quenched from 600°C

[1991Ell], x = 0.152, quenched from 600°C

( Gd)

1313-1235

~630°C (10.5 at.% Cu)

cI2

Im3m

W

a = 406 [Mas2]

~10 to 15 at.% Cu at 675°C, [1994Sub]

0 to ~3 at.% Al at 1200°C, [2000Sac]

( Gd)

< 1235

hP2

P63/mmc

Mg

a = 363.36

c = 578.10

at 25°C [Mas2]

0 to ~2 at.% Cu at 630°C, [1994Sub]

0 to ~0.9 at.% Al at 1200°C, [2000Sac]

, Cu3Al(h)

1049-559

cI2

Im3m

W

a = 294.6

a = 295.64

~70 to 82 at.% Cu [1985Mur], [1998Liu]

at 580°C

at 672°C in two-phase (Cu)+ alloy

43


MSIT®

Al–Cu–Gd

2, Cu100-xAlx< 363

t**

TiAl3long period

super-lattice

a = 366.8

c = 368.0

22 x 23.5 [1985Mur]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu (subcell only)

0, Cu100-xAlx Cu~2Al

1037-800

cI52

I43m

Cu5Zn8

31.5 x 37 [Mas2],

63 to 68.5 at.% Cu [1998Liu]

1, Cu9Al4< 890

cP52

P43m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu [Mas2, 1998Liu];

from single crystal [V-C] at 68 at.% Cu

from single crystal [V-C]

, Cu100-xAlx< 686

hR*

R3m

a = 1226

c = 1511

38.1 x 40.7 [1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

1, Cu100-xAlx958-848

cubic? 37.9 x 40.6

59.4 to 62.1 at.% Cu [Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6-x

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.45 x 0.78

55 to 61 at.% Cu [Mas, 1985Mur, V-C2],

NiAs in [Mas2, 1994Mur]

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 57 at.% Cu [Mas2, 1994Mur]


2, Cu11.5Al9(r)

< 570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu [Mas2, 1985Mur]


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu

[V-C2, Mas2, 1985Mur]


2, CuAl(r)

< 560

mC20

C2/m

CuAl

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu [V-C]

, CuAl2< 592

tI12

I4/mcm

CuAl2 a = 606.7

c = 487.7

32.05 to 32.6 at.% Cu at 549°C

32.4 to 32.8 at.% Cu at 250°C [1996Goe]

single crystal [V-C2, 1989Mee]

Gd2Al

< 940

oP12

Pnma

Co2Si

a = 674.2

b = 525.4

c = 975.6

a = 661.2

b = 515.0

c = 957.8

a = 660.6

b = 514.6

c = 953.1

as cast, [2000Sac]

cooled 10 K min-1, [2000Sac]

[1988Gsc]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

44


MSIT®

Al–Cu–Gd

Gd3Al2< 970

tP20

P42/mnm

Zr3Al2

a = 832.0

c = 762.8

a = 833.9

c = 762.0


[1988Gsc]

GdAl

< 1070

oP16

Pmma

ErAl

a = 589.3

b = 1159

c = 569.5

a = 588.8

b = 1153

c = 565.6


[1988Gsc]

Gd(CuxAl1-x)2

GdAl2< 1520

cF24

Fd3m

MgCu2

a = 790.6

a = 790.0

a = 782.37

0 x 0.075 at 600°C [2001Gum]

at x = 0 cooled 10 K min-1, [2000Sac]

at x = 0 [1988Gsc]

at x = 0.25 [1994Mag]

GdAl3< 1125

hP8

P63/mmc

Ni3Sn

a = 633.1

c = 460.0

[1988Gsc]

GdCu

< 830

cP2

Pm3m

CsCl

a = 350.1 to 350.5 [1994Sub]

Gd(Cu1-xAlx)2

GdCu2

< 860

oI12

Imma

CeCu2 a = 432 to 433

b = 686 to 689

c = 733 to 738

0 x 0.06 at 600°C (from diagram

reported in [2001Gum])

x = 0 [1994Sub]

Gd2Cu7

~870-825

[1994Sub]

high temperature phase

Gd2Cu9

< 930

t** a = 500

c = 1390

[1994Sub]

GdCu5

925-~870

Gd(Cu1-x Al x)5

hP6

P6/mmm

CaCu5

a = 502 to 504

c = 412 to 410

a = 531

c = 431

at x = 0 [1994Sub]

a homogeneity range of 0 x 0.6

reported by [1988Pre, 2001Gum] and

presented in their isothermal sections at

500 and 600°C, respectively. However at

these temperatures, the CaCu5 type phase

should be metastable according to

[1994Sub]

at x = 0.6 [1988Pre]

GdCu5

< ~870

cF24

F43m

AuBe5

a = 706 [1994Sub]

GdCu6

< 865

oP28

Pnma

CeCu6

a = 803 to 804

b = 502 to 501

c =1001 to 999.5

[1994Sub]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

45


MSIT®

Al–Cu–Gd

GdCu7

~850 to ~700 (?)

hP8

P6/mmm

TbCu7

a = 495.1

c = 417.1

[1994Sub]

closely related to hP6 - CaCu5

* 1, Gd(CuxAl1-x)12

GdCu6Al6

tI26

I4/mmm

ThMn12 a = 874.8

c = 514.6

a = 875.6

c = 514.5

a = 869.1

c = 506.2

0.33 x 0.5

0.39 x 0.41 at 600°C [2001Gum]

at x = 0.33, as cast samples [1976Bus]

at x = 0.39 [2001Gum]

observed on a sample at x = 0.5 annealed at

~800°C [1980Fel]

* 2, GdCu7.8Al3.2 tI48

I41/amd

BaCd11

a = 1026.9

c = 660.54

[2001Gum]

* 3, GdCu6.6Al4.4 oF*

Fddd

Tb(Cu0.58Al0.42)11

a = 1430.3

b = 1496.2

c = 657.4

[2001Gum]

* 4, Gd2(CuxAl1-x)17

Gd2Cu9.4Al7.6

hR57

R3m

Th2Zn17 a = 883.0

c = 1283

a = 884.5

c = 1290.1

a = 896.8

c = 1298.4

a = 883.0

c = 1285.7

0.394 x 0.47 at 500°C [1988Pre]

0.394 x 0.55 at 600°C [2001Gum]

x = 0.47 [1988Pre]

x = 0.41 [1982Pre]

x = 0.394 [1988Pre]

x = 0.55 [2001Gum]

*, Gd2Cu6Al11 hP38

P63/mmc

Th2Ni17

a = 892.3

c = 901.6

[1978Pop] not shown in the isothermal

section

* 5, Gd3Cu2.1Al8.9

GdCuAl3

oI12

Immm

La3Al11 or

tI10

I4/mmm

BaAl4

a = 423.98

b = 1255.3

c = 993.93

a = 415.91

c = 1063.6

[2001Gum]

[1988Pre]

* 6, GdCu0.9Al2.1 hR36

R3m

PuNi3

a = 551.53

c = 2551.9

[2001Gum]

* 7, GdCuAl hP9

P62m

Fe2P or ZrNiAl

a = 707.77

c = 406.49

a = 705.1

c = 406.0

[1968Dwi]

[2001Gum]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

46


MSIT®

Al–Cu–Gd

20

40

60

80

20 40 60 80

20

40

60

80

Gd Cu


Axes: at.%

γ1

δ

ζ2

η2

θ

GdAl3

GdAl2

GdAl

Gd3Al2

Gd2Al

GdCu GdCu2 GdCu4GdCu5 GdCu6

Gd3Al

τ1

τ4

τ3

τ7

(Cu)

τ2

(Al)

τ5

τ6

(αGd)

20

40

60

80

20 40 60 80

20

40

60

80

Gd Cu


Axes: at.%

γ2

δ

ε2

η1

(Al)

GdAl3

GdAl2

GdCu2 GdCu5GdCu6

β

τ1

τ4

τ7

τ5

τ6

τ3

τ2

Gd2Cu9

(Cu)

L

Fig. 1: Al-Cu-Gd.

Isothermal section at

500°C

Fig. 2: Al-Cu-Gd.


600°C

47


MSIT®

Al–Cu–Mg

Aluminium – Copper – Magnesium

Günter Effenberg, Alan Prince†, updated by Nathalie Lebrun, Hans Leo Lukas, Mireille G. Harmelin

Literature Data

This system was previously evaluated by [1991Eff]. Their evaluation has been used by two groups as the

basis for thermodynamic assessments and phase diagram calculations [1993Zuo, 1996Zuo, 1997Che] and

[1998Buh, 2003Jan]. Some experiments have been performed to support these calculations [1995Hua,

1995Kim, 1995Soa, 1998Fau] and [1999Fau]. The equilibria in the Al-Cu-Mg system are complicated by

the existence of four ternary phases. There is need for experiments to clarify the ternary equilibria involving

the three Laves phases, 1-3, which have clearly been identified as three separate phases. The 1 phase with

a Cu2Mg type structure is a solution phase of the binary Cu2Mg compound with replacement of the Cu

atoms by Al along the 33.3 at.% Mg section. At a composition close to the Cu3Mg2Al formula, the 1 phase

melts congruently at ~910°C. Further replacement of Cu by Al stabilizes the 2 phase with a MgNi2 type

structure and then the 3 phase with a MgZn2 type structure. A variety of polytype structures with different

atom layer stacking sequences have been observed between the MgNi2 and MgZn2 type phases. The 2-3

phases appear to be formed by peritectic reaction and each Laves phase is associated with a region in which

it forms as the primary phase on solidification of melts. Four additional ternary compounds have also been

studied extensively. The S phase is based on the CuMgAl2 composition, V on Cu6Mg2Al5 and Q on

Cu3Mg6Al7. These three phases exist over very limited homogeneity ranges. The T phase has a broad range

of homogeneity. A formula (Cu1-xAlx)49Mg32 is derived from the crystal structure [1952Ber], but also some

mutual replacement between Mg and Cu+Al takes place.

The liquidus projection, presented by [1952Ura], does not include the monovariant curves associated with

the L + 1 2 and L + 2 3 peritectic reactions. The Laves phase 1 is the predominant primary phase,

but also the regions for primary solidification of (Al) and (Mg) are relatively large. Six pseudobinary

reactions have been identified experimentally, and the pseudobinary reaction e3 (Table 2b) has been

suggested. The invariant reactions associated with the primary (Al) phase region are well characterized by

numerous workers. The invariant reactions associated with the primary V, Q and T phase regions have been

elucidated by Russian workers, summarized by [1952Ura]. The liquidus surface across the Mg2Al3, T and

Mg17Al12 phase regions is exceptionally flat and ranges in temperature from 420 to 475°C. [1952Ura] gave

a complete reaction scheme. The thermodynamic calculations referred to above in principle reproduce this

reaction scheme, but differ in some details.

Binary Systems

Assessments of the Al-Cu system by [2003Gro], of the Al-Mg system by [2003Luk] and of the Cu-Mg

system by [2002Iva] are accepted. They are based on [1994Mur, 1998Liu] for Al-Cu, [1982Mur, 1998Lia1]

for Al-Mg and [1994Nay] for Cu-Mg. The thermodynamic data set of the COST 507 action [1998Ans,

1998Buh] was updated recently in some details [2003Jan]. It was used for the calculated figures and the

reaction scheme presented in this assessment. The homogeneity ranges of the phases Mg2Al3, and were

simplified to stoichiometric phases. 1 and 2 were treated as a single phase, . 1 and 2 were also not

distinguished and called .

Solid Phases

There are four well-defined ternary phases, designated in the literature as Q, S, T and V phases. It is quite

interesting to note that all ternary compounds in the Al-Cu-Mg system are formed at maxima of three-phase

equilibria involving the liquid phase, except the V phase, which is formed in a four-phase peritectic reaction

(P1). In addition the section at 33.3 at.% Mg contains a complex series of ternary Laves-Friauf phases that

are designated as 1, 2, 3, 5L, 6L, 9L and 16L in this assessment, Table 1. The Q phase is based on the

chemical formula Cu3Mg6Al7 [1947Str, 1951Mir1] and has a very limited homogeneity range. The S phase

48


MSIT®

Al–Cu–Mg

has been extensively studied [1936Lav1, 1937Nis1, 1938Pet1, 1938Pet2, 1940Kuz, 1941Obi, 1943Per,

1944Lit, 1946Pet, 1946Ura, 1947Str, 1949Mir]. It also has a limited homogeneity range, based on the

chemical formula CuMgAl2. Its structure was determined by [1943Per] and confirmed by [1949Mir]. The

T phase has been equally thoroughly investigated [1919Vog, 1923Gay, 1935Lav, 1937Nis1, 1940Kuz,

1943Gue, 1944Lit, 1946Pet, 1946Ura, 1948Str, 1949Ura1, 1949Ura2, 1950Phr, 1952Ber, 1966Aul,

2000Tak] and a variety of chemical formulae assigned to it. From the crystal structure determined by

[1952Ber], the formula (Cu1-x Alx)49Mg32 is adequate. It is found that very few Al atoms occupy site A,

which is the center of an isochahedral cluster being almost empty [2000Tak]. The V phase has a small

region of homogeneity centered on the Cu6Mg2Al5 formula [1936Lav1, 1936Lav2, 1937Sch, 1943Gue,

1947Str, 1948Str, 1949Sam, 1949Ura1, 1951Mir3, 1952Ura] although other chemical formulae have been

quoted in the literature. Its structure was determined by [1949Sam] with the ideal formula Cu6Mg2Al5. New

recent results using DSC and EDS/WDX techniques [2001Fau] confirmed small solubility ranges of the Q

and S phases. Moreover, the solubility domain of the V phase seems to be parallel to the Al-Cu binary edge

[2001Fau]. Addittional experiments are needed to confirm it.

The Laves-Friauf phases, although well studied, have not been integrated experimentally into the ternary

equilibria in a satisfactory manner. The 1 phase with a Cu2Mg type structure is based on the Cu2Mg binary

compound with a substitution of Al atoms for Cu to form a solid solution series. At a composition close to

Cu3Mg2Al, the 1 phase melts congruently [1936Lav1, 1952Ura]. With further replacement of Cu by Al on

the 33.3 at.% Mg section, an MgNi2 type phase is stable, 2. There is general agreement between [1953Kle,

1965Sli, 1977Kom, 1981Mel1] and [1981Mel2] on the extent of the 2 phase region. Earlier work did not

detect 2 [1934Lav, 1943Gue, 1949Ura1] or regarded it as stable at high temperature only [1936Lav1]. The

MgZn2 type structure, 3, is formed with further substitution of Cu atoms by Al. The results from the

different workers are summarized in Fig. 1. Polytype structure Laves phases with variations in the layer

stacking sequences have been studied by [1962Kom, 1977Kit, 1977Kom] and [1981Mel1]. They are

located between 1 and 2, but their ranges of stability could not exactly be separated from those of 1 and

2. [1998Che] proposed a “new intermetallic compound Mg1.75Cu1.0Al0.4” at a composition, where

[1991Eff, 2000Fau] and the calculations [1997Che, 1998Buh, 2003Jan] assume two phases, 1 and (Mg).

The characteristics of this “new phase”, however, clearly identify it as the 1 phase [2000Fau]. The presence

of (Mg) and 1 phases were confirmed by [2000Fau] who made XRD experiments on alloys having the

same composition as those reported by [1998Che]. Most probably the also present (Mg) phase was not

detected in the X-ray patterns of [1998Che] due to line broadening by cold deformation.


A number of pseudobinary systems have been reported. The calculation [2003Jan] found 13 maxima of

three-phase equilibria, but some of them are less than 1 K above an adjacent four-phase equilibrium and

must be taken as tentative only. The (Mg)- 1 section is a pseudobinary eutectic [1932Por, 1933Bas,

1934Por, 1949Ura2], e13, Table 2. The (Al)-S section contains a pseudobinary eutectic e14 [1937Nis1,

1946Ura, 1948Bro, 1952Han]. The calculated temperatures [2003Jan] of both equilibria are far below those

given by [1946Ura] and accepted by [1991Eff]. The sections Mg2Al3-T, e19, and Mg17Al12-T, e16, are also

pseudobinary eutectic sections at Cu contents below the beginning of the primary Q phase region.

[1943Gue, 1949Ura1, 1949Ura2, 1951Mir2] and [2003Jan] are in agreement on the nature of these two

sections, Table 2. The investigation [1951Mir2] of the region of primary solidification of Q led to the

conclusion that the T phase is formed by peritectic reaction with Q at p13, Fig. 2. A pseudobinary reaction

was indicated by [1946Ura] who found a maximum on the curve U8U11 corresponding with the peritectic

formation of S by reaction of liquid with a Laves phase. [1949Ura1, 1949Ura2] and [1952Ura] refer to the

cubic Cu2Mg type phase 1 or to a composition CuMgAl. They take no account of the 2 and 3 Laves

phases. The calculation of [2003Jan] gives 2 as the Laves phase participating in this reaction, p10, which

is also favoured by [1991Eff]. [1938Pet1] regarded the CuAl2-S section as a pseudobinary, but later work

has disproved this assumption.

49


MSIT®

Al–Cu–Mg


Table 2 lists the invariant reactions following from the thermodynamic calculation of [2003Jan] for the

Al-Cu-Mg ternary system and may be read in conjunction with Fig. 2. The reaction scheme, following from

this calculation is given in Fig. 3. In this calculation, 1 and 2 as well as 1 and 2 were considered as single

phases and called and , respectively. The ternary eutectic reaction E5 has been widely studied, Table 3.

The flat nature of the liquidus surface near to E7 has led to a considerable scatter in quoted compositions

and temperatures, Table 4. The reaction has normally been quoted as a ternary eutectic reaction and this is

accepted. The transition reaction U16 has also been widely studied, Table 5. The work of [1946Ura,

1949Ura2] and [1948Bro] rests on an examination of a greater number of alloys than other work and

allowed a more precise determination of the liquid composition at U16. Ternary eutectic reactions in

Mg-rich alloys occur at E6 and E9. The reaction temperature at E6 is 1°C [1932Por, 1933Bas, 1934Por] or

2°C [1949Ura2] below the binary Cu-Mg eutectic temperature. The ternary eutectic E9, Table 6, was

initially regarded as involving a Laves phase, but the work of [1951Mir2] indicates that this eutectic

involves the Q phase, which was not detected by the previous workers. Faudot et al. [1998Fau, 1999Fau]

confirmed the eutectic, Table 6. The ternary eutectic reaction at E9 was found by [1949Ura2] at 423°C, what

agrees well with that calculated by [2003Jan], 424°C. The reaction at U13 was regarded as a transition

reaction by [1937Nis1, 1952Han], as calculated by [2003Jan], whereas [1946Ura] and [1949Ura2]

considered it to be a ternary peritectic reaction, L+ 1+S T. [1951Mir2] gives it as L+ 1+S Q. There is

doubt about this reaction on two counts. The Q phase lies virtually on the L- 1 tie line [1952Ura] and it is

unlikely that the Laves phase is 1. For the reactions U15 and U18 [2003Jan] reproduced those given by

[1951Mir2] with 3°C deviation. For U18 Faudot et al. [1998Fau] gave 427°C as calculated by [1998Buh,

2003Jan]. But later [1999Fau] found it at 451°C with a more Al-rich liquid, Table 6. The transition reaction

at U17 was given by [1951Mir2] as L+ 1 (Mg)+Q, but the work of [1981Mel2] indicates 3 as the reactant

rather than 1, whereas [1998Fau, 1999Fau, 2003Jan] assume 2. The reactions in the Cu-rich corner have

been little studied. In Table 2 are given those calculated by [2003Jan]. [1949Ura2] assumed an eutectic

instead of U2 and a transition reaction instead of E4. The temperatures of the invariant equilibrium in this

area calculated by the two groups [1997Che] and [1998Buh, 2003Jan] deviate up to 20°C. The regions of

primary solidification of the Laves phases 1, 2 and 3 have not been experimentally defined, but the

calculation [2003Jan] gives them as shown in Fig. 2. [1997Che] did not distinguish these Laves phases.

Liquidus Surface

A liquidus projection, Fig. 2b, is taken from the calculation of [2003Jan] with some minor modifications on

the edges according to the binary systems accepted in this assessment. It should be compared with the

projection, Figs. 2 and 2a, deduced also from the calculations of [2003Jan]. The liquidus in the ternary

diagram was also calculated by [2001Che, 2002Che] using the multicomponent phase diagram calculation

software PANDAT. [1999Xie] also studied the liquidus projection in the Al rich corner. Results are in

agreemnt with those calculated by [2003Jan]. According to the liquidus of the binary systems accepted in

this assessment, the liquidus projection was modified at the edge boundaries. The liquidus isotherms

reproduce fairly well those assessed by [1991Eff]. The primary (Al) region has been widely studied with

general agreement on the form of the liquidus. The isotherms for the region of primary solidification of the

series of Cu-rich Al-Cu phases are uncertain.

Isothermal Sections

The calculated 400°C isothermal section calculated by [2003Jan], Fig. 4, agrees with Fig. 4 of [1991Eff]

except the broadening of the homogeneity range of 1 near 25 at.% Al, which in calculation needs to model

an anomaly in the Gibbs energy description at that composition, but there is no other evidence for an

anomaly. The phase Mg2Al3 is simplified as a stoichiometric phase as well as the CuMg2, , and phases.

The solubility of Cu and Mg in Al-rich alloys at 460°C was determined by [1944Lit] and [1947Str], Fig. 5.

[1944Lit] also produced data for 375°C. The results of [1932Dix] agree with the solubilities given in Fig. 5.

[1946Pet] found lower Mg solubilities but used fewer alloys. [1955Zam] published solubility curves with a

50


MSIT®

Al–Cu–Mg

series of cusps that cannot be reconciled with the alloy constitution. The solubilities of Mg and Cu in (Al)

reported in the accepted binary systems have also been taken into account in Fig. 5. The calculated solvus

isotherms of [1986Cha] and [2003Jan], Fig. 6, are in good agreement with [1944Lit] and [1947Str].

[1957Rog] reported the solubility of Al and Mg in (Cu), Fig. 7. No comparable work has appeared. In this

area the calculation is less reliable, as it cannot be based on adjacent experimental data. More extensive

isothermal sections were determined by [1946Pet] at 400°C in the region from Al to S and T. [1949Mir]

reported on the S phase region at 420°C, [1949Ura1] on the T and 1 phase region at 400°C, [1951Mir1]

on the Q phase region at 400°C, [1952Ura] on an almost complete isothermal section at 400°C and

[1981Mel2] on the region from 33.3 to 100 at.% Mg at 400°C. [1944Lit] and [1947Str] studied the 460°C

isothermal section from Al to the , S, Q and T phases.


The liquidus and solidus of the Al rich alloys along the isopleth Al-Cu0.5Mg0.5 were calculated by

[1997Che, 1999Xie, 2000Lia] using thermodynamic descriptions. The measured solidus data found by

[1988Mur] was found to be 0.5 at.% higher than the model-calculated values, while the measured liquidus

is in good agreement with the model-calculation. The inaccuracy for the solidus is explained by

microsegregations occuring in ternary Al-Cu-Mg alloys [1999Xie].

Several isopleths were calculated by [1997Che, 2003Jan] from thermodynamic descriptions. Figs. 8 and 9a,

9b, 9c show isopleth sections at 33.3 at.% Mg and x mass% Al (x =60, 70 and 95.5) respectively. The

calculated isopleth, taken from [2003Jan] and reported on Fig. 8, is in agreement with the experimental data

reported by [1936Lav1] and [1953Kle]. The calculated isopleths reported on Figs. 9a, 9b and 9c are taken

from [1998Buh] and describe quite well the experimental information reported by [1937Nis1, 1937Nis2,

1952Han] and [1946Ura]. The calculated isopleths at 37 at.% Al (Fig. 10a) and 43.75 at.% Al (Fig. 10b)

show the 2 and the Q phases formations respectively [2003Jan].

Thermodynamics

[1972Pre] studied the enthalpy of formation of alloys on the 33.3 at.% Mg section. Substitution of Cu by Al

increases the stability of the 1 phase although there is a decrease of stability at a valency electron

concentration of 1.5 (76.9Cu, 17.3Mg). [1987Hoc] calculated the enthalpy of a ternary alloy containing

33.3% “MgAl2”; agreement with [1972Pre] is fair. [1985Kuz] applied a thermodynamic model to predict

the ternary solidus from the ternary liquidus and the binary solidus-liquidus for Al-rich alloys. [1973Dav]

used quasi-chemical regular solution theory to calculate the monovariant curve e2E5 of Fig. 2a. With the

introduction of a ternary interaction parameter the calculated ternary eutectic point E5, Table 3, shows

reasonable agreement with the assessed composition. [1987Lac] calculated the Al-rich region of the phase

diagram using an extended Redlich-Kister formalism. Excellent agreement was obtained with the assessed

liquidus, Fig. 2b. [1985Far] calculated the composition of the ternary eutectic E5, Fig. 2a and Table 2,

assuming both ideal solution behaviour and regular solution behaviour. The calculated eutectic

compositions, 34.4Cu-8.8Mg (mass%) for ideal solutions and 30.3Cu-7.5Mg (mass%) for regular solutions,

approximate to the assessed values. The calculated eutectic temperatures are surprisingly low at 273°C and

271°C, respectively. Recently two groups [1997Che] and [1998Buh, 2003Jan] calculated the whole ternary

system, describing the Gibbs energies of all phases involved by the compound energy formalism. Both

calculations show very similar results, only in the Cu-rich part there is some disagreement of the invariant

temperatures (up to 20°C). The first group also calculated solidification paths using the model of Scheil

[1993Zuo, 1996Zuo].

[1986Che] measured the enthalpy of fusion of the ternary eutectic E5 as 365 J g-1 corresponding to 11.8

kJ mol-1 of atoms. [1986Not] measured the enthalpy of formation of the S phase as -63.2 ± 4.0 kJ mol-1 of

CuMgAl2. [1995Kim] measured the enthalpy of mixing of ternary liquids by a high temperature calorimeter

at 713°C along three lines with constant Al/Mg ratios up to 40 at.% Cu and along Al/Cu = 13/7 up to 27

at.% Mg. [1995Soa] measured the chemical potential of Mg in ternary melts by an isopiestic method.

51


MSIT®

Al–Cu–Mg


The mechanical properties such as tensile strengh were investigated by [2002Dav] on

0.02Zn-0.05Ti-0.42Mn-0.27Fe-4.5Cu-1.5Mg-Al-0.17Si alloys.

[2002Zhu] reported that a small addition of Ag (< 0.1 at.%) to an Al-Cu-Mg alloy with a high content of Al

promote an increasing strength and creep resistance when compared to Al-Cu-Mg alloys that contain only

the CuAl2 precipitate.

Miscellaneous

[1940Kuz] and [1946Kuz] measured lattice spacings of the (Al) phase along sections from Al with various

Cu:Mg ratios. [1951Poo] measured the lattice spacings of the (Al) phase along sections from 99 at.% Al, 1

at.% Mg to 99.5 at.% Al, 0.5 at.% Cu and from 98 at.% Al, 2 at.% Mg to 99 at.% Al, 1 at.% Cu, Table 7.

A small addition of Mg to Al-Cu alloys accelerates the formation of Guinier-Preston (GP) zones through

the Mg/Cu/vacancy complexes mechanism [2000Hir, 2002Hir].

The crystal structure of a metastable variant of S on aging Al alloys was studied by [1950Bag]. Aging

studies of single crystals of an alloy containing 1.2 at.% Cu, 1.2 at.% Mg [1978Ale] showed S particles to

be coherent with the Al matrix. The effect of aging on mechanical properties of Al-rich alloys have been

reported by [1939Han, 1941Mec] and [1948Sha]. More recent studies on metastable precipitates in (Al) are

from [1990Gar] and [1991Jin].

[1959Pal] prepared thin film Al-rich ternary alloys by evaporation on to Al substrates. The constitution is

claimed to correspond with bulk samples. There is a growing literature on the formation of a

non-equilibrium icosahedral quasicrystalline phase by rapid solidification of alloys in the T phase region.

[1986Cas] tentatively outlined the phase region that produces quasicrystals on rapid solidification as

containing 10 to 13.5 at.% Cu, 35 to 37 at.% Mg. This composition range is on the low Mg side of the

equilibrium T phase region. Annealing a rapidly solidified alloy with 1 at.% Cu, 5 at.% Mg for 100 h at

190°C gave both the icosahedral phase and the equilibrium T phase at the grain boundaries of the Al matrix.

For anneals of 24 h at 250°C only the T phase was observed at the grain boundary [1986Cas, 1987Cas] with

precipitation of the S phase in the Al matrix. [1987San1] and [1987San2] rapidly solidified an alloy

corresponding to CuMg4Al6. This composition lies in the T phase region. DSC measurements gave a

melting point of 474.9°C which is in good agreement with the assessed temperature of the pseudobinary

reaction p6, L+Q T, Fig. 3. A polymorphic transformation of the T phase, reported at 356.5°C, has not been

noted by other workers. [1988She] rapidly solidified an alloy containing 12.5Cu-36.5Mg-51Al (at.%) and

found it to be a single phase icosahedral quasicrystal. This composition is within the phase region given by

[1986Cas]. A wider, but less exact, delineation of the icosahedral quasicrystal phase region was given by

[1988Shi]. They quote the composition as typically CuMg4Al5, as proposed by [1937Nis1] for the stable T

phase. [1988San] rapidly solidified the composition CuMg4Al6 and carried out a detailed X-ray study of the

quasicrystalline phase and its transformation to the crystalline T phase by annealing for 1 h at 340°C.

[1989She] used high resolution X-ray diffraction to study atomic distribution in quasicrystalline phases as

well as differential scanning calorimetry (DSC) to get thermodynamic properties. [1991Wit] prepared and

studied an icosahedral alloy with composition Cu12.5Mg36.5Al51 by electrical resistivity measurements and

DSC.

References

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[1923Gay] Gayler, M.L.V., “The Constitution and Age-Hardening of the Ternary Alloys of Al with Mg

and Cu”, J. Inst. Met., 29, 507-528 (1923) (Equi. Diagram, Experimental, 8)



[1932Dix] Dix, E.H., Sager, G.F., Sager, B.P., “Equilibrium Relations in Al-Cu-Mg and Al-Cu-Mg2Si

of High Purity”, Trans. AIME, 99, 119-131 (1932) (Equi. Diagram, Experimental, 8)

52


MSIT®

Al–Cu–Mg

[1932Por] Portevin, A., Bastien, P., “Contribution to the Study of the Mg-Al-Cu Ternary System” (in

French), Compt. Rend., 195, 441-443 (1932) (Equi. Diagram, Experimental, 6)

[1933Bas] Bastien, P., “Study of the Ultra-Light Alloys of Mg-Al-Cu” (in French), Rev. Met., 6,


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[1936Lav2] Laves, F., Werner, S., “The Crystal Structure of Mg2Zn11 and its Isomorphy with

Mg3Cu7Al10” (in German), Z. Kristallogr., 95, 114-128 (1936) (Crys. Structure, Equi.


[1937Nis1] Nishimura, H., “The Al Corner of the Al-Cu-Mg System” (in Japanese), Nippon Kinzoku

Gakkai-Shi, 1, 8-18 (1937) (Equi. Diagram, Experimental, 8)

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(in Russian), Metallurgia, 3, 88-91 (1938) (Experimental, 4)

[1938Pet2] Petrov, D.A., “On the Problem of the Age-Hardening of Duralumin”, J. Inst. Met., 62,

81-100 (1938) (Experimental, 31)

[1939Han] Hansen, M., Dreyer, K.L., “The Influence of the Cu and Mg Contents on the Age-Hardening

of Al-Cu-Mg Alloys” (in German), Z. Metallkd., 31, 204-209 (1939) (Experimental, 6)

[1940Han] Hanemann, H., “A Note on the System Al-Cu-Mg” (in German), Z. Metallkd., 32, 114


[1940Kuz] Kuznetsov, V.G., Guseva, L.N., “X-Ray Investigation of Al-rich Al-Mg-Cu Alloys” (in

Russian), Izv. Akad. Nauk SSSR, Ser. Khim., 6, 905-928 (1940) (Crys. Structure, Equi.


[1941Mec] Mechel, R., “Contribution to the Metallography of Precipitated CuAl2 Phase in Commercial

Al-Cu-Mg Alloys” (in German), Luftfahrtforschung, 18, 107-110 (1941) (Experimental, 7)

[1941Obi] Obinata, I., Mutuzaki, K., “On the Composition and Crystal Structure of the “S” Compound,

the Main Hardening Element of Duralumin” (in Japanese), Nippon Kinzoku Gakkai-Shi, 5,


[1943Gue] Guertler, W., Rassmann, G., “The Application of the X-Ray Fine Structure Diagram for the

Recognition of the Phase Equilibria of Ternary Systems in the Crystalline State” (in

German), Metallwirtschaft, 22, 34-42 (1943) (Crys. Structure, Equi. Diagram,

Experimental, 30)

[1943Per] Perlitz, H., Westgren, A., “The Crystal Structure of Al2CuMg”, Arkiv Kemi, Mineral. Geol.,

B16, 13, 1-5 (1943) (Crys. Structure, Experimental, 4)

[1944Lit] Little, A.T., Hume-Rothery, W., Raynor, G.V., “The Constitution of Al-Cu-Mg Alloys at

460°C”, J. Inst. Met., 70, 491-506 (1944) (Equi. Diagram, Experimental, 7)

[1946Kuz] Kuznetsov, V.G., “X-Ray Investigation of Al-Base Ternary Alloys” (in Russian), Izv. Sekt.

Fiz.-Khim. Anal., 16, 232-250 (1946) (Equi. Diagram, Crys. Structure, Experimental, 29)

53


MSIT®

Al–Cu–Mg

[1946Pet] Petrov, D.A., Berg, G.S., “Investigation of the Region of Solid Solution of Cu and Mg in

Al” (in Russian), Zh. Fiz. Khim., 20, 1475-1488 (1946) (Crys. Structure, Equi. Diagram,

Experimental, 21)

[1946Ura] Urazov, G.G., Petrov, D.A., “Investigation of the Al-Cu-Mg Phase Diagram” (in Russian),

Zh. Fiz. Khim., 20, 387-398 (1946) (Equi. Diagram, Experimental, 10)

[1947Str] Strawbridge, D.J., Hume-Rothery, W., Little, A.T., “The Constitution of Al-Cu-Mg-Zn

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Experimental, 11)

[1948Bro] Brommelle, N.S., Phillips, H.W.L., “The Constitution of Al-Cu-Mg Alloys”, J. Inst. Met.,

75, 529-558 (1948-49) (Equi. Diagram, Experimental, 39)

[1948Sha] Sharma, A.S., “The Metallography of Commercial Alloys of the Duralumin Type”, Trans.

Indian Inst. Met., 1, 11-44 (1948) (Experimental, 11)

[1948Str] Strawbridge, D.J., “Correspondence on the Paper by N.S. Brommelle and H.W.L. Phillips,

The Constitution of Al-Cu-Mg Alloys”, J. Inst. Met., 75, 1116-1119 (1948-49) (Review, 4)

[1949Mir] Mirgalovskaya, M.S., Makarov, E.S., “The Crystal Structure and Properties of the S Phase

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[1949Sam] Samson, S., “The Crystal Structure of Mg2Cu6Al5” (in German), Acta Chem. Scand., 3,


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System” (in Russian), Izv. Sekt. Fiz.-Khim. Anal., 19, 522-530 (1949) (Equi. Diagram,

Experimental, 19)

[1950Bag] Bagaryatsky, Yu.A., “Structural Changes on Aging Al-Cu-Mg Alloys” (in Russian),

Zh. Tekhn. Fiz., 20, 424-427 (1950) (Crys. Structure, Experimental, 7)

[1950Phr] Phragmen, G., “On the Phases Occurring in Alloys of Al with Cu, Mg, Mn, Fe and Si”,

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[1951Mir3] Mirgalovskaya, M.S., “On Similar Crystallochemical Characteristics in the Mg-Zn and

Mg-Al-Cu Systems” (in Russian), Dokl. Akad. Nauk SSSR, 78, 909-911 (1951) (Crys.

Structure, Experimental, Theory, 7)

[1951Poo] Poote, O.M., Axon, H.J., “Lattice-Spacing Relationships in Al-rich Solid Solutions of the

Al-Mg and Al-Mg-Cu Systems”, J. Inst. Met., 80, 599-604 (1951) (Crys. Structure,

Experimental, 11)

[1952Ber] Bergman, G., Waugh, J.L.T., Pauling, L., “Crystal Structure of the Intermetallic Compound

Mg32(Al,Zn)49 and Related Phases”, Nature, 169, 1057-1058 (1952) (Crys. Structure,

Experimental, 4)

[1952Han] Hanemann, H., Schrader, A., “Ternary Alloys of Al”, in “Atlas Metallographicus”, (in

German), Verlag Stahleisen M.R.H. Dsseldorf, 3(2), 73-81 (1952) (Equi. Diagram,

Experimental, Review, 9)

[1952Ura] Urazov, G.G., Mirgalovskaya, M.S., “The Al-Cu-Mg System” (in Russian), Dokl. Akad.

Nauk SSSR, 83, 247-250 (1952) (Equi. Diagram, Experimental, 8)

[1953Kle] Klee, H., Witte, H., “Magnetic Susceptibilities of Ternary Mg Alloys and their Significance

from the Standpoint of the Electron Theory of Metals” (in German), Z. Phys. Chem.

(Leipzig), 202, 352-378 (1953) (Experimental, 32)

54


MSIT®

Al–Cu–Mg

[1955Zam] Zamotorin, M.I., “Solubility of Cu and Mg in the Solid State in Al at Various Temperatures”

(in Russian), Tr. Leningrad. Polytekhn. Inst., 180, 32-37 (1955) (Equi. Diagram,

Experimental, 12)

[1957Rog] Rogel'berg, I.L., “Solubility of Mg in Cu and Combined Solubility of Mg and Al in Cu” (in

Russian), Tr. Gosud. N.-I. Pr. Inst. Obrab. Tsvetn. Met., 16, 82-89 (1957) (Equi. Diagram,

Experimental, 12)

[1959Pal] Palatnik, L.S., Fedorov, G.V., Gladkikh, N.T., “Study of Al Alloys of the Al-Cu-Mg System

in Samples of Variable Compositions” (in Russian), Fiz. Met. Metalloved., 8, 378-386


[1962Kom] Komura, Y., “Stacking Faults and Two New Modifications of the Laves phase in the

Mg-Cu-Al System”, Acta Crystallogr., 15, 770-778 (1962) (Crys. Structure, Experimental,

15)

[1965Sam] Samson, S., “The Crystal Structure of the Phase Mg2Al3”, Acta Crystallogr. 19, 401-413

(1965) (Experimental, Crys. Structure, 16)

[1965Sli] Slick, P.I., Massena, C.W., Craig, R.S., “Electronic Specific Heats of Alloys of the

MgCu2-xAlx System”, J. Chem. Phys., 43, 2788-2794 (1965) (Experimental, 13)

[1966Aul] Auld, J.H., Willians, B.E., “X-Ray Powder Data of T Phases Composed of Al and Mg with

Ag, Cu or Zn”, Acta Crystallogr., 21, 830-831 (1966) (Crys. Structure, Experimental, 4)

[1967Coo] Cooksey, D.J.S., A. Hellawell, A., “The Microstructures of Ternary Eutectic Alloys in the

Systems Cu-Sn-(Pb, In, Tl), Al-Cu-(Mg, Zn, Ag) and Zn-Sn-Pb”, J. Inst. Met., 95, 183-187


[1968Sam] Samson, S., Gordon, E.K., “The Crystal Structure of Mg23Al30”, Acta Crystallogr., B B24,

1004-1013 (1968) (Experimental, Crys. Structure, 32)

[1972Gar] Garmong, G., Rhodes, C.G., “Structure and Mechanical Properties of the Directionally

Solidified Al-Cu-Mg Eutectic”, Metall. Trans., 3, 533-544 (1972) (Experimental, 26)

[1972Pre] Predel, B., Ruge, H., “Investigation of Enthalpies of Formation in the Mg-Cu-Zn,

Mg-Cu-Al and Mg-Cu-Sn Systems as a Contribution to the Clarification of the Bonding

Relationships in Laves Phases” (in German), Mater. Sci. Eng., 9, 141-150 (1972)

(Thermodyn., Experimental, 61)

[1973Dav] Davison, J.E., Rice, D.A., “Application of Computer Generated Phase Diagrams to

Composite Synthesis”, in “In-Situ Composites. III-Physical Properties”, 33-60 (1973)

(Equi. Diagram, Thermodyn., Experimental, 10)

[1976Mon] Mondolfo, L.F., Aluminium Alloys: Structure and Properties, Butter Worths,

London-Boston, 497-505 (1976) (Equi. Diagram, Review, 70)

[1977Kit] Kitano, Y., Komura, Y., Kajiwara, H., “Electron-Microscope Observations of Friauf-Laves

Phase Mg(Cu1-xAlx)2 with x = 0.465”, Trans. Japan Inst. Met., 18, 39-45 (1977) (Crys.


[1977Kom] Komura, Y., Kitano, Y., “Long-Period Stacking Variants and their Electron-Concentration

Dependence in the Mg-Base Friauf-Laves Phases”, Acta Crystallogr., 33B, 2496-2501


[1978Ale] Alekseev, A.A., Ber, L.B., Klimovich, L.G., Korohov, O.S., “The Structure of the Zones in

an Al-Cu-Mg Alloy” (in Russian), Fiz. Metall. Metalloved., 46, 548-556 (1978) (Crys.


[1980Bir] Birchenall, B.E., Riechman, A.F., “Heat Storage in Eutectic Alloys”, Metall. Trans.A, 11A,

1415-1420 (1980) (Experimental, 13)

[1981Mel1] Mel'nik E.V., Kinzhibalo, V.V., “Compounds with Laves Phase Structures in the Systems

Mg-Al-Cu, Mg-Ga-Cu and Mg-Ga-Ni” (in Russian), Vestn. L'vov. Univ. Khim., 23, 40-43


[1981Mel2] Mel'nik, E.V., Kinzhibalo, V.V., “Investigation of the Mg-Al-Cu and Mg-Ga-Cu Systems

from 33.3 to 100 at.% Mg”, Russ. Metall., 3, 154-158 (1981), translated from Izv. Akad.

Nauk SSSR, Met., 3, 154-158 (1981) (Crys. Structure, Equi. Diagram, Experimental, 5)

55


MSIT®

Al–Cu–Mg

[1982Mur] Murray, J.L., “The Al-Mg (Aluminum-Magnesium) System”, Bull. Alloy Phase Diagrams,

3, 60-74 (1982) (Equi. Diagram, Review, 132)

[1985Kuz] Kuznetsov, G.M., Konovalov, Yu.V., “Prediction of the Solidus Surface of the Al-Cu-Mg

System from Data on the Liquidus Surface” (in Russian), Izv. V.U.Z., Tsvetn. Metall., 6,

72-76 (1985) (Theory, 15)

[1985Far] Farkas, D., Birchenall, C.E., “New Eutectic Alloys and Their Heats of Transformation”,

Metall. Trans. A, 16A, 323-328 (1985) (Thermodyn., 18)

[1985Mur] Murray, J.L., “The Al-Cu System”, Int. Met. Rev., 30 (5), 211-233 (1985) (Equi. Diagram,

Review, 230)

[1986Cas] Cassada, W.A., Shen, Y., Poon, S.J., Shiflet, G.J., “Mg32(Zn,Al)49-Type Icosahedral

Quasicrystals Formed by Solid-State Reaction and Rapid Solidification”, Phys. Rev. B,

Condens. Matter, 34, 7413-7416 (1986) (Crys. Structure, Experimental, 17)

[1986Cha] Chakrabarti, D.J., “Interactive Computer Graphics of Phase Diagrams in Al-Based Systems,

Computer Modelling of Phase Diagrams”, Proc. Symp. Met. Soc. A.I.M.E., Bennett, L.H.

(Ed.), 399-416 (1985) (Equi. Diagram, Theory, 6)

[1986Che] Cherneeva, L.I., Rodionova, E.K., Martynova, N.M., “Determination of the Energy

Capacity of Metallic Alloys as Promising Heat-Storage Materials” (in Russian), Izv.

Vyss.Uchebn.Zaved. Energia, (12), 78-82 (1986) (Thermodyn., Experimental, 7)

[1986Not] Notin, M., Dirand, M., Bouaziz, D., Hertz, J., “Determination of the Partial Molar Enthalpy

at Infinite Dilution of Liquid Mg and Solid Cu in Pure Liquid Al and of the Enthalpy of

Formation of the S-Phase (Al2CuMg)” (in French), Compt. Rend. Acad. Sci., Paris, Ser. II,

302, 63-66 (1986) (Thermodyn., Experimental, 3)

[1987Cas] Cassada, W.A., Shiflet, G.J., Poon, S.J., “Quasicrystalline Grain Boundary Precipitates in

Al Alloys Through Solid-Solid Transformations”, J. Microsc., 146, 323-335 (1987) (Crys.


[1987Hoc] Hoch, M., “Application of the Hoch-Arpshofen Model to the Thermodynamics of the

Cu-Ni-Sn, Cu-Fe-Ni, Cu-Mg-Al and Cu-Mg-Zn Systems”, Calphad, 11, 237-246 (1987)

(Thermodyn., 16)

[1987Lac] Lacaze, J., Lesoult, G., Relave, O., Ansara, I., Riquet, J.-P., “Thermodynamics and

Solidification of Al-Cu-Mg-Si Alloys”, Z. Metallkd., 78, 141-150 (1987) (Equi. Diagram,

Thermodyn., 10)

[1987San1] Sanyal, M.K., Sahni V.C., Dey, G.K., “Evidence for Endothermic Quasicrystalline -

Crystalline Phase Transitions in Al6CuMg4”, Nature, 328, 704-706 (1987) (Crys. Structure,

Experimental, 10)

[1987San2] Sanyal, M.K., Sahni, V.C., Dey, G.K., “Endothermic Quasicrystalline Phase Transition in

Al6CuMg4”, Pramna - J. Phys., 28, L709-712 (1987) (Crys. Structure, Experimental, 7)

[1988Mur] Murray, J.L., Private Communication, Alcoa Laboratory, Aluminium Co. of America,

Alcoa, PA (1988)

[1988San] Sanyal, M.K., Sahni, V.C., Chidambaram, R., “X-Ray Structural Study of Crystalline and

Quasicrystalline Al6CuMg4”, Solid State Commun., 66, 1043-1045 (1988) (Crys. Structure,

Experimental, 19)

[1988She] Shen, Y., Dmowski, W., Egami, T., Poon, S.J., Shiflet, G.J., “Structure of Al-(Li,Mg)-Cu

Icosahedral Alloys Studied by Pulsed Neutron Scattering”, Phys. Rev. B, Condens. Matter,


[1988Shi] Shibuya, T., Kimura, K., Takeuchi, S., “Compositional Regions of Single Icosahedral Phase

in Ternary Nontransition Metal Systems”, Japan. J. Appl. Phys., 27, 1577-1579 (1988)


[1989Mee] Meetsma, A., De Boer, J.L.,Van Smaalen, S., “Refinement of the Crystal Structure of

Tetragonal Aluminum-Copper (Al2Cu)”, J. Solid State Chem., 83(2), 370-372 (1989) (Crys.


[1989She] Shen, Y., “The Formation and Structure of Al-Cu-(Li,Mg) Icosahedral Alloys”, Thesis,

University of Virginia, (1989) (Crys. Structure, Experimental)

56


MSIT®

Al–Cu–Mg

[1990Gar] Garg, A., Chang, Y.C., Howe, J.M., ”Precipitation of the Omega Phase in an

Al-4.0Cu-0.5Mg Alloy”, Scr. Metall. Mater., 24, 677-680 (1990) (Crys. Structure,

Experimental, 12)

[1991Eff] Effenberg, G., Prince, A., “Aluminium-Copper-Magnesium”, MSIT Ternary Evaluation





Enthalpy of Aluminium in some Phases with Cu and Cu3Au Structures”, J. Less-Common

Met., 170, 171-184 (1991) (Experimental, Crys. Structure, 57)

[1991Jin] Jin, Y., Li, C., Yan, M., “A Precipitate Phase in AA2124”, J. Mater. Sci., 26, 3244-3248


[1991Wit] Wittmann, R., Löbl, P., Lüscher, E., Fritsch, G., Wollgarten, M., Urban, K., “Electrical

Resistivity and Crystallization Behaviour of Icosahedral Al51Cu12.5Mg36.5”, Z. Phys. B -

Condens. Matter., 83, 193-198 (1991) (Crys. Structure, Experimental, 30)

[1993Gin] Gingl, F., Selvam, P., Yvon, K., “Structure Refinement of Mg2Cu and a Composition of the

Mg2Cu, Mg2Ni and Al2Cu Structure Types”, Acta Crystallogr., Sect. B: Struct. Crystallogr.

Crys. Chem., B49, 201-203 (1993) (Crys. Structure, Experimental, *, 15)

[1993Zuo] Zuo, Y., Chang ,Y.A., “Calculation of Phase Diagram and Solidification Paths of Al-rich

Al-Mg-Cu Ternary Alloys”, Light Met.(Warrendale Pa), 935-942 (1993) (Equi. Diagram,

Thermodyn., Assessment, 29)


Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E., (Eds.), ASM International,

Materials Park, OH, 18-42 (1994) (Equi. Diagram, Crys. Structure, Thermodyn., Review, #,

*, 226); similar to [1985Mur]

[1994Nay] Nayeb-Nashemi, A.A., Clark J.B., “Cu-Mg (Copper-Magnesium)” in “Phase Diagrams of

Binary Copper Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E., (Eds.), ASM

International, Materials Park, OH, 245-252 (1994) (Equi. Diagram, Crys. Structure,

Thermodyn., Review, #, 44)

[1995Hua] Huang, C., Chen, S., “Phase Equilibria of Al-rich Al-Cu-Mg Alloys”, Metall. Mater. Trans.

A, 26A, 1007-1011 (1995) (Equi. Diagram, Experimental, 18)

[1995Kim] Kim, Y.B., Sommer, F., Predel, B., “Determination of the Enthalpy of Mixing of Liquid

Aluminum-Copper-Magnesium Alloys”, Z. Metallkd., 86, 597-602 (1995) (Thermodyn.,

Experimental, 15)

[1995Soa] Soares, D., Malheiros, L.F., Hämäläinen, M., Castro, F., “Isopiestic Determination of the

Coefficients of Activity of Magnesium in Al-Cu-Mg Liquid Alloys”, J. Alloys Comp., 220,

179-181 (1995) (Thermodyn. Experimental, 3)

[1996Zuo] Zuo, Y., Chang, Y.A., “Calculation of Phase Diagram and Solidification Paths of Ternary

Alloys: Al-Mg-Cu”, Mater. Sci. Forum, 215-216, 141-148 (1996) (Equi. Diagram,

Thermodyn, Assessment, 32)

[1997Che] Chen, S., Zuo, Y., Liang, H., Chang, Y.A., “A. Thermodynamic Description for the Ternary

Al-Cu-Mg System”, Metall. Mater. Trans. A, 28A, 435-446 (1997) (Equi. Diagram,


[1998Ans] Ansara, I., Dinsdale, A.T., Rand, M.H., COST 507, Thermochemical Database for Light

Metal Alloys, Vol. 2, European Communities, Luxembourg, 311-315 (1998) (Equi.

Diagram, Thermodyn., Calculation)

[1998Buh] Buhler, T., Fries, S.G., Spencer, P.J., Lukas, H.L., “A Thermodynamic Assessment of the

Al-Cu-Mg Ternary System”, J. Phase Equilib., 19, 317-333 (1998) (Equi. Diagram,


[1998Che] Chen, Y., “A New Intermetallic Compound Mg1.75Cu1.0Al0.4”, J. Mater. Sci. Lett., 17,


57


MSIT®

Al–Cu–Mg

[1998Don] Donnadieu, P., Harmelin, M.G., Seifert, H.J., Aldinger, F., “Commensurately Modulated

Stable States Related to the Phase in Mg-Al Alloys”, Philos. Mag. A, 78(4), 893-905


[1998Fau] Faudot, F., P. Ochin, M.G., Harmelin, S.G., Fries, T., Jantzen, Spencer, P.J., Liang, P.,

Seifert, H.J., “Experimental Investigation of Ternary Invariant Reactions Predicted by

Thermodynamic Calculations for the Al-Cu-Mg System”, Proceedings of the JEEP’98,

173-176, Nancy 1998 (Equi. Diagram, Experimental, 14)

[1998Lia1] Liang, P., Su, H.L., Donnadieu, P., Harmelin, M.G., Quivy, A., Effenberg, G., Seifert, H.J.,

Lukas, H.L., Aldinger, F., “Experimental Investigation and Thermodynamic Calculation of

the Central Part of the Mg-Al Phase Diagram”, Z. Metallkd., 98, 536-540 (1998) (Equi.


[1998Lia2] Liang, P., Tarfa, T., Robinson, J.A., Wagner, S., Ochin, P., Harmelin, M.G., Seifert, H.J.,

Lukas, H.L., Aldinger, F., “Experimental Investigation and Thermodynamic Calculation of

the Al-Mg-Zn System”, Thermochim. Acta, 314, 87-110 (1998) (Experimental, Calculation,

Thermodyn., Equi. Diagram, 69)


the Cu-Al Binary System”, J. Alloys Compd., 264, 201-208 (1998) (Equi. Diagram,


[1999Fau] Faudot, F., Harmelin, M.G., Fries, S.G., Jantzen, T., Liang, P., Seifert, H.J., Aldinger, F.,

“DSC Investigation of Invariant Equilibria in the Mg-Rich Side of the Al-Cu-Mg System”,

Proceedings of the JEEP’99, in press, Annecy, 1999 (Equi. Diagram, Experimental, 14)

[1999Xie] Xie, F.Y., Kraft, T., Zuo, Y., Moon, C.H., Chang, Y.A., “Microstructure and

Microsegregation in Al-rich Al-Cu-Mg Alloys”, Acta Mater., 47, 489-500 (1999)

(Experimental, Calculation, Equi. Diagram, 42)

[2000Fau] Faudot, F., Dallas, J.P., Harmelin, M.G., “Comment on the Paper a New Intermetallic

Compound Mg1.75Cu1.0Al0.4”, J. Mater. Sci. Letter., 19, 539-540 (2000) (Experiment,

Crys. Structure, 9)

[2000Hir] Hirosawa, S., Sato, T., Kamio, A., Flower, H.M., “Classification of the Role of

Microalloying Elements in Phase Decomposition of Al Based Alloys”, Acta Mater., 48,

1797-1806 (2000) (Experimental, Calculation, 35)

[2000Lia] H. Liang, T. Kraft, Y.A. Chang, “Importance of Reliable Phase Equilibria in Studying

Microsegregation in Alloys Al-Cu-Mg”, Mater. Sci. Eng. A, A292, 96-103 (2000)

(Experimental, Equi. Diagram, 31)

[2000Tak] Takeuchi, T., Mizuno, T., Banno, E., Mizutani, U., “Magic Number of Electron

Concentration in the Isocahedral Cluster of AlxMg40X60-x (X=Zn, Cu, Ag and Pd) 1/

1-Cubic Approximants”, Mater. Sci.Eng. A, 294-296, 522-526 (2000) (Experiment, Crys.

Struct., 14)

[2001Che] Chen, S.L., Daniel, S., Zhang, F., Chang, Y.A., Oates, W.A., Schmid-Fetzer, R., “On the

Calculation of Multicomponent Stable Phase Diagrams”, J. Phase Equilib., 22, 373-378

(2001) (Calculation, Equi. Diagram, 26)

[2001Fau] Faudot, F., Harmelin, M., Liang, P., Seifert, H., Private communication (2001)

[2002Che] Chen, S.L., Daniel, S., Zhang, F., Chang, Y.A., Yan, X.Y., Xie, F.Y., Schmid-Fetzer, R.,

Oates, W.A., “The PANDAT Software Package and its Applications”, Calphad, 26,

175-188 (2002) (Calculation, Equi. Diagram, 24)

[2002Cze] Czeppe, T., Zakulski, W., Bielanska, E., “Determination of the Thermal Stability of Phase

in the Mg-Al System by the Application of DSC Calorimetry”, J. Phase Equilib., 23, in

press (2002) (Experimental, Equi. Diagram, 10)

[2002Dav] Davydov, V.G., Ber, L.B., “TTT and TTP Ageing Diagrams of Commercial Aluminum

Alloys and Their use for Ageing Acceleration and Properties Improvement”, Mater. Sci.

Forum, 396-402, 1169-1174 (2002) (Equi. Diagram, Phys. Prop., Experimental, 10)

58


MSIT®

Al–Cu–Mg

[2002Gul] Gulay, L.D, Harbrecht, B., “The Crystal Structures of the 1 and 2 Phases in the Al-Cu

System”, in “Crystal Chemistry of Intermetallic Compounds”, Abstr. VIII Int. Conf, Lviv,


[2002Iva] Ivanchenko, V., Ansara, I., “Cu-Mg (Copper-Magnesium)”, MSIT Binary Evaluation




[2002Hir] Hirosawa, S., Sato, T., “Atomistic Behavior of Microalloying Elements in Phase

Decomposition of Al Based Alloys”, Mater. Sci. Forum, 396-402, 649-654 (2002)

(Calculation, 7)

[2002Zhu] Zhu, A.W., Gable, B.M., Shiflet, G.J., Starke Jr., E.A., “The Intelligent Design of the High

Strength, Creep-Resistant Aluminium Alloys”, Mater. Sci. Forum, 396-402, 21-30 (2002)

(Experimental, Calculation, Phys. Prop., 23)

[2003Gro] Groebner, J., “Al-Cu (Aluminium-Copper)”, MSIT Binary Evaluation Program, in MSIT



[2003Jan] Jantzen, T., Fries, S.G., Harmelin, M.G., Faudot, F., Lukas, H.L., Liang, P., Seifert, H.J.,

Aldinger, F., Private Communication (1999)

[2003Luk] Lukas, H.L., “Al-Mg (Aluminium-Magnesium)”, MSIT Binary Evaluation Program, in

MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services

GmbH, Stuttgart; to be published, (2003) (Crys. Structure, Equi. Diagram, Assessment, 49)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.88 at 24°C [V-C]

100 to 81.4 at.% Al at 450°C

[1982Mur]

(Cu)

< 1084.62

Cu1-xAlx

cF4

Fm3m

Cu

a = 361.46

a = 361.52

a = 365.36

at 25°C [Mas2]

0 to 19.7 at.% Al [Mas2]

melting point [1994Mur]

[1991Ell], x=0,quenched from 600°C

[1991Ell], x=0.152,quenched from

600°C, linear da/dx

(Mg)

< 650

hP2

P63/mmc

Mg

a = 320.94

c = 521.01

at 25°C [V-C2]

0 to 11.5 at.% Al at 437°C

[1982Mur]

, CuAl2< 591

tI12

I4/mcm

CuAl2 a = 606.7

c = 487.7

31.9 to 33.0 at.% Cu

[1994Mur]

single crystal [V-C2, 1989Mee]

1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu,

[V-C, Mas2, 1985Mur]


59


MSIT®

Al–Cu–Mg

2, CuAl(r)

< 569

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

[1985Mur]

49.8 to 52.3 at.% Cu, [V-C2]

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2Cu47.8Al35.5

a = 812.67

b = 1419.85c = 999.28

55.2 to 59.8 at.% Cu [Mas2, 1994Mur]structure: [2002Gul]

2, Cu11.5Al9(r)

< 570

oI24 - 3.5

Imm2Cu11.5Al9

a = 409.72

b = 703.13c = 997.93


1, Cu100-xAlx958-848

cubic (?) 37.9 x 40.6

59.4 to 62.1 at.% Cu, [Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.47 x 0.78

55.0 to 61.1 at.% Cu, [Mas, 1985Mur,

V-C2],


, Cu100-xAlx< 686

hR*

R3m a = 1226

c = 1511

38.1 x 40.7 [Mas2, 1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

0, Cu100-xAlx Cu 2Al

1022-780

cI52

I43m

Cu5Zn8

- 31 x 40.2 [Mas2],

62 to 68 at.% Cu

[1998Liu]

1, Cu9Al4890

cP52

P43m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu, [Mas2, 1998Liu];

powder and single crystal [V-C2]

from single crystal [V-C2]

, Cu3Al(h)

1049-559

cI2

Im3m

W

a = 295.64

70.6 to 82 at.% Cu [1985Mur][1998Liu]

at 672°C in +(Cu) alloy

CuMg2

< 568

oF48

Fddd

CuMg2

a = 907

b = 528.4

c = 1825

a = 905

b = 528.3

c = 1824.7

a = 904.4 ± 0.1

b = 527.5 ± 0.1

c = 1832.8 ± 0.2

[Mas2, V-C2]

[1994Nay]

[1993Gin]

Cu2Mg

< 797

cF24

Fd3m

Cu2Mg

a = 702.1 64.7 to 69 at.% Cu [Mas2, V-C2]

Mg2Al3 452

cF1168

Fd3m

Mg2Al3

a = 2823.9 [1982Mur]

60-62 at.% Al [1982Mur, 2002Cze]

1168 atoms on 1704 sites per unit cell

[1965Sam, 1982Mur]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

60


MSIT®

Al–Cu–Mg

Mg17Al12

458

cI58

I43m

Mn

a = 1054.38 [1982Mur]

At 41.4 at.% Al, [V-C2]

39.5 to 51.5 at.% Al, [1998Lia11]

40 to 52 at.% Al, [2002Cze]

Space group from [1998Don]

Mg23Al30

410-250

hR159

R3

Mn44Si9

a = 1282.54

c = 2174.78

54.5-56.5 at.% Al [1998Lia1, 1998Lia2,

2002Cze]

Structure : 159 atoms refer to

hexagonal unit cell [1968Sam]

1, (Cu1-xAlx)2Mg

Cu2Mg

< 900

cF24

Fd3m

Cu2Mg a = 701.3

a = 715.42

0 x 0.433 [1936Lav1]

space group from [1936Lav1]

at x = 0

For Mg1.75Cu1.0Al0.4 at 480°C

[2000Fau]

* Q, Cu3Mg6Al7 cI96

Im3m

CuFeS2

a = 1208.7 [1951Mir1]

space group from [1991Eff]

* S, CuMgAl2 oC16

Cmcm

BRe3

a = 401

b = 925

c = 715

[1943Per]


* T, (Cu1-xAlx)49Mg32 cI162

Im3

Mg32(Al,Zn)49

a = 1428 to 1435

[1952Ber]

composition dependent

space group from [1981Mel2]

* V, Cu6Mg2Al5 cP39

Pm3

Mg2Zn11

a = 827 [1949Sam]


* 2, (Cu1-x Alx)2Mg

< 601.6

hP24

P63/mmc

MgNi2

a = 509.8 to 510.2

c = 1664 to 1676

0.492 x 0.576 [1936Lav1]


* 3, (Cu1-xAlx)2Mg

< 537.8

hP12

P63/mmc

MgZn2

a = 507 to 512

c = 829 to 839

0.598 x 0.613 [1936Lav1]


* 5L, (Cu,Al)2Mg hP30 a = 514

c = 2105

stacking variation of Laves phases

observed by electron diffraction

[1962Kom]

* 6L, (Cu,Al)2Mg hP36

P6m2

a = 510

c = 2500

a = 514

c = 2530



[1977Kit]

[1977Kom]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

61


MSIT®

Al–Cu–Mg

Table 2a: Invariant Four-Phase Equilibria

* 9L, (Cu,Al)2Mg hR18 a = 1297

= 22.50°

[1962Kom], stacking variation of Laves

phases observed by electron diffraction

[1977Kom]

* 16L, (Cu,Al)2Mg hP96

P63/mmc

a = 510

c = 6670

a = 514

c = 6740



[1977Kit]

[1977Kom]


Al Cu Mg

0 + 1 L + 1 876.4 U1 0

1

L

1

34.2

36.8

39.2

35.0

65.8

62.8

56.4

65.0

0.0

0.4

4.4

0.0

1 L + 1 + 2 827.6 E1 1

L

1

2

39.7

43.4

36.1

42.0

59.9

52.4

63.9

58.0

0.4

4.2

0.0

0.0

L 0 + 1 + 1 804.0 E2 L

0

1

1

25.1

31.8

32.7

16.3

59.6

68.2

67.3

50.6

15.3

0.0

0.0

33.1

L + 0 + 1 800.3 E3 L

0

1

21.8

27.5

31.3

14.2

62.8

71.4

68.7

52.8

15.4

1.1

0.0

33.0

L + (Cu) + 1 782.8 U2 L

(Cu)

1

12.9

20.7

17.8

8.6

70.2

78.3

81.1

58.7

16.9

1.0

1.1

32.7

0 + 1 + 1 782.1 U3 0

1

1

31.2

14.0

27.2

31.4

68.8

53.0

71.7

68.6

0.0

33.0

1.1

0.0

L + 1 2 + 1 739.9 U4 L

1

2

1

38.7

36.3

42.5

23.4

48.4

63.7

57.5

43.4

12.9

0.0

0.0

33.2

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

62


MSIT®

Al–Cu–Mg

2 + 1 , 1 690.2 D1 2

1

1

42.8

36.3

40.0

23.4

57.2

63.7

60.0

43.3

0.0

0.0

0.0

33.2

L + 2 + 1 V 683.9 P1 L

2

1

V

46.5

44.2

27.1

38.5

41.0

56.8

39.8

46.1

12.5

0.0

33.1

15.4

2 + 1 +V 641.8 U5 2

1

V

43.6

25.0

40.0

38.5

56.4

41.8

60.0

46.1

0.0

33.2

0.0

15.4

L + 2 + V 601.5 U6 L

2

V

58.3

45.8

49.0

38.5

33.5

54.2

51.0

46.1

8.1

0.0

0.0

15.4

2 + , V 582.7 D2 2

V

44.4

40.0

45.0

38.5

55.6

60.0

55.0

46.1

0.0

0.0

0.0

15.4

2 + , V 579.3 D3 2

V

47.5

48.9

45.0

38.5

54.3

51.1

55.0

46.1

0.0

0.0

0.0

15.4

(Cu) + 1+ 1 564.6 E4

(Cu)

1

1

22.8

20.4

29.6

10.2

76.9

79.3

10.4

56.7

0.3

0.3

0.0

33.1

L + 1 2 + V 562.0 U7 L

1

2

V

60.0

32.9

36.6

38.5

26.6

34.1

30.9

46.1

13.4

32.9

32.5

15.4

L + 2 S +V 561.2 U8 L

2

S

V

60.1

36.6

50.0

38.5

26.5

30.9

25.0

46.1

13.4

32.5

25.0

15.4

L + + V 559.4 U9 L

V

62.5

49.6

67.0

38.5

29.4

50.4

33.0

46.1

8.1

0.0

0.0

15.4

L + V + S 543.8 U10 L

S

V

63.0

67.0

50.0

38.5

28.9

33.0

25.0

46.1

8.1

0.0

25.0

15.4


Al Cu Mg

63


MSIT®

Al–Cu–Mg

L + 2 3 + S 534.7 U11 L

2

3

S

58.4

39.0

40.4

50.0

10.7

28.0

26.3

25.0

30.9

33.0

33.3

25.0

L + 3 2 + Q 524.9 U12 L

3

2

Q

46.7

40.1

38.5

43.8

7.7

26.5

28.3

18.7

45.6

33.4

33.2

37.5

L + 3 Q + S 513.2 U13 L

3

Q

S

58.6

41.0

43.8

50.0

8.2

25.6

18.7

25.0

33.2

33.3

37.5

25.0

L + (Al) + S 502.1 E5 L

(Al)

S

73.9

67.8

95.7

50.0

15.5

32.2

1.7

25.0

10.6

0.0

2.6

25.0

L + 1 2 + (Mg) 497.3 U14 L

1

2

(Mg)

18.6

31.0

34.6

3.8

7.1

35.5

32.0

0.0

74.3

33.5

33.4

96.2

L 1 + CuMg2 + (Mg) 481.2 E6 L

1

CuMg2

(Mg)

1.1

19.2

0.0

0.1

16.6

47.1

33.3

0.1

82.3

33.7

66.7

99.8

L + Q T + S 479.0 U15 L

Q

T

S

64.1

43.8

52.0

50.0

5.5

18.7

8.3

25.0

30.4

37.5

39.7

25.0

L + S T + (Al) 469.2 U16 L

S

T

(Al)

67.0

50.0

52.4

89.2

4.9

25.0

8.1

0.3

28.1

25.0

39.5

10.5

L + 2 Q + (Mg) 454.6 U17 L

2

Q

(Mg)

26.3

37.2

43.8

7.5

4.1

29.4

18.7

0.0

69.6

33.4

37.5

92.5

L T + Mg2Al3 + (Al) 447.6 E 7 L

T

Mg2Al3(Al)

63.5

55.4

61.1

83.6

0.5

4.1

0.0

0.0

36.0

40.5

38.9

16.4

L T + Mg2Al3 + Mg17Al12 447.6 E8 L

T

Mg2Al3Mg17Al12

57.4

55.1

61.1

51.9

0.3

3.4

0.0

0.0

42.3

41.5

38.9

48.1


Al Cu Mg

64


MSIT®

Al–Cu–Mg

Table 2b: Invariant Maxima of Two- and Three-Phase Equilibria

L + Q T + (Mg) 426.8 U18 L

T

Q

(Mg)

31.1

47.8

43.8

11.0

1.7

9.3

18.7

0.0

67.2

42.9

37.5

89.0

L (Mg) + T + Mg17Al12 424.7 E9 L

(Mg)

T

Mg17Al12

31.6

11.1

47.9

40.0

1.8

0.0

9.2

0.0

66.6

88.9

42.9

60.0

Mg2Al3 + Mg17Al12 Mg23Al30, T 409.8 D4 Mg3Al2Mg17Al12

Mg23Al30

T

61.1

50.6

56.6

55.2

0.0

0.0

0.0

3.4

38.9

49.4

43.4

41.4

Mg23Al30 Mg2Al3 + Mg17Al12, T 250.1 D5 Mg23Al30

Mg3Al2Mg17Al12

T

56.6

61.1

46.4

55.8

0.0

0.0

0.0

3.5

43.4

38.9

53.6

40.7


Al Cu Mg

L 1 909.3 congruent L

1

16.1

16.1

50.5

50.5

33.4

33.4

L 0 + 1 804.4 e3 L

0

1

24.2

31.6

15.8

60.4

68.4

51.1

15.4

0.0

33.1

L 1 + 1 804.0 e4 L

1

1

25.1

32.7

16.3

59.6

67.3

50.6

15.3

0.0

33.1

L + 1 800.4 e5 L

1

20.9

26.9

13.7

63.5

72.0

53.3

15.6

1.1

33.0

L+ 1 2 601.6 p8 L

1

2

51.5

33.9

37.0

16.4

32.9

29.9

32.1

33.2

33.1

L 1 + CuMg2 566.5 e10 L

1

CuMg2

0.2

9.3

0.0

33.9

56.6

33.3

65.9

34.1

66.7

L + 2 S 570.9 p10 L

2

S

60.2

37.5

50.0

20.8

29.8

25.0

19.0

32.7

25.0

L + 2 3 537.8 p11 L

2

3

54.4

38.8

40.3

9.7

28.1

26.4

35.9

33.1

33.3


Al Cu Mg

65


MSIT®

Al–Cu–Mg

Table 3: Reported Data for the Invariant Reaction E5, L (Al) + S +

L 1 + (Mg) 528.2 e13 L

1

(Mg)

7.8

26.3

1.1

10.7

40.1

0.0

81.5

33.6

98.9

L + 3 Q 527.5 p12 L

3

Q

49.1

40.3

43.8

7.9

26.3

18.7

43.0

33.4

37.5

L (Al) + S 505.5 e14 L

(Al)

S

73.5

95.2

50.0

12.6

1.1

25.0

13.9

3.7

25.0

L + Q T 495.4 p13 L

Q

T

53.5

43.8

51.1

4.8

18.7

8.3

41.7

37.5

40.6

L Mg17Al12 + T 457.2 e16 L

Mg17Al12

T

48.0

47.1

52.4

0.9

0.0

5.4

51.1

52.9

42.2

L Mg2Al3 + T 449.3 e19 L

Mg2Al3T

60.5

61.1

55.3

0.4

0.0

3.8

39.1

38.9

40.9

Temperature [°C] Liquid composition (mass%) References Comment

Cu Mg

500 26.8 6.2 [1937Nis1] -

500 29.7 7.2 [1946Ura, 1949Ura2] -

507 33 6.1 [1948Bro] -

- 29 6.5 [1950Phr] scaled from figure

506.5 33.1 6.8 [1952Han] -

506 33 7 [1967Coo] unidirect solidification

506 33.1 6.25 [1972Gar] unidirect solidification

507 33 7.1 [1973Dav] -

507 34 7.6 [1973Dav] calculated

507 30 6 [1976Mon] -

506±1 - - [1980Bir] d.s.c

506.6 33.4 7.2 [1987Lac] calculated

503 32 7.2 [1995Hua] DTA

503±2 33.4 6.95 [1997Che] calculated

503 30.4 8 [1998Buh] calculated

502.1 30.4 8 [2003Jan] calculated


Al Cu Mg

66


MSIT®

Al–Cu–Mg

Table 4: Reported Data for the Invariant Reaction E7, L T + (Al) + Mg2Al3

Table 5: Reported Data for the Invariant Reaction U16, L + S T + (Al)

Temperature [°C] Liquid Composition (mass%) References

Cu Mg

451 ~0.0 35 [1919Vog]

447 3 32 [1937Nis1]

445 1.5 33 [1946Ura, 1949Ura2]

451 ~2.7 ~ 32 [1948Bro]

450 ~ 3.5 ~ 32 [1952Han]

- 4 31.5 [1950Phr]

~ 450 2.8 32 [1951Mir2]

443 3.4 34 [1987Lac]

448±5 1.34 34.2 [1997Che]

448 1.5 33.3 [1998Buh]

447.6 1.3 33.4 [2003Jan]

Temperature [°C] Liquid Composition (mass%) References Comment

Cu Mg

471 10 27 [1919Vog] -

465 11 25 [1937Nis1] -

465 10 25.6 [1946Ura] -

462 10 25.6 [1949Ura2] -

467 10 26 [1948Bro] -

465 9.3 26.5 [1951Mir2] -

472.3 11.3 25.7 [1952Han] scaled from figure

467 10 26 [1976Mon] -

468 11.4 25.5 [1987Lac] assessment

467±4 10.7 26.1 [1997Che] calculated

469 11.1 24.6 [1998Buh] calculated

469.2 11.2 24.4 [2003Jan] calculated

67


MSIT®

Al–Cu–Mg

Table 6: Reported Data for the Mg-Rich Invariant Reactions E9, U17 and U18

Table 7: Lattice Parameter, a, of the (Al) Phase [1951Poo] at 25°C

Temperature [°C] Liquid Composition (mass%) References Invariant Reaction

Cu Mg

412

419-420

423

425

423.6

426

424.9

17

6

4.6

6

5.4

4.4

4.3

56.5

62.2

67

63

62.6

63.2

63.3

[1933Bas, 1934Por]

[1940Han]

[1949Ura2]

[1951Mir2]

[1997Che]

[1998Buh]

[2003Jan]

L (Mg) + Al11Mg17 +

L (Mg) + Al11Mg17 +

L (Mg) + Al11Mg17 +

L (Mg) + Al12Mg17 + Q

L (Mg) + Al12Mg17 + Q

L (Mg) + Al12Mg17 + Q

L (Mg) + Al12Mg17 + Q

452.0

456.6

11.3

9.9

62.7

63.7

[1997Che]

[2003Jan]

L + 2 (Mg) + Q

L + 2 (Mg) + Q

444.0

428

426.8

6.0

4.4

4.4

52.9

62.3

62.6

[1997Che]

[1998Buh]

[2003Jan]

L + T Al12Mg17 + Q

L + T Al12Mg17 + Q

L + T Al12Mg17 + Q

Analysed Composition (at.%) Observed a [pm] Intended Composition (at.%) Corrected a [pm]

Mg Cu Mg Cu

0.189 0.367 404.8 0.25 0.375 404.81

0.456 0.247 404.97 0.5 0.25 404.99

0.655 0.119 405.1 0.75 0.125 405.14

0.202 0.88 404.58 0.25 0.875 404.6

0.414 0.75 404.72 0.5 0.75 404.76

0.637 0.628 404.9 0.75 0.625 404.95

0.927 0.5 405.07 1 0.5 405.1

1.247 0.362 405.24 1.25 0.375 405.24

1.311 0.246 405.32 1.5 0.25 405.4

1.608 0.127 405.5 1.75 0.125 405.56

0.356 0.302 404.91 0.375 0.313 404.91

0.578 0.179 405.05 0.625 0.188 405.07

1.058 0.422 405.12 1.125 0.438 405.14

0.57 0.659 404.77 0.625 0.688 404.78

0.804 0.521 404.9 0.875 0.563 404.91

68


MSIT®

Al–Cu–Mg

20

40

60

80

20 40 60 80

20

40

60

80

Mg Cu


Axes: at.%

λ1

S

(Al)

(Mg)(Cu)

θ

β

U6

E5

U7

p8

p10 U8

E1

U1U4

γ1

ε2P1

U16

U2

e5

e3

e4

E3

E2

γ0

U9

η1

e10

E6

U14

U17

E9

λ2

λ3

e16

U 12

U11

U13

U15

p 13p 12

p11

T

Q

E7

E8

e13

e14

e1

p1

p2

e6

p4

e12

U10

U18

e15

p7

Mg17Al12

Mg2Al3p9

e11

ε1

V

CuMg2

e19

e20

Fig. 2: Al-Cu-Mg.

Liquidus univariant

lines and primary

phases

MgZn2Cu2Mg [1934Lav]

Cu2Mgprimary

Cu2Mg+MgNi2prim.

MgNi2

primaryMgZn2

primary[1936Lav1] as-cast

Cu2Mg MgNi2 MgZn2 [1953Kle]

Cu2Mg [1943Gue] annealed close to solidus

Cu2Mg Cu2Mg+MgZn2

[1949Ura1]

Cu2Mg MgZn2

MgNi2

[1936Lav1]

Cu2Mg MgNi2 [1965Sli]

Cu2Mg MgNi2 MgZn2 [1981Mel2]

20 40 60Al, at.%

0.0 Al33.3 Mg66.7 Cu

AlCuMg

MgNi2 MgZn2

stacking variants

[1977Kom]

MgNi2+MgZn2 [1962Kom] slowly cooled from melt

Cu2Mg = �1 MgNi2 = �2 MgZn2 = �3

33.3 Mg 66.7 Al

0.0 Cu

Fig. 1: Al-Cu-Mg.

Phases detected along

the 33.3 at.% Mg

section

69


MSIT®

Al–Cu–Mg

20

40

60

80

20 40 60 80

20

40

60

80

Mg Cu


Axes: at.%

600

550

900

500

550

650

700

750

800

850

600550

500

550

600

1050

1000

950

900

800850

Fig. 2b: Al-Cu-Mg.

Liquidus projection

with liquidus

isotherms

30

40

50

60

70

10 20 30 40 50

30

40

50

60

70

Mg 80.00Cu 0.00Al 20.00

Mg 20.00Cu 60.00Al 20.00

Mg 20.00Cu 0.00Al 80.00 Data / Grid: at.%

Axes: at.%

S

p8

U16

U17

E9 λ2

λ3

e16

U12

U11

U13

U15

p13

p12 p11

T

Q

E7

E8

U 18

Mg17Al12

Mg2Al3

e19

e20

(Mg)

Fig. 2a: Al-Cu-Mg.

Enlarged part of the

liquidus projetion

shown in Fig. 2

70


MSIT®

Al–Cu–Mg

Fig

. 3a:

Al-

Cu

-Mg.

Rea

ctio

n s

chem

e, p

art

1.

Al-

Cu

Al-

Mg

Cu

-Mg

Al-

Cu

-Mg

l (

Cu)

+ β

1036.1

e 1

l +

βγ 0

10

20

p1

l +

γ0

ε 1

95

9p2

l +

ε1

ε 2

850.9

p4

γ 0 +

ε1

γ 1 +

L876.4

U1

ε 1γ 1

+ ε2 +

L827.6

E1

Lγ 0

+ λ1

804.4

e 3

Lγ 0

+ γ1 +

λ1

80

4E2

Lγ 1

+ λ1

804.0

e 4

Lβ

+ γ 0

+ λ1

800.3

E3

L +

β (

Cu)

+ λ1

782.8

U2

γ 0 + ε1

γ1

880.7

p3

β +

γ0

γ 1

781.3

p5

ε 1γ 1

+ ε2

83

7e 2

l (

Cu)

+ λ1

72

5e 6

γ 0 + λ1

β +

γ 1782.1

U3

Lβ

+ λ 1

800.4

e 5

ε 2 +

λ1 +

L

γ 1 +

γ0 +

L

ε 2+

λ 1 +

γ1

β +

γ 1 +

λ1

P1

γ 1 +

ε2

δ690.2

p6

ε 2 +

γ1

δ, λ1

690.2

D1

ε 2 +

δ +

λ 1

β +

γ 0 + λ

1

γ 1 +

δ +

λ 1

ε 1 +

γ1 +

L

β +

λ 1 +

(Cu)

γ 0 +

γ1 +

λ 1

L +

γ1

ε 2 +

λ1

739.9

U4

γ 1 +

ε2

+ L

E4

E4

U5

71


MSIT®

Al–Cu–Mg

Fig

. 3b

:

Al-

Cu

-Mg.

Rea

ctio

n s

chem

e, p

art

2

Al-

Cu

Al-

Mg

Cu

-Mg

Al-

Cu

-Mg

β (

Cu) +

γ1

566.9

e 9

l (

Al)

+ θ

547.6

e 12

L +

ε2 +

λ1

V683.9

P1

L +

ε2

η +

V601.5

U6

ε 2 δ

+ ζ

, V582.7

D2

ε 2η

+ ζ,

V579.3

D3

β (

Cu)

+ γ 1

+ λ 1

564.6

E4

L +

λ1

λ 2 +

V5

62

U7

L +

ηθ

+ V

559.4

U9

L +

λ2

S +

V561.2

U8

L +

V

θ +

S543.8

U10

L +

λ2

λ 3 +

S534.7

U11

L +

λ1

λ 2

601.6

p8

Lλ 1

+ C

uM

g2

566.5

e 10

L +

λ2

S

570.9

p10

L +

λ2

λ 3

537.8

p11

lλ 1

+ C

uM

g2

55

2e 11

ε 2η

+ ζ

579.3

e 8

ε 2δ

+ ζ

582.7

e 7

l +

ηθ

595.8

p9

l +

ε2

η624.9

p7

L +

ε2

+ V

ε 2 +

λ1 +

V

V+

η +

ε 2

(Cu)

+ γ 1

+ λ1

V+

η +

θ

V+

λ 1 + λ

2

V+

S +

λ2

U12

ζ +

η +

V

D1

L+

λ 2+V

ε 2 +

λ1

δ +

V641.8

U5

L +

λ1 +

V

ε 2ζ,

V5

88

d(m

ax)

ζ +

δ +

V

λ 1 +

δ +

V

E5

S+

λ 2 +

λ3

L +

V +

θL

+ V

+ S

ε 2+

δ +

V

V+

S +

θ

U14

U2U3

L +

θ+

S

E5

L +

S +

λ3

U13

E6

U4

72


MSIT®

Al–Cu–Mg

Fig

. 3c:

A

l-C

u-M

g.

Rea

ctio

n s

chem

e, p

art

3

Al-

Cu

Al-

Mg

Cu

-Mg

Al-

Cu

-Mg

LT

+M

g2A

l 3+

Mg17A

l 12

447.6

E8

L T

+ M

g2A

l 3 +

(A

l)447.6

E7

L +

λ2

Q +

(M

g)

454.6

U17

L +

S

T +

(A

l)469.2

U16

L M

g17A

l 12 +

T

457.2

e 16

L M

g2A

l 3 +

T

449.3

e 19

L +

Q

T +

S4

79

U15

Lλ 1

+C

uM

g2 +

(M

g)

481.2

E6

L +

Q

T

495.4

p13

L +

λ1

λ 2 +

(M

g)

497.3

U14

lM

g2A

l 3+

Mg17A

l 12

449.5

e 18

450.5

e 17

l (

Al)

+ M

g2A

l 3

l C

uM

g2 +

(M

g)

48

5e 15

L (

Al)

+ S

505.5

e 14

Lθ

+ (

Al)

+S

502.1

E5

L +

λ3

Q +

S513.2

U13

L+

λ 2+

(Mg)

L +

Q +

(M

g)

L +

λ3

λ 2 +

Q524.9

U12

L +

λ3

Q

527.5

p12

Lλ 1

+ (

Mg)

528.2

e 13

p11

λ 3 +

Q +

S

(Mg)+

λ 1+λ

2

(Mg)+

Cu

Mg2+λ

1

Q+

S +

Τ

(Al)

+ S

+ Τ

(Mg)

+ Q

+ λ1

U18

E9

(Al)

+Τ+M

g2A

l 3M

g17A

l 12+Τ

+Mg2A

l 3

D4

U18

λ 2 +

λ3 +

Q

L+

T+

(Al)

(Al)

+ S

+ θ

e 12

U11

U10

p8

e 10

L +

Q +

S

L +

T +

S

L +

λ2 +

Q

73


MSIT®

Al–Cu–Mg

Fig

. 3d

: A

l-C

u-M

g.

Rea

ctio

n s

chem

e, p

art

4

Al-

Cu

Al-

Mg

Cu

-Mg

Al-

Cu

-Mg

Mg23A

l 30

Mg2A

l 3+

Mg17A

l 12

25

0e 21

Mg

2A

l 3+

Mg17A

l 12

Mg23A

l 30

41

0p14

Mg23A

l 30

Mg2A

l 3+

Mg17A

l 12,

T250.1

D5

Mg2A

l 3+

Mg17A

l 12

Mg23A

l 30,

T409.8

D4

L (

Mg)+

T+

Mg17A

l 12

424.7

E9

L +

Q

T +

(M

g)

426.8

U18

l (

Mg)+

Mg17A

l 12

43

6e 20

e 16

p13

U17

T +

Q +

(M

g)

E8

Mg23A

l 30 +

Mg2A

l 3+

T

T +

Mg17A

l 12

+ M

g2A

l 3

(Mg

)+T

+M

g17A

l 12

T+

Mg17A

l 12+

Mg23A

l 30

L +

T +

(Mg)

74


MSIT®

Al–Cu–Mg

10

10

90

Mg 20.00Cu 0.00Al 80.00

Mg 0.00Cu 20.00Al 80.00


Axes: at.%

(Al)+θ

(Al)

(Al)+S

(Al)+T

460°C

375°C

20

40

60

80

20 40 60 80

20

40

60

80

Mg Cu


Axes: at.%

(Cu)+λ1

T

γ1

η2

δ

S

Q

θ(Al)+S+θ

S+V+θ

CuMg2+λ1

CuMg2

Mg23Al30

λ2

λ3

V

λ2+S+V

(Al)+T+S

γ1+λ1

CuMg2+(Mg)+λ1

(Mg)+λ1

(Mg)+Q+λ 2

Mg2Al3

λ1+V

ζ

λ1

(Cu)

(Al)

(Mg)

Mg17Al12

(Mg)

+T+Q

Fig. 5: Al-Cu-Mg.

Isothermal sections in

the Al-rich corner at

460 and 375°C

Fig. 4: Al-Cu-Mg.


section at 400°C

75


MSIT®

Al–Cu–Mg

Mg 5.00Cu 0.00Al 95.00

Mg 0.00Cu 5.00Al 95.00


Axes: at.%

Q

S52

5500

475

450

425

375350

325

400

300

T

10

90

10

Mg 20.00Cu 80.00Al 0.00

Cu

Mg 0.00Cu 80.00Al 20.00 Data / Grid: at.%

Axes: at.%

(Cu)

25400

700

Fig. 6: Al-Cu-Mg.

Isotherms of the

(Al)-solvus and

phases in equilibrium

with (Al)

Fig. 7: Al-Cu-Mg.

Solubility of Al and

Mg in (Cu)

[1957Rog]

76


MSIT®

Al–Cu–Mg

60 50 40 30 20 10400

500

600

700

800

900

Cu 66.67Mg 33.33Al 0.00

Cu 0.00Mg 33.33Al 66.67Cu, at.%

Tem

pera

ture

, °C

L

L+λ1

L+T

λ1

λ1+λ2

L+λ3

L+λ2

λ 2+Q

λ2+λ3

λ3+S

λ 2+λ3+Q

λ2+λ3+S

L+λ2+λ3 L+Q

S+TQ

+S+

T

λ3+

Q+

S

L+Q+S

L+S+T L+T+Mg2Al3

(Al)+S+T(Al)+T+Mg2Al3

L+Mg2Al3

(Al)+Mg2Al3

10 20 30 40400

500

600

Mg 0.00Cu 22.06Al 77.94

Mg 42.53Cu 0.00Al 57.47Mg, at.%

Tem

pera

ture

, °C

L+Q

L+(Al)+Q

L+S+(Al)

S+(Al)+T

S+(A

l)L+S+Q

L+S

L+T

(Al)+T+L

(Al)

+T

+β

β+ε+T

(Al)+T

L

β+ζ+T

Fig. 8: Al-Cu-Mg.

Isopleth at 33.33 at.%

Mg showing the 1

congruent melting

Fig. 9a: Al-Cu-Mg.

Isopleth at 60 mass%

Al

77


MSIT®

Al–Cu–Mg

10 20 30400

500

Mg 0.00Cu 15.39Al 84.61

Mg 32.23Cu 0.00Al 67.77Mg, at.%

Tem

pera

ture

, °C

L+(Al)L+(Al)+Q

L+(Al)+S

(Al)+S+T

(Al)+S+Q

L+(Al)+T

(Al)+T+β(Al)+T

L

(Al)+S

100

200

300

400

500

600

700

Mg 0.00Cu 1.96Al 98.04

Mg 4.97Cu 0.00Al 95.03Mg, at.%

Tem

pera

ture

, °C

L+(Al)

(Al)

(Al)+Q

(Al)+ S

(Al)+S+T (Al)+T

(Al)+

T+β

(Al)+S+Q

L

4.02.0

Fig. 9b: Al-Cu-Mg.

Isopleth at 70 mass%

Al

Fig. 9c: Al-Cu-Mg.

Isopleth at 95.5

mass% Al

78


MSIT®

Al–Cu–Mg

30

600

Cu 25.00Mg 38.00Al 37.00

Cu 35.00Mg 28.00Al 37.00Cu, at.%

Tem

pera

ture

, °C

601.6

λ2

L+λ1

L+λ2

λ2+S+V

L+λ1+λ2

L+λ2

L+λ1+λ2

L+λ1+V

λ2+V

λ2+S

558554

550

20Cu 14.00Mg 42.25Al 43.75

Cu 24.00Mg 32.25Al 43.75Cu, at.%

Tem

pera

ture

, °C

L+λ 2+λ 3

L+λ2

L+λ3

527.5

527

513

Q+λ3+S

L+Q

L+λ3+Q

L+λ

3+S

L+λ3+Q

525

515

Fig. 10a:Al-Cu-Mg.

Isopleth at 37 at.% Al

showing the 2 phase

formation

Fig. 10b:Al-Cu-Mg.

Isopleth at 43.75 at.%

Al showing the Q

phase formation

79


MSIT®

Al–Cu–Mn

Aluminium – Copper – Manganese

Hans Leo Lukas

Literature Data

The most well-investigated details of the constitution are the equilibria of the (Al) solid solution. The first

papers [1927Kri, 1933Saw] assumed equilibrium between (Al), CuAl2 and the most Al-rich binary Al-Mn

phase, at that time assumed to be MnAl4. [1938Pet] and [1939Han] detected a ternary phase which was

verified by [1943Gue, 1944Ray] and [1947Day] and later papers. The liquidus surfaces after [1938Pet] and

[1947Day] disagree, as [1947Day] found lower temperatures for the U type invariant equilibria than

[1938Pet]. Although the most extensive constitutional investigation [1966Koe] accepted Petri's [1938Pet]

results, a newer paper, [1979Bar], determined the distribution coefficients of Cu and Mn between liquid and

(Al) by unidirectional solidification and stated the results to confirm the liquidus of [1947Day]. The

solubility of Cu and Mn in the (Al) solid solution was most precisely determined by [1950Hof] using

electric resistivity measurements. The data were confirmed and supplemented by [1954Bag]. A detailed

review of the liquidus, solidus and solvus of the Al corner is given by Phillips [1959Phi] and [1961Phi], the

liquidus based on [1947Day]. The kinetics of age hardening of the (Al) phase were studied by [1953Kus],

and those of rapidly quenched supersaturated (Al) by Polesya et al. [1968Pol] and [1970Pol]. Another part

of the constitution, studied several times, is the - equilibrium in the Cu corner. [1947Dea] reported 10

isothermal sections between 850 and 400°C in steps of 50°C. The results were confirmed and supplemented

by [1956Wes], giving 9 isothermal sections at 800, 700, 600, 550, 525, 500, 450, 425 and 400°C. Six

isotherms given by [1955Tur] and 8 isotherms given by [1964Rom] are slightly different, but within the

accuracy of the drawings, may be accepted to agree with [1947Dea] and [1956Wes]. A survey of the

constitution of the whole ternary system was first given by [1927Kri], who gave isotherms of the liquidus

surface, but without lines of double saturation. [1943Gue] determined the phases stable at room temperature

by X-ray diffraction. He found a ternary phase 2 additional to 1 detected by [1938Pet].

The most detailed investigation of the whole system is from [1966Koe]. These authors determined

experimentally the liquidus surface, 4 complete and 8 partial isothermal sections. For simplification they

did not distinguish between 0, 1and (denoted ), 0, , 1 and 2 (denoted ), 1 and 2 (denoted ).

The phases 2, 1 and 2 were ignored. The distinction between the phases MnAl(h) and Mn5Al8(h), as well

as between Mn4Al11(h) and Mn4Al11(r) is due to a later paper by the same group of authors [1971Goe].

Also, the distinction between and in the Al-Mn binary system was established later [1987McA]. The

MnAl(h) phase was later determined to be of the W-type [1990Ell] and thus should be treated as identical

to [1966Koe] accepted the results of [1938Pet, 1947Dea] and [1956Wes] and partially those of

[1943Gue].

[1979Wac] studied the field, containing two areas of ferromagnetic alloys. [1982Sca] and [1988Cou]

reported differences in the Cu-rich area. However, their suggestion that 3 is stable up to 900°C is not

convincing when compared with [1956Wes, 1966Koe] or [1979Wac].

The metals used for the experiments were generally of high purity. [1938Pet] and [1950Hof] prepared

Al-Mn master alloys from 99.99% pure Al and high purity crystalline MnCl2. The alloys of [1947Dea]

contained less than 0.005% Si and with a few exceptions less than 0.02% Fe; those of [1950Hof] contained

less than 0.005% Si and 0.0025% Fe. [1956Wes] used “super pure” Al and electrolytic Cu and Mn.

[1966Koe] used 99.9% pure elements. An important feature of the Al-Cu-Mn system are ferromagnetic

alloys, detected by F. Heusler in 1899 and called Heusler alloys. Many papers are dedicated to the study of

these alloys and to another group of ferromagnetic alloys detected later [1961Tsu1]. While [1927Har] could

not determine which phase was responsible for the ferromagnetism, [1928Heu] located the W type phase

to be the ferromagnetic one. Persson [1928Per] and [1929Per] assumed a superstructure with a

face-centered cubic cell with twice the lattice parameter of . This superstructure was confirmed by

[1933Heu, 1934Bra] and [1934Heu]. The phase is metastable below 400°C, but the decomposition into the

stable phases is very slow and needs prolonged annealing above 300°C. The degree of order of the

80


MSIT®

Al–Cu–Mn

superstructure is time dependent and leads to magnetic aging [1934Heu]. [1940Hir] studied the ternary

ordering by the Bragg Williams theory. In later papers the critical temperature of the superstructure

formation was studied. [1962Kim] found, by high temperature X-ray diffraction at 750°C, the absence of

the MnCu2Al type order, but still a CsCl type order. Using X-ray and neutron diffraction, [1968Joh1]

detected the presence of two different cubic lattices in aged nonstoichiometric Heusler alloys, due to the

miscibility gap between MnCu2Al and the metastable quenched Cu3Al. [1968Oho] assumed the

CsCl-MnCu2Al type transition at 650°C from resistivity measurements during rapid cooling. [1969Nes]

found this transition at 400°C and the CsCl to W type transition at 750 to 770°C. [1973Che] measured 620

± 20 and 780 ± 10°C for the two transitions. All these temperatures belong to the composition MnCu2Al.

[1998Kai] measured the two transition temperatures along the line of constant Al content of 25 at.% from

MnCu2Al to quenched Mn5Cu70Al25 by DTA and found nearly linear change from 794 to 679 and from

644 to 541°C, respectively. The Al content has a more pronounced influence on the transition temperature

than the Mn-content at constant 25 at.% Al. [1999Liu] found evidence for the W type/CsCl type transition

also in the binary Al-Mn system in the MnAl(h) phase at 965 to 967°C.

[1973Gra] heated the room temperature equilibrium phase mixture ( 3, Mn and Cu9Al4) at 290 K and thus

synthesized the Heusler alloy between 470 and 500°C. In several papers, the kinetics of decomposition of

the Heusler phase were studied [1968Joh1, 1969Nes, 1971Lis, 1973Che, 1973Gra, 1974Oka, 1975Bou,

1977Urs, 1979Dub, 1980Yam1, 1980Yam2, 1981Sol1, 1981Sol2, 1981Sol3, 1981Sol4, 1982Koz,

1983Koz1, 1983Koz2, 1983Koz3, 1983Tan, 1985Kok, 1987Koz]. Another area of ferromagnetic alloys

was detected in the CsCl type ordered phase by Tsuboya [1961Tsu1, 1961Tsu2] and [1962Tsu]. The

ferromagnetism is explained by antiferromagnetic coupling of the Mn atoms, which are in different site

fractions on the two sublattices of the CsCl type structure. This was confirmed by [1963Kat] by neutron

diffraction. A metastable tetragonal phase in the Al-Mn system is also ferromagnetic [1963Sug]. The

connection of this metastable phase with the CsCl type phase was studied by [1963Sug] and [1978Urs].

[1997Mue] studied this phase in ternary systems of Al-Mn with Cu, Fe, Ni and C. It is formed from the

(hcp) phase during moderately rapid cooling. These authors found the stability range of to extend below

700°C in the ternary Al-Cu-Mn system. [1979Wac] studied both ferromagnetic states of the phase and

determined their areas in the concentration triangle. [1982Kog] studied the ferromagnetism in the area

between the Heusler and CsCl type alloys. The present evaluation is the succesor of the detailed critical

assessment presented in [1991Luk].

Among the huge amount of literature, there is a number of references with minor relevance to the

constitution of the ternary system but providing related additional information. These are given under

“Additional References”, attached to the list of references.

Binary Systems

The binary Al-Cu and Al-Mn systems were accepted from the Landolt Börnstein series [2002LB]. They are

based on the assessments of [1998Sau] and [1999Liu], respectively. The Al-Cu is virtually the same as that

in the MSIT Workplace, from where the description of the Cu-Mn systems was accepted [2003Tur]. For

Al-Mn a very thorough assessment was done by [1987McA].

Solid Phases

The cI2, W type, phase ( ) at elevated temperatures has an extended range of ternary solid solutions and

forms two different superstructures, cP2, CsCl type, and cF16, MnCu2Al type. The latter structure exists

also metastably in quenched Cu3Al as BiF3 type.

Besides these superstructures, three ternary intermetallic phases exist in the Al-Cu-Mn system. 1 was

detected by Petri [1938Pet] and confirmed in all later papers investigating its area of stability. [1952Rob]

explained its existence by the good fit of its Brillouin zones with the Fermi surface, where the Brillouin

zones were derived from the strong X-ray reflections. [1954Rob] determined the crystal structure of the

isotypic phase Mn11Ni4Al60 with Pearson symbol oC156, but about 5 to 6 vacant sites per 156 sites. The

composition was first given by [1938Pet] as 19 mass% Cu and 24 mass% Al. [1943Gue] confirmed an alloy

of this composition to be single phase 1. This composition corresponds to a formula Mn6Cu4Al29, which

81


MSIT®

Al–Cu–Mn

is more rich in Mn and Cu than the formula Mn3Cu2Al20 given by [1952Rob]. [1966Koe] gave different

compositions for 1 participating in different invariant equilibria. These compositions range from

Mn6Cu4Al29 as the most Al-rich one to Mn8Cu5Al26 and include Mn8Cu4Al27, Mn7Cu4Al28 and

Mn7Cu5Al27. There is, however, no information on which sites of the oC156 structure (5 4-fold, 9 8-fold,

4 16-fold positions) this exchange takes place. The phase 2 was first detected by [1943Gue] and confirmed

by [1966Koe]. The unit cell is orthorhombic with about 380 atoms per cell, but the structure is not yet

resolved. 3 was found by [1956Wes] to be peritectoidally formed at 550°C, confirmed by [1966Koe] and

found by many authors as decomposition product of the Heusler alloy. Its structure was found by

[1968Joh2] to be of the cubic Laves phase MgCu2 type.

At and near the binary Al-Mn boundary besides these stable phases the metastable phases Mn3Al10 and

MnAl(m) (AuCu type) are formed at moderate cooling rates. At extremely fast cooling rates by melt

spinning icosahedral or decagonal quasicrystalline phases are formed [1988Tsa, 1991Maa, 1992Maa]. A

characteristic composition of the decagonal phase is Mn15Cu20Al65, Maâmar et al. investigated also

Mn15Cu10Al75 and Mn10.5Cu32.5Al57 [1990Eck] prepared quasicrystals of composition Mn15Cu20Al65 by

mechanical alloying in a ball mill. [1992Li] pointed out a relationship between the decagonal

quasicrystalline phases and the crystalline 1 phase. All crystalline phases are listed in Table 1.


A reaction scheme, mainly based on the work of Köster [1966Koe] is shown in Fig. 1a and Fig. 1b. The

temperatures in the Al corner are changed to those given by [1947Day] (U6 and U8). The simplification used

by [1966Koe] to treat groups of several phases as single phases was partially accepted. However, MnAl(h)

was taken to belong to the phase ( ) as its crystal structure was reported to be the same [1990Ell]. 2 with

a hexagonal, probably NiAs type, structure was treated as separate phase. Finally the following phases are

treated as single ones: 0, 1 and (called ), 0, 1, MnAl(h) and 1 (called ), 1 and 2 (called ),

Mn5Al8(h) and Mn5Al8(r) (called Mn5Al8), Mn4Al11(h) and Mn4Al11(r) (called Mn4Al11), and (called

MnAl4). The phases 2, 1 and 2 are ignored, as they do not seem to enter significantly in the ternary

equilibria. A four-phase equilibrium, L+ +MnAl(h), given by [1966Koe] is not accepted here as and

MnAl(h) are treated to belong to the same phase. The thermal arrests, which [1966Koe] assigned to this

reaction may be caused by the minimum of the L+ + three-phase equilibrium. Another four-phase

equilibrium, 2+ + , had to be added. The temperatures and phase-compositions of the invariant

equilibria are given in Table 2. Since [1966Koe] stated their concentrations to be uncertain by ± 1.5%, the

Al+Cu contents of ( Mn) and the Cu contents of Mn4Al11, MnAl4 and MnAl6 reported by [1966Koe] have

to be taken as tentative only.

Liquidus Surface

The liquidus surface of the whole system is shown in Fig. 2, that of the Al corner in Fig. 3. Figure 2 is based

on [1966Koe], but modified according to the modifications of the reaction scheme discussed in the previous

section. Figure 3 is taken from [1961Phi]. The solidus and solvus surfaces of the (Al) solid solution in

Figs. 4 and 5 are also taken from [1961Phi].

Isothermal Sections

In Figs. 6, 7, 8 and 9, isothermal sections are given, based mainly on the work of [1966Koe], in the Al-corner

on [1961Phi]. Phase notations are partly abbreviated as given under “Invariant Equilibria”.


The (Al) solid solution containing up to 4% Cu and some Mn is the essential phase of the most important

age hardenable aluminium alloys.

Alloys containing the Heusler phase ” MnCu2Al are widely used due to their unique electric and magnetic

properties.

82


MSIT®

Al–Cu–Mn

The metastable AuCu type phase formed during rapid cooling of the epsilon Al-Mn phase is interesting as

hard magnetic material.

Alloys near Cu3Al with small additions of Mn or other elements are used due to the shape memory effect

connected with their martensitic transformation.

Miscellaneous

Quenching of the phase between Cu3Al and MnCu2Al results in a martensite, which shows a shape

memory effect [1981Dob] and [1988Lop]. [1937Koe] measured the enthalpy of mixing of the liquid along

the section Cu67Mn33-Al.

References

[1927Har] Harang, L., “On the Crystal Structure of the Heusler Alloys”, (in German), Z. Kristallogr.,

65, 261-285 (1927) (Experimental, 7)

[1927Kri] Krings, W., Ostmann, W., “Contribution to the Knowledge of the Cu-Al-Mn Ternary

System and its Magnetic Properties”, (in German), Z. Anorg. Allg. Chem., 163, 145-164

(1927) (Equi. Diagram, Experimental, Magn. Prop., 22)

[1928Heu] Heusler, O., “On the Knowledge of the Heusler Alloys, on Mn-Al-Cu” (in German),

Z. Anorg. Allg. Chem., 171, 126-142 (1928) (Experimental, 15)

[1928Per] Persson, E., “X-Ray Analysis of the Heusler Alloys” (in German), Naturwissenschaften, 16,

45 (1928) (Crys. Structure, Experimental, 4)

[1929Per] Persson, E., “On the Structure of the Heusler Alloys” (in German), Z. Phys., 57, 115-133




[1933Heu] Heusler, O., “Crystal Structure and Ferromagnetism of the Mn-Al-Cu Alloys” (in German),

Z. Metallkd., 25, 261-285 (1933) (Crys. Structure, Experimental, 11)

[1933Saw] Sawamoto, H., “Equilibrium Diagram of the Al-Cu-Mn System” (in Japanese),

Suiyokwai-Shi, 8, 239-246 (1933) (Equi. Diagram, Experimental, 3)

[1934Bra] Bradley, A.J., Rogers, J.W., “The Crystal Structure of the Heusler Alloys”, Proc. Roy. Soc.,

A144, 340-359 (1934) (Crys. Structure, Experimental, 25)

[1934Heu] Heusler, O., “Crystal Structure and Ferromagnetism of the Mn-Al-Cu Alloys” (in German),

Ann. Physik, 19, 155-201 (1934) (Crys. Structure, Experimental, 54)

[1937Koe] Körber, F., Ölsen, W., Lichtenberg, H., “On the Thermochemistry of Alloys II, Direct

Determination of the Heat of Formation of the Ternary Alloys Fe-Ni-Al, Fe-Co-Al,

Cu-Ni-Al, Fe-Al-Si as well as of an Alloy Series of the Cu-Mn-Al System” (in German),

Mitt. K.-W.-Inst. Eisenforschung, 19, 131-159 (1937) (Thermodyn., Experimental, 50)

[1938Pet] Petri, H.-G., “The Aluminium Corner of the Al-Cu-Mn Ternary System” (in German),

Alum. Arch., (14), 5-14 (1938) (Equi. Diagram, Experimental, 7)

[1939Han] Hanemann, H., Schrader, A., “On some Ternary Systems with Al, II. Al-Fe-Mn, Al-Cu-Mn”

(in German), Z. Metallkd., 31, 183-185 (1939) (Equi. Diagram, Experimental, Review, #, 5)

[1940Hir] Hirone, T., Matuda, S., “Theory of the Order-Disorder Transformation in Ternary Alloys”

(in Japanese), Rikagaku-Kenkyusho-Iho, 19, 931-942 (1940) (Theory, 6)

[1943Gue] Guertler, W., Rassmann, G., “The Application of the X-Ray Diffraction for the

Determination of Phase Equilibria in Solid State of Ternary Alloys (Cu-Ni-Co; Al-Cu-Fe;

Al-Sb-Sn; Ag-Cu-Mg; Al-Cu-Mg and Al-Cu-Mn)” (in German), Metallwirtschaft, 22,


[1944Ray] Raynor, G.V., “The Effect on the Compound MnAl6 of Iron, Cobalt and Copper”, J. Inst.

Met., 70, 531-542 (1944) (Equi. Diagram, Experimental, 15)

[1947Day] Day M.K.B., Phillips, H.W.L., “The Constitution of Alloys of Aluminium with Copper and

Manganese”, J. Inst. Met., 74, 33-54 (1947/1948) (Equi. Diagram, Experimental, 33)

83


MSIT®

Al–Cu–Mn

[1947Dea] Dean, R.S., Long, J.R., Graham, T.R., Roberson, A.H., Armantrout, C.E., “The Solid

Solution Area of the Copper-Manganese-Aluminium System”, Trans. AIME., 171, 70-88


[1950Hof] Hofmann, W., “The Solubility of Copper and Manganese in Solid Aluminium” (in German),

Z. Metallkd., 41, 477-479 (1950) (Equi. Diagram, Experimental, 11)

[1952Rob] Robinson, K., “The Unit Cell and Brillouin Zones of Ni4Mn11Al60 and Related

Compounds”, Philos. Mag., 43, 775-782 (1952) (Crys. Structure, Experimental, 10)

[1953Kus] Kusumoto, K., Ohta, M., “Effect of Manganese on Aging of Al-Cu Alloys” (in Japanese),

Nippon Kinzoku Gakkaishi, 17, 561-564 (1953) (Experimental, 7)

[1954Bag] Bagchi, A.P., Axon, H.J., “The Constitution of Aluminium Rich Alloys Containing Copper,

Manganese and Silicon”, J. Inst. Met., 83, 176-180 (1954/1955) (Equi. Diagram,

Experimental, 15)

[1954Rob] Robinson, K., “The Determination of the Crystal Structure of Ni4Mn11Al60”, Acta

Crystallogr., 7, 494-497 (1954) (Crys. Structure, Experimental, 5)

[1955Tur] Turkin, V.D., Chernova, T.S., “Investigation of Alloys of the Cu-Al-Mn System” (in

Russian), Issled. Splavov Tsvet. Metallov., 1, 106-110 (1955) (Equi. Diagram,

Experimental, 1)

[1956Wes] West, D.R.F., Lloyd Thomas, D., “The Constitution of Copper Rich Alloys of the

Copper-Manganese-Aluminium System”, J. Inst. Met., 85, 97-104 (1956/1957) (Equi.


[1958Bla] Bland, J.A., “Studies of Aluminium-Rich Alloys with the Transition Metals Manganese and

Tungsten. II. The Crystal Structure of (Mn-Al)-Mn4Al11”, Acta Crystallogr., 11, 236-244


[1959Phi] Phillips, H.W.L., “Aluminium-Copper-Manganese”, in “Annotated Equilibrium Diagrams

of Some Aluminium Alloy Systems”, Inst. Metal., London, 35-40 (1959) (Equi. Diagram,

Review, 11)

[1959Tay] Taylor, M.A., “The Crystal Structure of Mn3Al10”, Acta Crystallogr., 12, 393-396 (1959)


[1961Phi] Phillips, H.W.L., “Al-Cu-Mn”, in “Equilibrium Diagrams of Aluminium Alloy Systems”,

Aluminium Development Association, London, 63-66 (1961) (Equi. Diagram, Review, 0)

[1961Tay] Taylor, M.A., “The Space Group of MnAl3”, Acta Crystallogr., 14, 84 (1961) (Crys.


[1961Tsu1] Tsuboya, I., Sugihara, M., “On the New Magnetic Phase in Manganese-Aluminium-Copper

System”, J. Phys. Soc. Jpn., 16, 571 (1961) (Crys. Structure, Experimental, 3)

[1961Tsu2] Tsuboya, I., “On the New Magnetic Phase in Manganese - Aluminium - Copper System”,

J. Phys. Soc. Jpn., 16, 1875-1880 (1961) (Crys. Structure, Experimental, 11)

[1962Kim] Kimura, R., Endo, K., Ohoyama, T., “A Partially Ordered Structure of the Heusler Alloy

Cu2MnAl at High Temperatures”, J. Phys. Soc. Jpn., 17, 723-724 (1962) (Crys. Structure,

Experimental, 1)

[1962Tsu] Tsuboya, I., Sugihara, M., “The Magnetic Phase in Mn-Al-Co, -Cu, -Fe and -Ni Ternary

Alloys”, J. Phys. Soc. Jpn., 17, 172-175 (1962) (Experimental, 5)

[1963Kat] Katsurai, H., Takada, H., Suzuki, K., “Neutron Diffraction Study of the CsCl Type Phase

Cu-Mn-Al Alloys”, J. Phys. Soc. Jpn., 18, 93-96 (1963) (Crys. Structure, Experimental, 3)

[1963Sug] Sugihara, M., Tsuboya, I., “Structural and Magnetic Properties of Copper Substituted

Manganese - Aluminium Alloy”, Japan. J. Appl. Phys., 2, 373-380 (1963) (Experimental,

Crys. Structure, Magn. Prop., 7)

[1964Rom] Romu, V.G., “Investigation of the Copper Corner of the Phase Diagram of the Cu-Al-Mn

System” (in Russian), Tr. Leningrad. Politekhn. Inst., 234, 57-61 (1964) (Equi. Diagram,

Experimental, 4)

[1966Koe] Köster, W., Gödecke, T., “The Ternary Copper - Manganese - Aluminium System” (in

German), Z. Metallkd., 57, 889-901 (1966) (Equi. Diagram, Experimental, #, *, 11)

84


MSIT®

Al–Cu–Mn

[1968Joh1] Johnston, G.B., Hall, E.O., “Studies on the Heusler Alloys - I. Cu2MnAl and Associated

Structures”, J. Phys. Chem. Solids, 29, 193-200 (1968) (Equi. Diagram, Experimental, 18)

[1968Joh2] Johnston, G.B., Hall, E.O., “Studies on the Heusler Alloys - II. The Structure of

Cu3Mn2Al”, J. Phys. Chem. Solids, 29, 201-207 (1968) (Crys. Structure, Experimental, 6)

[1968Oho] Ohoyama, T., Webster, P.J., Tebble, R.S., “The Ordering Temperature of Cu2MnAl”, Brit.

J. Appl. Phys., 1, 951-952 (1968) (Equi. Diagram, Experimental, 5)

[1968Pol] Polesya, A.F., Kovalenko, V.V., “Composition and Disintegration Kinetics of

Supersaturated Solid Solutions of Rapidly Solidified Alloys of Al-Cu-Mn”, Phys. Met.

Metallogr., 103-109 (1968), translated from Fiz. Metall. Metalloved., 25, 479-485 (1968)

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[1969Nes] Nesterenko, E.G., Osipenko, I.A., Firstov, S.A., “Structure of Cu-Mn-Al Ordered Alloys”,

Phys. Met. Metallogr., 135-139 (1969), translated from Fiz. Metall. Metalloved., 27,


[1970Pol] Polesya, A.F., Kovalenko, V.V., “Phase Diagram of Rapidly Solidified Al-Cu-Mn Alloys”,

Russ. Metall., (1), 114-117 (1970), translated from Izv. Akad. Nauk SSSR, Met., (1),

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[1971Goe] Gödecke, T., Köster, W., “An Addition to the Phase Diagram of the Al-Mn System” (in

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[1971Lis] Lisse, J.P., Dubois, B., “Preparation and Study of Certain Properties of the Heusler Alloy

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[1973Che] Chevereau, D., Gras, J.M., Dubois, B., “Ordering Phenomena in the Heusler Alloy

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Temperatures” (in French), Compt. Rend. Acad. Sci., Paris, Ser. C, 276, 643-645 (1973)

(Equi. Diagram, Experimental, 4)

[1973Gra] Gras, J.M., Chevereau, D., Dubois, B., “X-Ray Diffraction Study at High Temperature of

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French), Compt. Rend. Acad. Sci., Paris, Ser. C, 276, 483-486 (1973) (Equi. Diagram,

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[1979Dub] Dubois, B., Chevereau, D., “Decomposition of the Heusler Alloy Cu2MnAl at 360°C”,

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Copper Brass Res. Assoc., 19, 131-147 (1980) (Experimental, 19)

[1980Yam2] Yamane, T., Okamoto, H., Takahashi, J., “Aging of Cu-Mn-Al Heusler Alloys”,

Z. Metallkd., 71, 813-817 (1980) (Experimental, 14)

85


MSIT®

Al–Cu–Mn

[1981Dob] Dobrovol'skaya, T.L., Titov, P.V., Khandros, L.G., “Reversible Change of Shape in Alloy

Copper - Aluminium - Manganese”, Phys. Met. Metallogr., 51, 174-177 (1981), translated

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[1981Sol2] Soltys, J., Kozubski, R., “A Simple Model of the Order-Disorder Transitions in Ternary

Alloys and its Application to Several Selected Heusler Alloys”, Phys. Status Solidi A, 63,

35-44 (1981) (Experimental, 23)

[1981Sol3] Soltys, J., “Order-Disorder Phase Transitions in Ternary Alloys Cu3-xMnxAl”, Phys. Status

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[1982Kog] Koga, S., Narita, K., “Exchange Anisotropy in Cu-Mn-Al Alloy”, J. Appl. Phys., 53,

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[1982Koz] Kozubski, R., Soltys, J., “Decomposition of ( )Phase in the Heusler Alloy

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[1982Sca] Scarabello, J.M., Vicario, E., Mack, J., Counioux, J.J., “Contribution to the Study of the

Ternary Cu-Mn-Al System. Determination of the Section Cu-MnAl6 Limited to the Copper

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[1983Koz1] Kozubski, R., Soltys, J., “Precipitation from Metastable -Phase in the Heusler Alloy

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[1983Koz2] Kozubski, R., Soltys, J., Kuziak, R., “Electron Microprobe Analysis of Phase Segregation

in the Heusler Alloy Cu2.00Mn1.00Al1.00”, J. Mater. Sci., 18, 3079-3086 (1983)

(Experimental, 18)

[1983Koz3] Kozubski, R., Soltys, J., “X-Ray Diffraction Quantitative Analysis of the Heusler Alloy

Cu2.00Mn1.00Al1.00 Annealed at Temperatures Between 423 and 973 K”, J. Mater. Sci.

Lett., 2, 141-143 (1983) (Experimental, 17)

[1983Tan] Tanaka, K., Saito, T., Yasuda, M., “Soft X-Ray Emmission Spectra of Aluminium in

-Phase Cu-Ni-Al and Cu-Mn-Al Alloys”, J. Phys. Soc. Jpn., 52, 1718-1724 (1983)

(Experimental, 14)

[1985Kok] Kokorin, V.V., Osipenko, I.A., Cherekov, S.V., Shirina, T.V., “The Influence of Heating

under Pressure on the Structure State of Heusler Alloy Cu2MnAl”, Phys. Met. Metallogr.,

60, 155-160 (1985), translated from Fiz. Metall. Metalloved., 60, 584-589 (1985)

(Experimental, 10)

[1985Mur] Murray, J.L., “The Aluminium-Copper System”, Int. Met. Rev., 30, 211-233 (1985) (Equi.

Diagram, Review, #, 230)

[1987McA] McAlister, A.J., Murray, J.L., “The Al-Mn (Aluminum-Manganese) System”, Bull. Alloy

Phase Diagrams, 8, 438-447 (1987) (Equi. Diagram, Review, #, 59)

[1987Koz] Kozubski, R., Soltys, J., Dutkiewicz, J., Morgiel, J., “TEM Study of the Decomposition of

the Heusler Alloy Cu2MnAl”, J. Mater. Sci., 22, 3843-3846 (1987) (Experimental, 10)

[1988Cou] Counioux, J.J., Macqueron, J.L., Robin, M., Scarabello, J.M., “Phase Transformations and

Shape Memory Effect in Copper - Aluminium - Manganese Alloys”, Scr. Metall., 22,

821-825 (1988) (Experimental, 10)

[1988Lop] Lopez Del Castilio, G., Blazquez, M.L., Gomez, C., Mellor, B.G., De Diego J. Del Rio, N.,

“The Stabilization of Martensite in Cu-Al-Mn Alloys”, J. Mater. Sci., 23, 3379-3382 (1988)

(Experimental, 25)

[1988Tsa] Tsai, A.-P., Inoue, A., Masumoto, T., “New Quasicrystals in Al65Cu20M15 (M = Cr, Mn or

Fe) Systems Prepared by Rapid Solidification”, J. Mater. Sci. Letters, 7, 322-326 (1988)


86


MSIT®

Al–Cu–Mn

[1990Eck] Eckert, J., Schultz, L., Urban, K., “Progress of Quasicrystal Formation During Mechanical

Alloying in Al-Cu-Mn and the Influence of the Milling Intensity”, Z. Metallkd., 81, 862-868

(1990) (Experimental, Quasicrystals, 37)

[1990Ell] Ellner, M., “The Structure of the High-Temperature Phase MnAl(h) and the Displacive

Transformation from MnAl(h) to Mn5Al8”, Met. Trans. A, 21, 1669-1672 (1990)


[1991Maâ] Maâmar, S., Harmelin, M., “On the Transition of the Icosahedral and Decagonal Phases

Towards Equilibrium Phases in Al-Cu-Mn Alloys”, Phil. Mag. Lett., 64, 343-348 (1991)

(Experimental, Egui. Diagram,11)

[1991Luk] Lukas, H.L., “Aluminium - Copper - Manganese”, MSIT Ternary Evaluation Program, in


GmbH, Stuttgart; Document ID: 10.14272.1.20, (1991) (Crys. Structure, Equi. Diagram,

Assessment, 105)

[1992Li] Li, X.Z., Kuo, K.H., “Orthorhombic Crystalline Approximants of the Al-Cu-Mn Decagonal

Quasicrystal”, Phil. Mag. B, 66, 117-124 (1992) 348 (1991) (Experimental, 15)

[1992Maa] Maamar, S., Faudot, F., Harmelin, M., “Relationships Between the Liquidus Temperature

and the Formation of Quasicrystalline Phases in Rapidly Solidified Al-Cu-Mn Alloys”,

Thermochim. Acta, 204, 45-54 (1992) (Experimental, 11)


Subramanian, P.R., Chakrabati, D.T., Laughlin, D.E. (Eds.), ASM International, Materials

Park, OH, 18-42 1994 (Equi. Diagram, Review, 226)

[1997Mue] Müller, C., Stadelmaier, H.H., Reinsch, B., Petzow, G., “Constitution of Mn-Al-(Cu, Fe, Ni

or C) Alloys near the Magnetic Phase”, Z. Metallkd., 88, 620-624 (1997) (Experimental,

Equi. Diagram, 19)

[1998Kai] Kainuma, R., Satoh, N., Liu, X.J., Ohnuma, I., Ishida, K., “Phase Equilibria and Heusler

Phase Stability in the Cu-rich Portion of the Cu-Al-Mn System”, J. Alloy. Compd., 266,

191-200 (1998) (Experimental, Equi. Diagram, Crys Structure, 28)

[1998Sau] N. Sauter, “System Al-Ti” in “COST 507, Thermochemical Database for Light Metal

Alloys”, Vol. 2, I. Ansara, A.T. Dinsdale, M.H. Rand (Eds.), Office for Official Publications

of the European Communities, Luxembourg, 89-94 (1998) (Assessment, Equi. Diagram,

Thermodyn., Calculation, 27)

[1999Liu] Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K., “Thermodynamic Assessment of the

Aluminuim-Manganese (Al-Mn) Binary Phase Diagram”, J. Phase Equilib., 20(1) 45-56

(1999) (Equi. Diagram, Thermodyn., Assessment, Calculation, Experimental, 37)

[2002Gul] Gulay, L.D., Harbrecht,B., “The Crystal Structures of the 1 and 2 Phases in the Al-Cu

System”, in “Crystal Chemistry of Intermetallic Compounds”, Abstr. VIII Int. Conf., Lviv,


[2002LB] Landolt-Börnstein, Numerical Data and Functional Relationship in Science and

Technology, New Series, Ed. in Chief: W. Martienssen, Group IV: Physical Chemistry, Vol.

19, Thermodynamic Properties of Inorganic Materials compiled by SGTE, Subvolume B,

Binary Systems: Phase Diagrams, Phase Transition Data, Integral and Partial Quantities of

Alloys. Part 1 Elements and Binary System from Ag-Al to Au-Tl. Ed. Lehrstuhl f.

Werkstoffchemie, RWTH Aachen, Authors: Scientific Group Thermodata Europe (SGTE),

Springer Verlag, Berlin, Heidelberg, pp. 139-142 Al-Cu, pp. 164-169 Al-Mn (2002)

[2003Tur] Turchanin, M., Agraval, P., Gröbner, J., Matusch, D., Turkevich, V., “Cu - Mn (Copper -

Manganese)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.),

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(Equi. Diagram, Assessment, Crys. Structure, 25)

87


MSIT®

Al–Cu–Mn

Additional References

[1910Ros] Rosenhain W., Lantsberry, F.C.A.H., “On the Properties of Some Alloys of Cu, Al and Mn”,

9th Report Alloys Research Committee, Proc. Inst. Mech. Eng., London, 119-139 (1910)

(Experimental, Mechan. Prop.)

[1929Mor] Morlet, E., “On Cu-Al with Mn (Co)” (in French), Compt. Rend. Acad. Sci. Paris, 189,

102-104 (1929) (Experimental, Equi. Diagram, 2)

[1933Heu2] Heusler, O., “Lattice Structure and Ferromagnetism of Mn-Al-Cu Alloys. Part 2: Magnetic

and Electrical Investigations” (in German), Z. Elektrochem, 39, 645-646 (1933)

(Experimental, Crys. Structure, 2) see also [1934Heu]

[1933Val] Valentiner, S., Becker, G., “Investigations on Heusler Alloys” (in German), Z. Phys., 83,


[1934Fue] Fuess, V., “Al-Cu-Mn” (in German), in “Metallographie des Aluminiums und seiner

Legierungen”, Berlin, 144-148 (1934) (Review, 4)

[1935Val] Valentiner, S., Becker, G., “On Heusler Alloys” (in German), Z. Phys., 93, 629-633 (1935)

(Experimental, 2)

[1943Mon] Mondolfo, L.F., “Metallography of Aluminium Alloys”, Wiley & Sons. Inc., London, 79-81

(1943) (Review, 3)

[1947Ano] Anonymous, “Cu-Mn-Al Alloys”, The Engineer, 183(4766), 470-471 (1947) (Review, 5)

[1948Hum] Hume-Rothery, W., “The Effect of Mn, Fe and Ni on the / Brass Equilibrium”, Philos.

Mag., 39, 89-97 (1948) (Theory, Equi. Diagram, 13)

[1948Sha] Sharma, A.S., “The Metallography of Commercial Alloys of the Duralumin Type”, Trans.

Indian Inst. Met., (1), 39-53 and (2), 11-44 (1948) (Experimental, 43)

[1952Han] Hanemann, H., Schrader, A., “Ternary Alloys of Aluminium” (in German), in “Atlas

Metallographicus III”, part 2, Düsseldorf, 81-85 (1952) (Review, 6)

[1952Haw] Haworth, J.B., Hume-Rothery, W., “The Effect of Four Transitional Metals ob the / Brass

Type of Equilibrum”, Philos. Mag., 43 (7), 613-631 (1952) (Experimental, Equi. Diagram,

23)

[1954Iva] Ivanov-Skoblikov, N.N., “The System Cu-Mn-Al” (in Russian), Zap. Leningrad. Gornogo

Inst., 29(3), 152-180 (1954) (Review, 147)

[1960Spe] Spegler, H., “The Inportance of Research on Eutectics and its Application to Ternary

Eutectic Aluminiun Alloys” (in German), Metall, 14, 201-206 (1960) (Review, Theory, 11)

[1963Oxl] Oxley, D.P., Tebble, R.S., Williams, K.C., “Heusler Alloys”, J. Appl. Phys., 34, 1362-1364


[1964Tes] Teslyuk, M.Yu., Kripyakevich, P.I., Frankevich, D.P., “New Laves Phases Containing Mn”

(in Russian), Kristallografiya, 9, 558-559 (1964) (Experimental, Crys. Structure, 13)

[1966Sch] Schubert, K., “Structure Research on Metallic Phases” (in German), Metall, 20, 424-430

(1960) (Review, Theory, Crys. Structure, 12)

[1966Vul] Vul'f, B.K., Chernov, M.N., “Influence of Ternary Intermetallic Compounds on the Heat

Resistance of Deformed Aluminium Alloys” (in Russian), Tsvet. Metallurgiya, 147-152

(1960) (Experimental, Mechan. Prop., 15)

[1968Joh3] Johnston, G., “Neutron Diffraction Investigation of Ternary Manganese Alloys”, At.

Energiya, 11(4), 18-24 (1968) (Experimental, Crys. Structure, 15) see also [1968Joh1] and

[1968Joh2]

[1969Gai] Gaillard M., “The Influence of Addition Elements on the Structure of Cu-Al Alloys” (in

French), Mem. Artillerie Franc., 43, 11-42 (1969) (Experimental, Equi. Diagram, 21)

[1969Mai] Maitre, F.Le., “Phase Transformation of Cu-Al Alloys” (in French),

Cuivre-Laitons-Alliages, 107, 8-21 (1969) (Experimental, Equi. Diagram, 10)

[1974Lis] Lisse, J.P., Navrot, F., Pernot, N., Dubois, B., “Precipitation Phenomena during Heat

Treatment of the Phase in Solid Heusler Alloy Specimens” (in French), Mem. Sci. Rev.

Metall., 71, 63-66 (1974) (Experimental, Equi. Diagram, 7)

88


MSIT®

Al–Cu–Mn

[1975Gre] Green, M.L. Chin, G.Y. “Deformation and Fracture of Polycrystalline Cu2MnAl”, Metall.

Trans. A, 6A, 1118-1122 (1975) (Experimental, Mechan. Prop., 9)

[1980Bra] Brandes, E.A., Flint, R.F., “Mn-Phase Diagrams”, Manganese Phase Diagrams,

Manganese Center, Paris, France, 78-79 (1980) (Review, Experimental, 4)

[1981Bre] Brezina, P., “Heat Treatment of Complex Al Bronzes”, Int. Met. Rev., 27(2), 77-120 (1981)

(Review, Mechan. Prop., Equi. Diagram, 210)

[1981Wat] Watanabe H., Sato, E., “Phase Diagram in Al Alloys” (in Japanese), J. Jpn. Inst. Light Met.,

31(1), 64-79 (1981) (Review, Theory, Equi. Diagram, #, 22)

[1982Kan] Kang, S.-J., Stasi, M., Azou, P., “Influence of Mn on Phase Transformations in Cu-Al

Alloys” (in French), Mem. Sci. Rev. Met., 79(5), 229-234 (1982) (Experimental, 12)

[1983Koz4] Kozubski, R., Soltys, J., “Decomposition of the Heusler Alloys Cu2.00Mn1.00Al1.00 During

Isochronal Annealing”, Conference DIMETA-82, Tihany, Hungary, Trans. Tech.

Publications, Rockport, 549-551 (1983) (Experimental, 7) see also [1983Koz1-3]

[1987Sch] Shubert, K., “On the Bindings in the Elements between V and Ga (I). Phases from V to Fe”,

Crys. Res. Technol., 24(4), 517-525 (1987) (Theory, Crys. Structure, 33)

[1988Dan] Danilov, A.N., Likhachev, V.A., “Nature of Matrix Phases in CuAl(Ni,Mn) Alloys” (in

Russian), Fiz. Metall. Metalloved., 65(6), 1176-1181 (1988) (Experimental, Crys.

Structure, 7)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Mn)(h1)

1079-707

cP20

P4132

Mn

a = 631.5 [V-C2]

dissolves 40 at.% Al [1999Liu]

( Mn)(r)

< 710

cI58

I43m

Mn

a = 891.39 [V-C2]

(Al)

< 660

cF4

Fm3m

Cu

a = 404.88 pure Al, 24°C

[V-C2]

2, Cu1-xAlx< 363

-

TiAl3

- 0.22 x 0.235 [Mas, 1985Mur]

long period superlattice

0, Cu1-xAlx1037-964

- - 0.298 x 0.324

[Mas, 1985Mur]

0, Cu1-xAlxCu2Al

1022-780

- - 0.31 x 0.402

[Mas, 1985Mur]

1, Cu9Al4< 873

cP52

P43m

Cu9Al4

a = 871.32

a = 870.68

at 33.8 at.% Al, [V-C2]


, Cu1-xAlx< 686

hR*

a = 869

= 89.78°

0.381 x 0.407 [Mas, 1985Mur]

at x = 38.9 [V-C2]

1, Cu1-xAlx958-848

cI2 ?

W (?)

- 0.379 x 0.406

[Mas, 1985Mur]

89


MSIT®

Al–Cu–Mn

2, Cu1+xAl

850-560

hP4

P63/mmc

NiAs

a = 414.6

c = 506.3

0.47 x 0.78

[Mas, 1985Mur, V-C]

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 59.8 at.% Cu, [Mas2, 1994Mur]


2, Cu11.5Al9(r)

< 570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu, [Mas2, 1985Mur]


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu

[V-C2, Mas2, 1985Mur]


2, CuAl(r)

< 569

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

[V-C]

, CuAl2< 591

tI12

I4/mcm

CuAl2

a = 606.3

c = 487.2

[V-C]

, Mn4Al3(h)

1260-870

hP2

P63/mmc

Mg

a = 269.0 to 270.5

c = 438.0 to 426.1

40.0 to 46.8 at. % Al

[Mas, 1987McA, 1999Liu]

MnAl(m)

metastable

tP2

P4/mmm

AuCu

a = 277 to 279

c = 354 to 358

ferromagnetic, about 55 at.% Mn,

formed from at rapid or medium

cooling rates

Mn5Al8(h)

1048-957

- - 61.8 to 70.0 at.% Al

[Mas, 1987McA]

Mn5Al8(r)

< 987

hR26

R3m

Cr5Al8

a = 1274

c = 1586

53.0 to 68.6 at.% Al

[Mas, 1987McA]

Mn4Al11(h)

1002-895

oP160

Pnma

a = 1479

b = 1242

c = 1259

71.3 to 75.0 at. % Al

[Mas, 1987McA]

latt. par. from [1961Tay]

Mn4Al11(r)

< 915

aP15

P1

Mn4Al11(r)

a = 509.2

b = 886.2

c = 504.7

= 85.31°

= 100.41°

= 105.34°

[V-C, 1987McA]

Structure: [1958Bla]

Mn3Al10 hP26

P63/mmc

Mn3Al10

a = 754.3

c = 789.8

metastable, formed at cooling rates faster

than 0.2 K s-1 [1971Goe]

Structure: [1959Tay]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

90


MSIT®

Al–Cu–Mn


, MnAl4 (h)

< 923

hP*

or oP*

a = 1995

c = 2452

a = 679.5

b = 934.3

c = 1389.7

[1987McA]

[1987McA]

, MnAl4 (r)

< 690

hP* a = 2840

c = 1240

[1987McA]

MnAl6 oC28

Cmcm

MnAl6

a = 755.18

b = 649.78

c = 887.03

[V-C, 1987McA]

, Mn1-x-yCuxAly Mn(h2)

1246-1143

Cu

< 1083

cF4

Fm3m

Cu

a = 386.2

a = 361.48

0 x 1

at x = 0, y = 0 [V-C]

at x = 1, y = 0, 25°C [V-C]

, Mn1-x-yCuxAly Cu3Al

1049-761

( Mn)(h3)

1143-1079

MnAl(h)

1191-840

'

''

cI2

Im3m

W

cP2

Pm3m

CsCl

cF16

MnCu2Al

a = 294.6

a = 308.1

range see Figs. 6 to 9

at x = 0.757, y = 0.243,

680°C [1985Mur]

at x = 0, y = 0 [V-C]

48.7 to 65.5 at.% Al [1987McA],

structure [1990Ell]

superstructure of

superstructure of ´

* 1,

Mn6+xCu4+yAl29-x-y

< 1020

oB156

Bbmm

Mn6Cu4Al29

a = 2420

b = 1250

c = 772

[1938Pet],

structure: [1954Rob]

0 x 2, 0 y 1, y x [1966Koe]

* 2,

Mn3Cu5Al11

< 700

oP380 a = 1210

b = 2408

c = 1921

[1943Gue, 1966Koe]

* 3,

Mn(Cu0.75Al0.25)2

< 550

cF24

Fd3m

MgCu2

a = 690.46 [1968Joh2]

antiferromagnetic ordering

of the Mn atoms


Mn Cu Al

L + Mn5Al8 1 1020 p7 L

Mn5Al8

1

21.3

26.6

21.3

11.4

9.5

11.4

67.3

63.9

67.3

L + Mn5Al8 1 + Mn4Al11 970 U1 L

Mn5Al8

1

18.7

26.7

21.2

8.6

7.3

11.0

72.7

66.0

67.8

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

91


MSIT®

Al–Cu–Mn

L + Mn5Al8 + 1 830 U2 L

Mn5Al8

1

8,4

27.6

23.0

21.1

34.2

12.7

23.9

12.4

54.7

59.7

53.3

66.5

L + Mn4Al11 1 + MnAl4 825 U3 L

1

(6.4)

20.6

(8.5)

10.3

(85.1)

69.1

+ 1 2 700 p12

1

6.0

18.8

41.9

12.4

52.1

68.8

+ 2 638 e11 7.0

3.2

45.0

61.4

48.0

35.4

+ ( Mn) 638 e12

( Mn)

24.4

3.3

69.0

43.4

62.8

1.5

32.2

33.9

29.5

L + MnAl4 1 + MnAl6 625 U4 L

1

(3.8)

18.9

(3.9)

9.9

(92.3)

71.2

L + 2 + 623 U5

L + 1 + 622 U6 L

1

2.1

1.2

17.1

31.8

49.2

11.9

66.1

49.6

71.0

L + MnAl6 1 + (Al) 616 U7 L

1

(Al)

(1.1)

17.9

(0.8)

(7.4)

10.1

(0.5)

(91.5)

72.0

(98.7)

+ 1 + 2 603 U8

1

1.2

16.5

50.5

12.5

48.3

71.0

L + 1 + 582 U9 L

1

1.4

16.6

29.4

11.6

69.2

71.8

+ 2 + 565 U10 0.4

1.8

57.0

61.2

42.6

37.0

+ ( Mn) 3 550 p15

( Mn)

15.9

79.5

63.8

1.2

20.3

19.3

L (Al) + 1 + 547 E2 L

(Al)

1

(0.4)

(0.1)

16.0

(17.0)

(2.4)

9.9

(82.6)

(97.5)

74.1

+ ( Mn) 3 + 520 U11

( Mn)

18.3

80.3

24.7

65.1

1.2

68.8

16.6

18.5

6.5

+ ( Mn) 3 + 420 U12

( Mn)

14.6

78.7

4.6

61.6

1.2

62.3

23.8

20.1

33.1

3+ + 400 E3 7.9

3.6

2.8

68.1

77.6

66.3

24.0

18.8

30.9


Mn Cu Al

92


MSIT®

Al–Cu–Mn

Fig

. 1a:

A

l-C

u-M

n.

Rea

ctio

n s

chem

e, p

art

1

Cu

-Mn

Al-

Cu

Al-

Mn

Al-

Cu

-Mn

l +

βΓ

10

37

p6

β l

+ γ

10

97

e 1

L +

Mn5A

l 8 M

n4A

l 11+

τ 19

70

U1

l+

β ε

12

62

p1

L +

εβ

11

35

?p3

Mn5A

l 8+

Mn4A

l 11+

τ 1

(βM

n)

(αM

n),

γ7

06

d1

l +

ε2

η6

24

p13

β Γ

+ ε2

83

6e 8

l +

βε 2

85

1p10

l +

Γβ

95

8e 4

l γ

+ β

10

32

e 2

Lβ

+ Γ

94

0e 5

L

γ +

β8

90

e 6

L +

Mn5A

l 8τ 1

10

20

p7

L +

Mn5A

l 8β

+τ 1

83

0U2

β +

τ 1 τ2

70

0p12

L +

ε2

β +

η6

23

U5

L+β

+η

L +

Mn4A

l 11

MnA

l 4 +

τ1

82

5U3

β (β

Mn

) + Γ

63

8e 12

β τ2 +

Γ6

38

e 11

L +

MnA

l 4τ 1

+ M

nA

l 66

25

U4

l (

Al)

+ M

nA

l 6

65

8e 10

l +

MnA

l 4 M

nA

l 6

70

5p11

β(β

Mn

)+M

n5A

l 8

83

3e 9

ε β

+ (

βMn)

87

2e 7

l+

Mn4A

l 11

MnA

l 4

92

3p9

l+

Mn5A

l 8M

n4A

l 11

10

00

p8

β ε

+ (β

Mn)

10

27

e 3

l +

β

Mn5A

l 8

10

60

p5

γ +

β (β

Mn)

10

67

p4

l+

ε β

11

81

p2

Mn

4A

l 11+

MnA

l 4+

τ 1

L+

Mn4A

l 11+

τ 1

MnA

l 4+

MnA

l 6+

τ 1

Mn5A

l 8+

β+τ 1

L+

MnA

l 4+

τ 1

U12

L+

MnA

l 6+

τ 1U7

ε 2+β

+ηU8U10

U11

L+

β+τ 1

93


MSIT®

Al–Cu–Mn

Al-

Mn

Fig

. 1b

:

Al-

Cu

-Mn

. R

eact

ion s

chem

e, p

art

2

Cu

-Mn

Al-

Cu

Al-

Cu

-Mn

L +

η

θ5

91

p14

β +

τ1

τ 2+

η6

03

U8

β +

(βM

n)

τ 3

55

0p15

l (

Al)

+ θ

548.2

e 16

55

9e 15

βγ

+ Γ

ε 2Γ

+ η

56

0e 14

L +

η

τ 1+

θ5

82

U9

β +

τ 2

Γ+

η5

69

U10

β ε 2

+ Γ

+ η

56

2E1

L (

Al)

+ θ

+ τ1

547.5

E2

β τ3 +

Γ +

γ4

00

E3

β +

(βM

n)

τ3 +

Γ4

20

U12

β +

(βM

n)

τ 3+

γ5

20

U11

ε 2+β

+η

τ 1+τ2+η

β+Γ+

ητ 2

+Γ+η

γ+(β

Mn

)+τ 3

β+τ 3

+Γ(β

Mn

)+τ 3

+Γ

τ 3+Γ

+γ

L +

β

η +

τ1

62

2U6

L +

MnA

l 6τ 1

+ (

Al)

61

6U7

β+η+

τ 1(A

l)+

Mn

Al 6

+τ 1

L+

(Al)

+τ 1

L+

η+τ 1

β+Γ+

ε 2

L+

β+η

L+

β+τ 1

β+τ 1

+τ2

β+τ 2

+Γ

L+

MnA

l 6+

τ 1L

+(A

l)+

Mn4A

l 6β+

(βM

n)+

Γ

β+τ 2

+η

τ 1+θ

+η

L+

τ 1+θ

β+τ 3

+γ

(Al)

+ θ

+τ 1

94


MSIT®

Al–Cu–Mn

20

40

60

80

20 40 60 80

20

40

60

80

Mn Cu


Axes: at.%

p7

U4

U5

MnAl6 (Al)MnAl4

Mn4Al11

p2

p1

ε

800

U6

ηU9

θ

E2

U7

Γ

U3

U2

β

γ

850900

100095

0

900

950

1000

1050

1100

115012

001250

1300

e5

e6

p3

τ

1050

U1

Mn5Al8

ε2

10

10

90

Mn 12.00Cu 0.00Al 88.00

Mn 0.00Cu 12.00Al 88.00


Axes: at.%

650

640

630

620

610

660680

700

U7, 616

U4, 625

MnAl4

τ1

(Al)

MnAl6

Al

Fig. 2: Al-Cu-Mn.

Liquidus surface

Fig. 3: Al-Cu-Mn.

Liquidus surface of

the Al corner after

[1991Phi]

95


MSIT®

Al–Cu–Mn

Mn 3.00Cu 0.00Al 97.00

Mn 0.00Cu 3.00Al 97.00


Axes: at.%400

450

550

600

650 MnAl6 τ1

θ

U7

E2

(Al)+τ1+L

(Al)+MnAl6+L

500

Al

Mn 3.00Cu 0.00Al 97.00

Mn 0.00Cu 3.00Al 97.00


Axes: at.%

650

640

620

610

600

590

580

570

550

560

630

(Al)+MnAl6+L

(Al)+τ1+L

Al

Fig. 5: Al-Cu-Mn.

Solvus of the (Al)

solid solution after

[1961Phi]

Fig. 4: Al-Cu-Mn.

Solidus of the (Al)

solid solution after

[1961Phi]

96


MSIT®

Al–Cu–Mn

20

40

60

80

20 40 60 80

20

40

60

80

Mn Cu


Axes: at.%

γ

β

ΓβL

τ1

Mn4Al11

Mn5Al8

ε(βMn)

γ L+γ

L+β

ε+β

β+MnAl

βMn+ε

L+τ1

L+Γ

β+Γ

β+γ

L+γ

(βMn)+γ

β(βMn)+βL+β

β+γ

L+Mn5Al8

20

40

60

80

20 40 60 80

20

40

60

80

Mn Cu


Axes: at.%

γ

(βMn)

Mn5Al8

Mn4Al11

L

β Γ

τ1

β+γ(βMn)+γ

(βMn)+β

β+Mn 5Al8

L+τ1

L+β

β+Γ

MnAl4

Fig. 6: Al-Cu-Mn.


950°C

Fig. 7: Al-Cu-Mn.


850°C

Fig. 6: Al-Cu-Mn.


950°C

97


MSIT®

Al–Cu–Mn

20

40

60

80

20 40 60 80

20

40

60

80

Mn Cu


Axes: at.%

γ

(αMn)

Mn 5

Al 8

Mn4Al11

MnAl4

L

Γβ

τ1

τ2

(βMn)+β

(βMn)+γ

β+Γ

β+Mn 5Al 8

β+τ1

L+τ1

β+γ

L+β

L+MnAl6

Mn5Al8+(βMn)

(βMn)

(αMn)+γ

ε2

MnAl6

L+β+τ1

20

40

60

80

20 40 60 80

20

40

60

80

Mn Cu


Axes: at.%

γ

Γ

η

θ

MnAl6MnAl4

Mn4Al11

(βMn)

(αMn)

τ3

τ1

τ2

β

(αMn)+γ

(βMn)+Γ

β+(βMn) β+Γ

γ+Γ

η+Γ

η+θ

(αMn)+(βMn)+ γ

τ1 +τ

2

(βMn)+Γ+τ3 τ

3+γ+Γ

(βMn)+β+Γ

(Al)+τ1+θ

(Al)

Mn5Al8

Fig. 9: Al-Cu-Mn.


20°C

Fig. 8: Al-Cu-Mn.


700°C

98


MSIT®

Al–Cu–Nb

Aluminium – Copper – Niobium

Rainer Schmid-Fetzer

Literature Data

The ternary compound Nb(Cu,Al)2 ( ) has been prepared by solid state sintering of the constituent elements

between 1000 and 1100°C [1964Now] and [1965Oes] or by arc melting the components and annealing the

solidified samples [1965Ram] and [1968Hun]. The NbCuAl composition of this -phase occurring in

diffusion couples of Nb with Al-Cu-In alloys has also been observed by electron microprobe analysis

[1978Dew]. The structure of the Laves phase has been investigated by X-ray powder diffraction and the

lattice parameters agree reasonably well [1964Mar, 1964Sch, 1965Oes, 1965Ram] and [1968Hun].

Observation of a cubic Laves phase (MgCu2 type) in samples quenched from above 1000°suggests that

may exhibit polymorphism [1965Oes]. A second ternary compound, Nb6(Cu,Al)7 ( ) has been prepared by

similar methods and studied by powder X-ray [1965Oes] and [1968Hun]. A composition of Nb(Cu,Al)

might be possible for the phase [1965Oes]. However, the occurrence of was not observed by [1978Sav]

and [1980Sav] in their microstructural and X-ray study of Nb-Al-rich samples which had been melted,

quenched and annealed at 800°C. Phase relations in ternary alloys have been studied using X-ray diffraction

with about 40 samples annealed at 1000°C in evacuated silica capsules and air-cooled [1968Hun]. Other

results from fewer samples both for the same temperature [1964Now] and [1965Oes] and for 900°C

[1965Ram] are in agreement with [1968Hun]. The solubility of Cu in Nb-Al phases are in mutual agreement

[1968Hun, 1978Sav] and [1980Sav]. Both the occurrence of a four-phase reaction (Nb)+ Nb2Al+ and

the possible existence of an additional ternary phase at 1300°C are mentioned [1965Oes]. Phase equilibria

at 1000°C and 1400°C have also been studied with 7 and 5 samples, respectively, using similar techniques

by [1990Ric]. An assessment of the then available literature data was published by [1991Bae].

Binary Systems

The three binary systems are accepted from the MSIT Binary Evaluation Program [2002Rom, 2003Gro,

2003Vel] which go substantially beyond the recent reviews given for Al-Cu [1994Mur] and Al-Nb

[1981Ell], and to some extent also for Cu-Nb [1994Cha].

Solid Phases

Data on all solid phases are given in Table 1. Crystal structure data of ternary phases related to the phase

are compiled by [1969Tes].

Isothermal Sections

The isothermal section at 1000°C, given in Fig. 1, is based mainly on the observations of [1968Hun], but

has been revised in order to be consistent with the edge binaries, especially with the liquid phase. In his

original work, [1968Hun] presented some solid state equilibria which do not pertain to the 1000°C isotherm,

but which may develop during his slow air cooling process. These are the equilibria +CuAl+NbAl3 and

NbAl3+CuAl+CuAl2. The tie lines shown erroneously for these equilibria at 1000°C have been repeated in

several reviews [1990Kum, 1979Dri, 1979Cha, 1970Ali].

The single phase regions of and given by [1968Hun] have also been modified in Fig. 1 in order to take

into account other work [1965Oes]. The questionable binary Nb3Al2 phase was not found in ternary

samples.

The isothermal section at 1400°C, Fig. 2, is less well established and based on the 15 sintered samples of

[1990Ric] which were all above 25 at.% Nb. The tie line directions towards the liquid Al-Cu rich phase

could only be estimated.

99


MSIT®

Al–Cu–Nb


Recent interest is in shape memory alloys for high temperature applications. Addition of 0.27 mass% Nb to

Cu86.5-Al13.5 (mass%) alloy increases the Ms temperature from 250 to 313°C, which decreases with

further Nb addition up to 7.86 mass%. In these alloys precipitation of and to a smaller extent also of

phase was found [2000Mor]. Similar data are found in [1999Lel].

The influence of Cu on the critical temperature for superconductivity in the Nb3Al phase has been measured

by [1978Sav] and [1980Sav] and is found to increase from 7.2 K to 9.7 K upon addition of 2.4 at.% Cu.

References



[1964Mar] Markiv, V.Ya., Voroshilov, Yu.V., Kripyakevich, P.I., Cherkashin, E.E., “New Compounds

of the MnCu2Al and MgZn2 Types Containing Aluminium and Gallium”, Sov. Phys.

-Crystallogr. (Engl. Transl.), 9(5), 619-620 (1964), translated from Kristallografiya, 9,


[1964Now] Nowotny, H., Oesterreicher, H., “The Crystal Structures of -TaNi3, Ta(Cu,Al)2,

Nb(Cu,Al)2 and Ta6(Cu,Al)7” (in German), Monatsh. Chem., 95, 982-989 (1964) (Crys.


[1964Sch] Schubert, K., Raman, A., Rossteutscher, W., “Some Structure Data of Metallic Phases (10)”

(in German), Naturwissenschaften, 51, 506-507 (1964) (Crys. Structure, Experimental, 0)

[1965Oes] Oesterreicher, H., Nowotny, H., Kieffer, R., “Study on the Ternaries (V,Nb,Ta)-Cu-Al and

Ta-Ni-Cu” (in German), Monatsh. Chem., 96, 351-359 (1965) (Equi. Diagram, Crys.


[1965Ram] Raman, A., Schubert, K., “On the Constitution of Alloys Related to TiAl3. III: Study on

some T-Ni-Al and T-Cu-Al Systems” (in German), Z. Metallkd., 56, 99-104 (1965) (Crys.


[1968Hun] Hunt, Jr.C.R., Raman, A., “Alloy Chemistry of F(U)-Related Phases I. Extension of - and

Occurrence of ’-Phases in the Ternary Systems Nb(Ta)-X-Al (X = Fe, Co, Ni, Cu, Cr,

Mo)”, Z. Metallkd., 59, 701-707 (1968) (Equi. Diagram, Crys. Structure, Experimental, #,

*, 14)

[1969Tes] Teslyuk, M.Yu., “Intermetallic Compounds with Structure of Laves Phases”, in

“Intermetallic Compounds with Structure of Laves Phases”, (in Russian), Moscow, Nauka,

1969, 1-138 (1969) (Crys. Structure, Review, Theory)

[1970Ali] Alisova, S.P., Budberg, P.B., “Al-Cu-Nb” (in Russian), Diag. Sost. Metal. Sistem, Mater.

Vses. Sovesh., 125 (1970) (Equi. Diagram, 1)

[1978Dew] Dew-Hughes, D., Luhmann, T.S., “The Thermodynamics of A15 Compound Formation by

Diffusion from Ternary Bronzes”, J. Mater. Sci., 13, 1868-1876 (1978) (Crys. Structure,

Experimental, 41)

[1978Sav] Savitsky, E.M., Jefinov, Yu.V., Muchin, G.G., Frolova, T.M., “Structure and Properties of

Equilibrium and Rapidly Quenched Cu-Containing Alloys”, Rapidly Quenched Metals III,

1, 167-170 (1978) (Equi. Diagram, Experimental, #, 20)

[1979Cha] Chang, Y.A., Neumann, J.P., Mikula, A., Goldberg, D., “Cu-Al-Nb”, in “Phase Diagrams

and Thermodynamic Properties of Ternary Cu-Metal Systems”, INCRA Monograph VI,

NSRDS, USA (1979) (Equi. Diagram, Crys. Structure, Review, #, 4)

[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova V., Rokhlin, L.L.,

Turkina, N.I., “Cu-Al-Nb” in “Binary and Multicomponent Copper-Base Systems” (in

Russian), Nauka Moskow, 78-79 (1979) (Equi. Diagram, 1)

[1980Sav] Savitsky, E.M., Jefimov, Yu.V., Frolova, T.M., Shomova, N.A., “Microstructure and

Properties of Alloys V(Nb)-Al(Ga,Si,Ge,Sn)-Cu” (in German), J. Less-Common Met., 76,

81-98 (1980) (Equi. Diagram, Experimental, #, 41)

100


MSIT®

Al–Cu–Nb

[1981Ell] Elliott R.P., Shunk, F.A., “The Al-Nb System”, Bull. Alloy Phase Diagrams, 2, 75-81

(1981) (Equi. Diagram, Crys. Structure, Review, #, 31)

[1985Mur] Murray, J.L., “The Al-Cu System”, Int. Met. Rev., 30, 211-233 (1985) (Equi. Diagram,

Crys. Structure, Review, #, 230)




[1990Kum] Kumar, K.S., “Ternary Intermetallics in Aluminium-Refractory Metal-X Systems (X = V,

Cr, Mn, Fe, Co, Ni, Cu, Zn)”, Int. Mater. Rev., 35(6), 293-327 (1990) (Crys. Structure, Equi.

Diagram, Review, 158)

[1990Ric] Rickes, B., “Reactiones in the Al-Cu-Nb-(O) System, Constitutional sTudies of Syntered

Engineering Materials”, Dissertation, Univ. Stuttgart, (1990) (Experimental, Equi.

Diagram, 161)


Enthalpy of Aluminium in Some Phases with Cu and Cu3Au Structures”, J. Less-Common


[1991Bae] Bätzner, Ch., Hayes, F., Ran, Q., Schmid, E.E., Schmid-Fetzer, R. , ”Aluminium - Copper

- Niobium”, MSIT Ternary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.),

MSI, Materials Science International Services GmbH, Stuttgart; Document ID:

10.16131.1.20, (1991) (Crys. Structure, Equi. Diagram, Assessment, 14)

[1993Bar] Barth, E.P., Sanchez, J.M., “Observation of a New Phase in the Niobium-Aluminium

System” Scr. Metall. Mater., 28, 1347-1352 (1993) (Crys. Structure, Equi. Diagram,

Experimental, 9)

[1994Cha] Chakrabarti, D.J., Laughlin, D.E., “Cu-Nb (Copper-Niobium)” in “Phase Diagrams of

Binary Copper Alloys”, ASM International, Materials Park, OH, 266-270 (1994) (Equi.

Diagram, Crys. Structure, Thermodyn., Review, 22)


Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM International,






[1999Lel] Lelatko, J., Morawiec, N., Koval’, Yu.N., Kolomyttsev, V.I., “Structure and Properties of

High-Temperature Alloys with the Effect of Shape Memory in the System Cu-Al-Nb”, Met.

Sci. Heat Treat., 41(7-8), 351-353 (1999) (Experimental, Magn. Prop., Mech. Prop., 5)

[2000Mor] Morawiec, H., Leltko, J., Koval, Yu., Kolomytzev, V., “High-Temperature Cu-Al-Nb

Shape memory Alloys”, Mater. Sci. Forum, 327-328, 291-294 (2000) (Experimental,

Mechan. Prop., 8)







[2002Rom] van Rompaey, T., “Cu-Nb (Copper-Niobium)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart; Document ID: 20.12479.1.20, (2002) (Crys. Structure, Equi. Diagram,

Assessment, 16)

[2003Gro] Gröbner, J., “Al-Cu (Aluminium-Copper)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart; to be published, (2003) (Equi. Diagram, Assessment, Crys. Structure, 68)

101


MSIT®

Al–Cu–Nb

[2003Vel] Velikanova, T., Ilyenko, S., “Al-Nb (Aluminium-Niobium)”, MSIT Binary Evaluation


Services GmbH, Stuttgart; to be published, (2003) (Crys. Structure, Equi. Diagram,

Assessment, 81)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 pure Al at 25°C [Mas2]

0 to 2.48 at.% Cu [Mas2]

(Cu)

< 1084.62

cF4

Fm3m

Cu

a = 361.46

a = 361.52 +

25.26xAl

at 25°C [Mas2],

0 to 19.7 at.% Al [Mas2]


[1991Ell], quenched from 600°C,

xAl=0 to 0.152

practically no solubility for Nb

[1994Cha]

(Nb)

< 2469

cI2

Im3m

W

a = 330.04 pure Nb, [1994Cha]

dissolves up to 1.2 at.% Cu at 1080°C

[1994Cha]

dissolves up to 21.5 at.% Al [Mas2]

, Cu3Al(h)

1049-559

cI2

Im3m

W

a = 295.64

70.6 to 82 at.% Cu [1985Mur]

at 672°C in +(Cu) alloy (Ti free)

[1998Liu]

dissolves at least 0.81 at.% Ti [2001Liu]

1 cF16

Fm3m

BiF3

a = 585 metastable [1994Mur]

supercell of

2, Cu100-xAlx< 363

-

TiAl3long period

super-lattice

-

a = 366.8

c = 368.0

22 x 23.5 [Mas, 1985Mur]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu

(subcell only)

0, Cu100-xAlx Cu 2Al

1037-800

cI52

I43m

Cu5Zn8

- 31 x 40.2 [Mas2],

62 to 68 at.% Cu

[1998Liu]

1, Cu9Al4< 890

cP52

P3m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu [Mas2, 1998Liu];



, Cu100-xAlx< 686

hR*

R3m

a = 1226

c = 1511

38.1 x 40.7 [Mas2, 1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

1, Cu100-xAlx958-848

cubic? - 37.9 x 40.6

59.4 to 62.1 at.% Cu [Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.47 x 0.78

55.0 to 61.1 at.% Cu [Mas, 1985Mur,

V-C2], NiAs in [Mas2, 1994Mur]

102


MSIT®

Al–Cu–Nb

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2Cu47.8Al35.5

a = 812

b = 1419.85c = 999.28


2, Cu11.5Al9(r)

< 570oI24 - 3.5

Imm2Cu11.5Al9

a = 409.72

b = 703.13c = 997.93


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200c = 863.52

49.8 to 52.4 at.% Cu

[V-C2, Mas2, 1985Mur]Pearson symbol: [1931Pre]

2, CuAl(r)

< 560

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu

[V-C2]

Cu2Al3 hP5

Pm1

Ni2Al3

a = 410.6

c = 509.4

metastable [1994Mur]

~40 to 50 at.% Cu

, CuAl2< 591

tI12

I4/mcm

CuAl2

a = 606.7

c = 487.7

31.9 to 33.0 at.% Cu [1994Mur]

single crystal

[V-C2, 1989Mee]

’ tP6

distorted CaF2

a = 404.82

c = 581.17

Metastable [1994Mur]

Nb3Al cP8

Pm3n

Cr3Si

a = 518.6 [V-C2]

18.6 to 25 at.% Al [Mas2]

Nb2Al tP30

P42/mnm

CrFe

a = 994.3

c = 518.6

[V-C2]

30 to 42 at.% Al [Mas2]

NbAl3 tI8

I4/mmm

Al3Ti

a = 384.1 ± 1

c = 860.9 ± 2

[V-C2]

Nb3Al21350 < T < 1590

tP20

P42/mnm

Al2Zr3

a = 707 ± 8

c/a ~ 0.05

[1993Bar]

42.4 at.% Nb, equilibrium needs to be

checked

* ,

Nb(CuxAl1-x)2

hP12

P63 /mmc

MgZn2

a = 502

c = 830

a = 502.3

c = 809.0

a = 502

c = 808

x = 0.25 [1965Oes]

x = 0.50 [1968Hun]

x = 0.60 [1965Oes]

homogeneity range, see Fig. 1

[1965Oes];

probability of a cubic high temperature

polymorph (a = 711 pm) [1965Oes]

* ,

Nb6(Cu0.5Al0.5)7

hR13

R3m

(W6Fe7)

a = 502.9

c = 2736

prototype is tentative

[1965Oes, 1968Hun]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

103


MSIT®

Al–Cu–Nb

20

40

60

80

20 40 60 80

20

40

60

80

Nb Cu


Axes: at.%

L

NbAl3

τ

(Cu)

µ

Nb2Al

(Nb)

γ0

βθ´

L+τ

(Nb)+µ+(Cu)

τ+γ0

τ+β

τ+(Cu)

Nb2Al+τ

Fig. 1: Al-Cu-Nb.


1000°C

20

40

60

80

20 40 60 80

20

40

60

80

Nb Cu


Axes: at.%

L

(Nb)+L

(Nb)+θ´+L

Ni2Al+L

ττ+L

Ni2Al+τ

NbAl3

Ni2Alθ´

(Nb)

Fig. 2: Al-Cu-Nb

Partial isothermal

section at 1400°C

[1990Ric]

104


MSIT®

Al–Cu–Ni

Aluminium – Copper – Nickel

Alan Prince†, updated by K.C. Hari Kumar

Literature Data

Over the last many years several researchers have investigated the Al-Cu-Ni system due to the interest in

thermoelastic martensitic transformation exhibited by certain alloys of this system. This property is

responsible for the unique mechanical behavior of these alloys such as shape memory effect, superplasticity

and stress-induced martensitic transformations. These alloys have the potential to be used at higher

application temperatures ( 200°C) than the conventional shape memory alloys found in Al-Cu-Zn and

Ni-Ti systems ( 100°C) [1990Ye, 1998Pel, 2001Mot], even though it suffers from deterioration of

mechanical properties due to grain boundary embrittlement [1984Hus, 2001Mot].

Although much work has been reported on the constitution of the Al-Cu-Ni system, there is still no

definitive interpretation of the complete equilibria. Nevertheless, there is broad agreement on the major

features of the ternary phase diagram. Early constitutional studies were done by [1923Aus, 1923Bin,

1928Nis, 1936Gri1, 1936Gri2, 1938Ale, 1938Bra, 1940Bra, 1940Rap, 1941Tur, 1945Tur, 1948Koe,

1952Han, 1952Haw, 1956Bow, 1957Lu1, 1957Lu2, 1957Ray, 1972Bed, 1978Tho, 1983Haf, 1983Rud,

1985Li, 1988Ahm]. Later works include publications by [1990Sun, 1994Jia, 1998Pel, 2001Liu, 2003Wan].

[1923Aus] investigated the complete ternary system using 250 alloy compositions, with emphasis on

Cu-rich alloys containing 0 to 20 mass% Al, Ni. Thermal analysis was used to construct a ternary liquidus

surface and, from it, a series of vertical sections on which only the liquidus was given. The Al used by

[1923Aus] contained 0.7 mass% impurities. The salient information provided by this work is the presence

of a maximum in the liquidus surface running from NiAl to Cu3Al, the presence of a eutectic trough joining

the binary Ni-rich eutectic reaction L ( ,NiAl)+Ni3Al to the binary Al-Cu eutectic reaction

L (Cu)+( ,Cu3Al) and the claim that there is a further eutectic trough. This latter trough was said to join

the Al-Cu eutectic L (Al)+ , to the Al-Ni eutectic L (Al)+NiAl3. They concluded that there was neither

a ternary eutectic reaction nor the existence of a liquidus surface associated with any ternary compound.

[1923Bin] studied the liquidus surface Al-rich corner up to 12 mass% Cu, 10 mass% Ni, using low purity

Al (99.65 mass%). Using thermal analysis (5 K·min–1 cooling and heating rates), metallography and

high-temperature electrical resistance techniques they detected the presence of a ternary eutectic reaction,

L (Al)+ + , at about 540°C and another invariant reaction L+Ni2Al3 (Al)+ at 585 ± 5°C. [1923Bin] was

the first to mention the occurrence of a ternary phase and attributed the stoichiometry as NiCu2Al5. This

composition lies close to the Al-rich boundary of the phase as shown later by [1938Bra, 1948Koe,

1957Lu1] and [1957Lu2]. [1928Nis] confirmed the ternary eutectic reaction that [1923Bin] found and gave

the liquid composition as 67.5Al-0.5Ni (mass%) at 540°C. This is close to compositions quoted by later

investigators. Two ternary transition reactions were also detected with reaction temperatures of 600 and

585°C. [1928Nis] considered these reactions to be L+NiAl3 (Al)+ (585°C) with L at 74.5Al-2.5Ni

(mass%) and L+Ni2Al3 NiAl3+ (600°C) with L at 73Al-4Ni (mass%). Later works, [1948Koe] and

[1952Han], have established that these two transition reactions are L+Ni2Al3 (Al)+ and

L+NiAl3 (Al)+Ni2Al3, although there is discrepancy with respect to the temperature. [1936Gri1] reported

that the addition of 2 mass% Ni to 11.5 to 13.0 mass% Al bronzes raised the binary eutectoid horizontal,

( ,Cu3Al) (Cu)+ 1, from 570 to 605°C. [1936Gri2] refers to the effect of 6 mass% Ni and states that an

alloy with 10 mass% Al has a eutectoid at 780°C. This is not agreed by other researchers. [1938Ale] studied

over 100 alloy compositions in characterizing the equilibria in the region Cu-Ni-NiAl-Cu3Al. Total

impurities in the alloys, as determined spectrographically, were less than 0.1 mass%, which was an

improvement over the starting materials used by [1923Aus]. Thermal analysis, metallography and X-ray

powder diffraction techniques were used to elucidate the equilibria. Both liquidus and solidus surfaces were

reported in addition to five isothermal sections in the range 500-900°C. Thirteen vertical sections at constant

Al or Ni content and the section NiAl-Cu3Al were presented. The liquidus of the Cu3Al-NiAl section shows

good agreement with that of [1923Aus]. An invariant reaction, L+Ni3Al (Ni,Cu)+NiAl, is found to occur

105


MSIT®

Al–Cu–Ni

at 1250°C. The corresponding liquid composition is not given by [1938Ale] but a small region of primary

Ni3Al is shown in the vertical section at 60 mass% Ni. The most significant finding of [1938Ale] was of a

complete solid solution series between ordered bcc phase ( ,NiAl) and the disordered bcc phase ( ,Cu3Al)

with the appearance of solid immiscibility at 800°C with breakdown of the solid solution into two phases.

[1938Bra] used X-ray diffraction techniques to determine the phases present in the complete ternary system.

Very pure materials were used (99.992% Al, electrolytic Cu, 99.97% Ni) and all alloys were annealed for

72 h at temperatures that varied with composition. Powders were prepared from bulk samples and heated to

various temperatures (470-950°C), followed by cooling to room temperature at 10 K/h. They did not detect

the ( ) phase, but observed three related type phases (denoted , 1 and 2). The extent of the ternary

phase was delineated for the first time and its structure given as a deformed bcc. The simplest formula

proposed by [1938Ale] was NiCu3Al6. In a later paper [1940Bra] estimated that the constitution represented

the state of affairs at a temperature between 500 and 700°C. [1940Rap] determined the constitution from 0

to 40 mass% Cu, 0 to 30 mass% Ni using thermal, microscopic and X-ray techniques. A total of 162 alloy

compositions, prepared from 99.996 mass% Al, electrolytic Cu and 99.8 mass% Ni, were studied as-cast,

after slow cooling and after annealing at 530°C for 2 to 6 weeks followed by water quenching. Surprisingly

little detail is given of the results of this work. A liquidus projection is also reported by [1940Rap], but no

isothermal or vertical sections are given to substantiate the liquidus proposed. The projection shows five

ternary phases, designated X, Y, Z, T and U, with regions of primary separation within the range 1 to 10

mass% Ni. Eight invariant reactions are proposed. The ternary eutectic reaction at 546.6°C is the only

reaction that has been confirmed and is well-established. [1941Tur] examined the Cu3Al-NiAl section and

reported a value of 585°C for the ternary eutectoid temperature. [1946Smi] determined the ternary eutectoid

temperature by dilatometry and quoted 597 to 603°C. [1954Hay] re-determined the binary Al-Cu eutectoid

temperature as 565 ± 2°C and reported the ( ,Cu3Al) phase to have a composition 12.1Al-3.1Ni (mass%)

at the four-phase plane (605 ± 2°C). [1979Kuz] also found 605°C for the eutectoid temperature when 2

mass% Ni was added to the binary eutectoid. A major contribution was also made by [1948Koe]. A total of

250 alloy compositions in the region AlCu3Al-NiAl were studied. The region Cu-Ni-NiAl-Cu3Al was

excluded in the study and the liquidus isotherms down to 1000°C were taken from [1923Aus]. [1948Koe]

accepted the transition reaction L+Ni3Al (Ni,Cu)+ , reported by [1938Ale] and placed it at 10Al-47Ni

(mass%). [1948Koe] also determined the primary solidification fields in alloys cooled from the melt.

Isothermal sections were also determined at 900°C (48 h anneal), 700°C (72 h), 500°C (672 h) and 600°C

(unspecified annealing time). In a review of work on Al-rich alloys [1952Han] re-determined the

temperature and location of three invariant reactions near the Al-corner, established by previous

investigators. The transition reaction L+NiAl3 (Al)+Ni2Al3 was placed at 598.8°C, but it differs

substantially from the 630°C found by [1948Koe] and confirmed by [1982Ask]. The transition reaction

L+Ni2Al3 (Al)+ was placed at 561°C compared with 585°C [1923Aus] and [1928Nis] and ~590°C

[1948Koe]. Whereas the liquid phase composition quoted by [1952Han] for L+NiAl3 (Al)+Ni2Al3 agrees

closely with [1948Koe], 81.2Al-4.7Ni as against 80Al-4Ni (mass%), the liquid composition for the reaction

L+Ni2Al3 (Al)+ is 4 to 5 mass% Al lower than that reported by [1928Nis, 1948Koe]. [1957Ray]

questioned how accurately the boundaries of primary separation were determined by [1948Koe] and they

reinvestigated the region of primary separation of using 40 alloy compositions. It is a reflection of the

inconsistency between results in the Al-rich alloys that led [1961Phi] to conclude that it was not possible to

draw liquidus isotherms. [1952Haw] determined the phase boundaries adjoining the (Ni,Cu) and ( ,Cu3Al)

phase regions up to 1.5 at.% Ni at 672°C. For this very small composition range, 0 to 1.5 at.% Ni, 64 alloy

compositions were studied. The results agree with the phase boundaries of [1938Ale] at 700°C. [1956Bow]

examined the crystal structure of the ternary phase, using crystals extracted from slowly cooled melts. He

found evidence for two modifications. The 1 phase has a rhombohedral unit cell and corresponds to the

formula Ni1.2Cu4.8Al7. The 2 phase is cubic, a superstructure of the CsCl type, with the formula NiCu3Al6,

as noted for by [1938Bra]. Both 1 and 2 are based on a CsCl type arrangement of Al and heavy atoms,

the large unit cells being produced by two different ordered distributions of vacancies in place of heavy

atoms. [1957Lu1] and [1957Lu2] studied the phase region using 58 alloy compositions prepared from

very pure materials (99.992% Al, 99.999% Cu, 99.99 mass% Ni). All alloys were homogenized for 1680 h

at 650°C, powdered and the powders annealed for 24 h at 600°C, followed by cooling at 5 to 10 K/h to room

106


MSIT®

Al–Cu–Ni

temperature. Eight types of closely-related structures were found in the region. [1972Bed] studied the

effect of Ni additions on the extent of the 1 phase region at room temperature. Alloys were prepared from

high-purity elements, homogenized for 12 h at 900°C, cooled to 850°C and held for 24 h, then cooled to

750°C and held for a further 24 h. This stepwise cooling was continued with the temperature being dropped

by 50°C and the sample held for 48 h each temperature from 700 to 100°C. In total, alloys were soaked for

720 h throughout the temperature range. Alloys were examined by X-ray diffraction and metallography.

The solubility of Ni in the 1 phase was 3.4 at.% Ni on the section from 33.33Al-66.67Cu (at.%) towards

Ni, 1.8 at.% Ni on the 66.67 at.% Cu section and 5.4 at.% Ni on the 33.33 at.% Al section. This data is in

excellent agreement with [1938Bra] and [1948Koe]. Alloys in the Al-rich corner, with up to 33Cu-10Ni

(mass%) were homogenized at 375°C by [1983Haf]. Metallography was used to identify the phases in two-

and three-phase regions. Of 25 alloy compositions studied, 23 fell into the phase regions given by

[1938Bra]. [1983Rud] used microprobe analysis of a diffusion couple held for 8 h at 600 to 900°C between

5Al-90Cu (mass%) and Ni. There is fair agreement between [1983Rud] and [1938Ale] for the phase

boundary between (Ni,Cu) and (Ni,Cu)+Ni3Al at 900°C, but differs considerably at lower temperatures.

The (Ni,Cu)+Ni3Al boundary with Ni3Al is placed at higher Al contents by [1983Rud], who shows that Cu

substitutes for Ni in Ni3Al. This agrees with the data of [1985Mis]. [1985Li] examined an alloy containing

14.2Al-4.3Ni (mass%). At 900°C, only ( , Cu3Al) was observed; from 800 to 600°C ( ,Cu3Al)+ 1 coexist

and at 500°C (Ni,Cu)+ 1+( ,NiAl) are in equilibrium. This data agrees with results of [1938Ale].

[1988Ahm] reported that an alloy containing 14Al-10Ni (mass%) after heating to 350°C formed

(Ni,Cu)+ 1+( ,NiAl). This is in agreement with the 500°C section of [1948Koe] and the data of [1938Bra].

[1990Sun] reported that as-cast alloys 0.1-4.5Al86.4-90.7Cu9.1-9.7Ni (mass%) contained a martensite

phase, which transformed into equilibrium phases (Cu,Ni), 1 and the NiAl on tempering in the temperature

range 540-750°C. [1990Sun] also observed that Ni addition to Al-Cu pushes (Cu,Ni)/(Cu,Ni)+ 1 phase

boundary towards Al-end and the solubility of Ni in (Cu,Ni) increases with temperature. [1994Jia] reported

tie lines in the (Ni,Cu)+Ni3Al and Ni3Al+NiAl phase fields, occurring near the Al-Ni side of the system.

Samples were diffusion couples, annealed in sealed quartz capsules for 10-1000 h in the temperature range

800-1300°C and were subjected to microstructure as well as EPMA examination. [1998Pel] observed that

an alloy 3Ni-Cu-12Al (mass%) annealed at temperature greater than 415°C contained two phases consisting

of 1 and Cu-rich (Ni,Cu). [2001Liu] established tie lines in (Ni,Cu)+ 1 and ( 1+ ) phase fields, occurring

near the Al-Cu side of the system, at 700 and 800°C by preparing diffusion couples. EDS was used to

determine the phase compositions. [2003Wan] examined 112 water quenched samples prepared by

arc-melting and annealing in vacuum (10–3 torr) at 800°C for 30 days, using metallography, XRD and

EPMA. In three samples they observed NiAl coexisting as a separate phase with the disordered Cu-rich bcc

phase ( ,Cu3Al). They reported an isothermal section at 800°C with an unusual shape for the NiAl

phase-field.

Publication up to the year 1988 have been reviewed thoroughly by Alan Prince within the MSIT Evaluation

Program [1991Pri]. The present work proceeds with the evaluation, taking into account the new ternary and

edge binary data.

Binary Systems

Binary systems are accepted from the MSIT Binary Evaluation Program: Al-Cu from [2003Gro], Al-Ni

from [2003Sal] and Cu-Ni from [2002Leb].

Solid Phases

In addition to the solid phases associated with the binary systems a ternary phase region, designated in

Figs. 1, 3 to 5, has been well-established [1938Bra, 1948Koe, 1955Bow, 1956Bow, 1957Lu1, 1957Lu2,

1957Ray]. The definitive work is that of [1957Lu1, 1957Lu2]. They found 8 types of closely-related

structures of the phase; all show lines of the CsCl structure with superlattice reflections. The phase

structures are described as being based on the sequence of occupation of the cube centre position in the CsCl

lattice by heavy atoms (M = Cu or Ni) or by vacancies (V). Conventionally, the subscript of the notation i

is the number of layers in the unit cell. The 2 structure reported by [1955Bow, 1956Bow] is 5 of [1957Lu1,

107


MSIT®

Al–Cu–Ni

1957Lu2] and can be represented by the sequence (V)(M)(M)(M)(V) repeated, where M = Cu or Ni and V

= vacancy. The structure identified by [1955Bow, 1956Bow] is same as 8 of [1957Lu1, 1957Lu2]. It can

be represented by the sequence (V)(M)(M)(M)(M)(M)(M)(V) repeated. The region of homogeneity of

was originally determined by [1938Bra], Fig. 3. There is good agreement between this work and that of

[1948Koe], Fig. 4 and [1957Lu1, 1957Lu2], Fig. 5. [1957Lu1, 1957Lu2] also established the equilibrium

ranges of the different stacking variants of in this field (Fig. 5). [1957Ray] chemically extracted primary

crystals of from solidified melts and analyzed their compositions. Analyses were given for two crystals of

which the first lies within the phase region defined by [1938Bra, 1948Koe, 1957Lu1, 1957Lu2]; its

composition was 58Al-33.4Cu-8.6Ni (at.%). The second crystal contained 60.3Al-31.0Cu-8.7Ni (at.%) and

is within the phase region given by [1948Koe], just within the + region of [1938Bra] and on the / +

boundary of [1957Lu1, 1957Lu2].


There are no pseudobinary sections in the system, though the section Cu3Al-NiAl may be treated as a

pseudobinary above 800°C (Fig. 14). This is discussed below in “Temperature-Composition Sections”.


The invariant equilibria associated with the liquid phase are given in Table 2. This table is an assimilation

of results from [1923Bin, 1928Nis, 1938Ale, 1940Rap, 1948Koe, 1952Han, 1982Ask], with amendments

to incorporate the Al-Cu phases that are known to be in equilibrium with the melt in the binary system.

Although [1923Aus] gave no ternary invariant reactions, re-interpretation of the original data, with the

benefit of the knowledge gained from later works, indicates the presence of an invariant reaction at ~ 600°C

which can be identified as reaction U5 in Table 2. [1923Bin] found an invariant transformation reaction at

585 ± 5°C; it would currently be equated with U7, Table 2. As [1948Koe] only recognized the ( ,Cu3Al),

, and phases from the Al-Cu system, the reaction they proposed for U2, L+ +NiAl, has been

changed to L+ 0 1+( ,NiAl) and the reaction at U4, L+NiAl + according to [1948Koe] has been

altered to L+( ,NiAl) 2+ . Reactions U3 and U6 are additional to those given by [1948Koe]. The reaction

scheme is given in Fig. 6. It takes no account of the 0 1, 1 2 and 1 2 transformation in the Al-Cu

binary system.

An important invariant equilibrium is the one concerned with the eutectoidal decomposition of ( ,Cu3Al)

in the ternary system. There is general agreement on the effect of Ni in raising the binary eutectoid

temperature from 559°C [1938Ale, 1941Tur, 1946Smi, 1954Hay, 1979Kuz]. At higher temperatures the tie

triangles (Ni,Cu)+( ,Cu3Al)+( ,NiAl) and 1+( ,Cu3Al)+( ,NiAl) exist. The formation of these tie

triangles originates with the occurrence of a solid-state miscibility gap in the ( ,Cu3Al)/( ,NiAl) solid

solution at below 800°C, whereby equilibrium is established between the disordered ( ,Cu3Al) phase and

the ordered ( ,NiAl) phase. The tie lines in this two-phase region lie in the direction Cu3Al-NiAl but do not

coincide with the binary compositions. The two-phase region coalesces with the (Ni,Cu)+( ,NiAl)

two-phase region and with the 1+( ,NiAl) two-phase region to produce the tie triangles. The two tie

triangles meet at about 600°C, defining the four phase plane representing the transition reaction

( ,Cu3Al)+( ,NiAl) 1+(Ni,Cu). As shown by [1954Hay] the composition of the ( ,Cu3Al) phase at

600°C lies near the (Ni,Cu)- 1 tie line. Below 600°C the (Ni,Cu)+ 1+( ,NiAl) equilibrium is established

and the ( ,Cu3Al)+(Ni,Cu)+ 1 tie triangle descends to the binary Al-Cu eutectoid reaction.

Liquidus and Solidus Surfaces

Figure 1 is the liquidus surface mainly based on the data from [1948Koe], but incorporating the data of

[1938Ale] for the Ni-Cu-Cu3Al-NiAl region, the data of [1957Ray] for the region of primary separation of

the phase and the amendments to provide consistency with the accepted binary phase diagrams. It shows

the dominating role played by the surface of primary separation of the phase. The liquidus projection

reported by [1940Rap] is not considered in view of major disagreement with other works. Figure 2 is the

solidus surface, primarily based on the data of [1938Ale].

108


MSIT®

Al–Cu–Ni

Isothermal Sections

Majority of the published isothermal sections concentrate on the region of the ternary system defined by

Cu-Cu3Al-NiAl-Ni. In this category, the major work has been reported by [1937Ale, 1938Ale, 1941Tur,

1945Tur, 1978Tho] and [1983Rud]. The remaining portion of the ternary system has been studied primarily

by [1938Bra] and [1948Koe], with contributions from [1952Haw, 1972Bed, 1983Rud, 1985Li, 1988Ahm,

2001Liu] and [2003Wan]. All isothermal sections are amended to match with the accepted binary systems.

Figure 3 summarizes the phase observations by [1938Bra] of slowly-cooled alloys. It approximately

corresponds to phase relations at 500°C. As mentioned in the section “Literature Data”, [1938Bra] did not

observe the phase, but found three variants of the phase. Figure 4 is the isothermal section at 500°C

based on diagrams given by [1938Ale] and [1948Koe]. It agrees fairly well with Fig. 3. The section includes

three tie triangles 1+ + , + 2+ , 2+ 2+ in place of the + + tie triangle shown by [1948Koe]. The

Ni5Al3 and Ni3Al4 phases, which were not observed by [1938Ale] and [1948Koe], are also included in the

diagram. At 500°C the equilibrium between (Ni,Cu), 1 and ( ,NiAl) is well-established [1938Ale,

1985Li]. Figure 7 is the isothermal section at about 600°C, based on the data from [1938Ale], [1948Koe]

and [1983Rud]. This section is very close to four phase invariant planes for reactions L+ 1 + (U8),

( ,NiAl)+ 1+Ni2Al3, 1+ 2 + , ( ,NiAl)+( ,Cu3Al) 1+(Ni,Cu) and L+Ni2Al3 (Al)+ (U7). It

should be noted that [1938Ale] did not detect the reaction of ( ,NiAl) and ( ,Cu3Al) in the 600°C

isothermal section. As discussed under “Invariant Equilibria” 600°C is accepted in this assessment as the

transition temperature. Figure 7 should be regarded as relating to a temperature slightly above 600°C. Figure

8 is the isothermal section at 700°C, based on studies by [1938Ale], [1941Tur], [1945Tur], [1948Koe],

[1983Rud] and [2001Liu]. The isothermal section at 700°C reported by [1948Koe] showed a continuous

solution phase, designated between ( ,Cu3Al) and ( ,NiAl). This is contrary to the findings of [1938Ale]

and [1941Tur], who observed a two-phase ( ,Cu3Al)+( ,NiAl) region. It is not clear how much study was

made of this part of the ternary system by [1948Koe]. According to the vertical sections reported by

[1938Ale] and [1941Tur] and isothermal sections at 700°C, there exists at this temperature a tie triangle

(Ni,Cu)+( ,Cu3Al)+( ,NiAl). The latter equilibrium is accepted, with modifications to obey the

Schreinemakers rule. There is an obvious need for a re-determination of the equilibria between the phases

( ,Cu3Al), 1 and ( ,NiAl) using alloys of a higher Al content than those examined by [1938Ale]. It should

be noted that [1948Koe] designated the 2 phase region as . The isothermal section at 800°C is shown in

Fig. 9. It is based on data from [1938Ale], [1983Rud], [2001Liu] and [2003Wan]. This isothermal section

is very close to the critical region corresponding to the demixing ( ,NiAl)+( ,Cu3Al). Therefore, two tie

triangles on either side of ( ,Cu3Al) phase region is shown as degenerated. According to the Al-Cu binary,

at this temperature there should be a very small region of 0 near the ( 1) phase field. It is omitted for the

sake of clarity. The 900°C isothermal section, Fig. 10, is based on data from [1938Ale], [1948Koe] and

[1983Rud]. It is above the region of demixing of the ( ) phase. As with the 700°C section, the phase

(reported by [1948Koe]) has been replaced by the ( 1) phase. Partial isothermal sections are reproduced for

550°C [1945Tur], Fig. 11; 650°C [1941Tur], Fig. 12; 1000°C [1941Tur], Fig. 13.


Vertical section through Cu3Al-NiAl is depicted in Fig. 14. It has been drawn on the basis of data provided

by the works of [1938Ale, 1941Tur, 1946Smi, 1954Hay, 1979Kuz]. Although [1938Ale] considered this

section to be pseudobinary throughout the temperature range, this is not accepted due the presence of the

three-phase regions associated with the invariant reaction ( ,NiAl)+( ,Cu3Al) 1+(Ni,Cu) at lower

temperatures. [1938Ale] regarded the ( ,Cu3Al)-( ,NiAl) tie line of the (Ni,Cu)+( ,Cu3Al)+( , NiAl) tie

triangle as lying on the plane of Cu3Al-AlNi section. [1941Tur], showed the Cu3Al-NiAl section as

intersecting the ( ,Cu3Al)+ 1+( ,NiAl) tie triangle. Also shown was a necessary ( ,Cu3Al)+ 1 phase

region. It would seem that there should be an order-disorder phase boundary between the disordered

( ,Cu3Al) and ordered ( ,NiAl) phases in what [1938Ale] reported as the solid solution series. The lower

part of this boundary would form a tri-critical point at about 800°C where phase separation occurs. In the

section on “Invariant Equilibria” the formation of the two triangles (Ni,Cu)+( ,Cu3Al)+( ,NiAl) and

1+( ,Cu3Al)+( ,NiAl) and the subsequent eutectoidal decomposition of ( ,Cu3Al) were discussed. It is

109


MSIT®

Al–Cu–Ni

concluded that the Cu3Al-NiAl section published by [1941Tur] is more probable than that reported by

[1938Ale]. Fig. 14 represents the preferred section.

Early work [1924Iit] on vertical sections at constant Ni contents in Cu-Ni rich alloys was superseded by

publications of [1938Ale, 1941Tur] and [1945Tur]. Sections at 4 mass% Al [1941Tur] and [1938Ale], 10Al

[1938Ale], 14Al [1938Ale], 3Ni [1938Ale], 4Ni [1945Tur], 6Ni [1938Ale] and [1941Tur], 8Ni [1945Tur],

10, 20, 40 and 60 mass% Ni [1938Ale] and sections Cu-Ni3Al and Cu-NiAl have been reported. The 4 and

10 mass% Al sections are given in Fig. 15 and Fig. 16, respectively. Sections at 6 and 60 mass% Ni are

reproduced in Fig. 17 and Fig. 18, respectively.

Thermodynamics

A direct determination of the enthalpy of formation of ternary alloys was made by [1937Koe]. Isoenthalpy

curves relating to the as-cast condition, i.e. non-equilibrium, were given. Alloying of Al-Ni with Cu lowers

the enthalpy of formation. [1975Hen] determined precisely by solution calorimetry the enthalpy of

formation of the ( ,NiAl) phase as a function of concentration and with addition of Cu. [1993Sto] measured

enthalpy of mixing of liquid Al-Cu-Ni alloys at 1427°C along eight isopleths using a high-temperature

mixing calorimeter. An analysis of the data by [2000Wit] revealed that the enthalpy of mixing has a

minimum at -42.8 kJ mol-1 corresponding to the stoichiometry Ni45Cu10Al45.

Miscellaneous

Extensive data have been reported on the lattice parameters of the (Al) phase [1952Han] and the (Ni,Cu)

phase [1938Bra, 1936Gri1] and [1941Tur]. The effect of Cu additions on the structure of NiAl was studied

by [1939Lip]. The number of atoms in the unit cell decreases across the ( ,NiAl) phase region as the Al

content increases. Vacant lattice sites are formed on the Al-rich side of the NiAl stoichiometry. [1971Jac]

measured the lattice spacings in the ( ,NiAl) phase along sections from 16.67Cu-83.33Ni (at.%) to Al and

8.33Cu-91.67Ni (at.%) to Al and on the 50 at.% Al section. Alloys were annealed 7 days at 1050°C and

cooled to room temperature at a rate of 100 K/h. [1985Mis] examined the effect of Cu additions on the

lattice parameter of Ni3Al at a constant Al content of 25 at.%. The lattice parameter was increased by Cu

up to the 15 at.% Cu limit studied. This finding agrees with data summarized by [1984Och]. Magnetic

properties of the (Ni,Cu) phase along the 77 and 87 at.% Ni sections were determined for alloys quenched

from 1100°C by [1983Lup]. The Curie temperature of alloys on a section from Ni towards 25Al-75Cu

(at.%) were studied by [1952Mar]. A linear decrease in Curie temperature from 361°C at Ni to 90°C at 20

at.% Al+Cu was observed.

References

[1923Aus] Austin, C.R., Murphy, A.J., “The Ternary System Cu-AlNi”, J. Inst. Met., 29, 327-367


[1923Bin] Bingham, K.E., Haughton, J.L., “The Constitution of Some Alloys of Al with Cu and Ni”,

J. Inst. Met., 29, 71-112 (1923) (Equi. Diagram, Experimental, 13)

[1924Iit] Iitaka, I., “Investigation of the Ternary Cu-Al-Ni System” (in Japanese), Tetsu to Hagane,

10, 1-32 (1924) (Equi. Diagram, Experimental)

[1928Nis] Nishimura, H., “Investigations of Al-Base Al-Cu-Ni Alloys” (in Japanese), Suiyokwai-Shi,

5, 616-626 (1928) (Equi. Diagram, Experimental, 3)



[1936Gri1] Gridnev, V., Kurdjumov, G., “The Influence of Ni on the Solubility Limits of the -Phase

in Cu-Al Alloys” (in German), Metallwirtschaft, 15, 229-231, 256-259 (1936) (Crys.


[1936Gri2] Gridnev, V., Kurdjumov, G., “The Effect of a Third Element on the Aging of Binary

Systems. Cu-Al-Ni System” (in Russian), Teor. Prakt. Metall., (2), 100-109 (1936) (Crys.


110


MSIT®

Al–Cu–Ni

[1937Ale] Alexander, W.O., Hanson, D., “Cu-Rich Ni-Al-Cu Alloys. Part 1. The Effect of

Heat-Treatment on Hardness and Electrical Resistivity”, J. Inst. Met., 61, 83-99 (1937)

(Experimental, 8)

[1937Koe] Koerber, F., Oelsen, W., Lichtenberg, H., “On the Thermochemistry of Alloys. II. Direct

Determination of the Heat of Formation of Ternary Alloys of the System Fe-Ni-Al,

Fe-Co-Al, Cu-Ni-Al, Fe-Al-Si, as well as Certain Alloys of the Cu-Mn-Al System” (in

German), Mitt. K.-W.-Inst. Eisenforschung, 19, 131-159 (1937) (Experimental,

Thermodyn., 50)

[1938Ale] Alexander, W.O., “Cu-Rich Ni-Al-Cu Alloys. Part II. The Constitution of the Cu-Ni-Rich

Alloys”, J. Inst. Met., 63, 163-183 (1938) (Crys. Structure, Equi. Diagram,

Experimental, 14)

[1938Bra] Bradley, A.J., Lipson, H. “An X-Ray Investigation of Slowly Cooled Cu-Ni-Al Alloys”,

Proc. Roy. Soc., 167A, 421-438 (1938) (Crys. Structure, Equi. Diagram, Experimental, 13)

[1939Lip] Lipson, H., Taylor, A., “Defect Lattices in Some Ternary Alloys”, Proc. Roy. Soc., 173A,


[1940Bra] Bradley, A.J., Bragg, W.L., Sykes, C., “Researches Into the Structure of Alloys”, J. Iron

Steel Inst., London, 141, 104-163 (1940) (Crys. Structure, Equi. Diagram, Experimental,

Review, 61)

[1940Rap] Rapp, A., “The Al Corner of the Ternary System Al-Cu-Ni” (in German), Alum. Arch., (28),

1-17 (1940) (Crys. Structure, Equi. Diagram, Experimental, 9)

[1941Tur] Turkin, V.D., “Investigation of Alloys of the Cu-Ni-Al System” (in Russian), Tsvetn. Met.,

17, 26-34 (1941) (Crys. Structure, Equi. Diagram, Experimental, 11)

[1945Tur] Turkin, V.D., “Investigation of Alloys of the Cu-Ni-Al System” (in Russian), Struk. Legkih

Splavov Tsvetnikh Metallov, 5-21 (1945) (Crys. Structure, Equi. Diagram, Experimental,

33)

[1946Smi] Smiryagin, A.P., “Boundaries of the Solid Solution Phase in the Cu-Al-Ni System” (in

Russian), Izv. Sekt. Fiz.-Khim. Anal., 16, 180-196 (1946) (Equi. Diagram, Experimental, 40)

[1948Koe] Koester, W., Zwicker, U., Moeller, K., “Microscopic and X-Ray Studies Towards the

Understanding of the Cu-Ni-Al System” (in German), Z. Metallkd., 39, 225-231 (1948)


[1952Han] Hanemann, H., Schrader, A., “Al-Cu-Ni”, in “Ternary Alloys of Al”, Atlas

Metallographicus, Verlag Stahleisen M.B.H., Duesseldorf, 3(2), 85-90 (1952) (Crys.

Structure, Equi. Diagram, Review, 3)

[1952Haw] Haworth, J.B., Hume-Rothery, W., “The Effect of Four Transition Metals on the / Brass

Type of Equilibrium”, Philos. Mag., 43, 613-629 (1952) (Equi. Diagram, Experimental, 23)

[1952Mar] Marian, V., Maxim, I., Tintea, M., “Curie Points for Ni-Cu-Al Solid Solutions. Preliminary

Note” (in Romanian), Comm. Acad. Rep. Populare Romine, Fiz., 11, 527-531 (1952)

(Experimental, 0)

[1954Hay] Haynes, R., “Isothermal Transformations of Eutectoid Al Bronzes”, J. Inst. Met., 83,

105-114 (1954) (Experimental, 23)

[1955Bow] Bown, M.G., “The Crystal Structures of Certain Metallic Phases”, Thesis, Univ. Cambridge,


[1956Bow] Bown, M.G., “The Structure of Rhombohedral T(NiCuAl)”, Acta Crystallogr., 9, 70-74


[1957Lu1] Lu, S.S., Chang, T., “Systematic Structure Changes in a Single-Phase Field - an

Extraordinary Phenomenon Observed in Al-Cu-Ni Alloys”, Sci. Rec., Peking, 1, 41-44


[1957Lu2] Lu, S.S., Chang, T., “Crystal Structure Changes in the J-Phase of Al-Cu-Ni Alloys” (in

Chinese), Acta Phys. Sin. (Chin. J. Phys.), 13, 150-178 (1957) (Crys. Structure, Equi.


[1957Ray] Raynor, G.V., Ward, B.J., “Al-Rich Alloys of the Quarternary System Al-Fe-Cu-Ni”,

J. Inst. Met., 86, 135-144 (1957-1958) (Equi. Diagram, Experimental, 20)

111


MSIT®

Al–Cu–Ni

[1961Phi] Phillips, H.W.L., “Al-Cu-Ni”, in “Equilibrium Diagrams of the Al-Alloy Systems”,

Information Bulletin 25, Aluminium Development Association, London, 67-69 (1961)

(Review, 3)

[1971Jac] Jacobi, H., Engell, M.J., “Defect Structure in Non-Stoichiometric -(Ni,Cu)Al”, Acta

Metall., 19, 701-711 (1971) (Crys. Structure, Experimental, Theory, 19)

[1972Bed] Bedel'baev, G.E., Begimov, T.B., Melikhov, V.D., Presnyakov, A.A., Ashirimbetov, Yh.A.,

“Study of the Structure of the Compound Cu9Al4 With Ni Additions” (in Russian), Prikl.

Teor. Fiz., (3), 276-281 (1972) (Crys. Structure, Experimental, 4)

[1975Hen] Henig, E.-Th., Lukas, H.L., “Calorimetric Determination of the Enthalpy of Formation and

Description of the Defect Structure of the Ordered -Phase (Ni,Cu)1-xAlx” (in German),

Z. Metallkd., 66, 98-106 (1975) (Thermodyn., Experimental, 22)

[1978Tho] Thomson, R., Edwards, J.O., “The P Phase in Ni-Al Bronzes. I. Slow-Cooled

Microstructures”, Amer. Foundrymen's Soc. 82nd Annual Conf. Detroit, Mich., 385-394


[1979Kuz] Kuznetsov, G.M., Fedorov, V.N., Nikonova, I.V., Trofimova, E.A., “Investigation of the

Cu-Ni-Al System” (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., (4), 98-100

(1979) (Equi. Diagram, Experimental, Thermodyn., 6)

[1982Ask] Askarov, M.S., Smagulov, D.U., Omarov, A.K., “Study of the Phase Diagram, Phase

Composition and Alloy Structure in the Al-Ni-Cu System” (in Russian), Vopr. Teo. Prakt.

Per. Syr. Prod. Tsv. Met. Kaz., 98-103 (1982) (Equi. Diagram, Experimental, 11)

[1983Haf] Hafez, H.A., Taha, M.A., El-Sabagh, A.S., “The Microstructure of Al-Rich Al-Cu-Ni

Alloys”, Prakt. Metallogr., 20, 507-533 (1983) (Experimental, Crys. Structure, 14)

[1983Lup] Lupsa, I., Burzo, E., “Magnetic Properties of NiCuAl Solid Solutions”, J. Magn. Magn.

Mater., 37, 147-154 (1983) (Experimental, Magn. Prop., 34)

[1983Rud] Rudolph, G., “Microprobe Measurements to Determine Phase Boundaries and Diffusion

Paths in Ternary Phase Diagrams taking a Cu-Ni-Al System as an Example”, Mikrochimica

Acta, Suppl., 10, 241-251 (1983) (Equi. Diagram, Experimental, 8)

[1984Hus] Husain, S.W., Clapp, P.C., Ahmed, M., “Phase Transformations on Aging

Copper-Aluminum-Nickel Phase Alloys”, Mater. Res. Soc. Symp. Proc., 21, 729-734


[1984Och] Ochiai, S., Mishima, Y., Suzuki, T., “Lattice Parameters of Ni( ), Ni3Al( ') and Ni3Ga( ')

Solid Solutions”, Bull. P.M.E., (53), 15-28 (1984) (Crys. Structure, Experimental, 66)

[1985Li] Li, S., Sum, X., Qian, C., “X-Ray Diffraction Analysis of the Martensitic Transformation in

Cu-Ni-Al Alloy” (in Chinese), J. Cent.-South Inst. Min. Metall. (China), (1), 71-77 (1985)


[1985Mis] Mishima, Y., Ochiai, S., Suzuki, T., “Lattice Parameters of Ni( ), Ni3Al( ') and Ni3Ga( ')

Solid Solutions With Additions of Transition and B-Sub Group Elements”, Acta Metall., 33,




[1988Ahm] Ahmed, M., Husain, S.W., Iqbal, Z., Hashmi, F.H., Khan, A.Q., “Phase Transformations in

Rapidly Solidified Cu-Al-Ni Phase Alloys”, Scr. Metall., 22, 803-808 (1988)

(Experimental, 11)

[1989Ell] Ellner, M., Kek, S., Predel, B., “Ni3Al4 - A Phase with Ordered Vacancies Isotypic to

Ni3Ga4”, J. Less-Common Met., 154(1), 207-215 (1989) (Experimental, Crys. Structure, 26)




[1990Sun] Sun, Y.S., Lorimer, G.W., Ridley, N., “Microstructure and its Development in Cu-Al-Ni

Alloys”, Metall. Trans., 21A, 575-588 (1990) (Experimental, 16)

112


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Al–Cu–Ni

[1990Ye] Ye, J., Tokonami, M., Otsuka, K., “Crystal Structure Analysis of 1' Cu-Al-Ni Martensite

Using Conventional X-Ray and Synchrotron Radiations”, Metall. Trans., 21A, 2669-2678


[1991Pri] Prince, A., ”Aluminium - Copper - Nickel”, MSIT Ternary Evaluation Program, in MSIT



Assessment, 43)

[1993Sto] Stolz, U.K., Arpshofen, I., Sommer, F., “Determination of the Enthalpy of Mixing of Liquid

Aluminium-Copper-Nickel Ternary Alloys”, Z. Metallkd., 84, 552-556 (1993) (Calculation,

Equi. Diagram, Experimental, Thermodyn., 8)

[1994Jia] Jia, C.C., Ishida, K., Nishizawa, T., “Partition Of Alloying Elements Between (A1),

'(L12) and (B2) Phases in Ni-Al Base Systems”, Metall. Mater. Trans., 25A, 473-485



Alloys”, Subramanian,. P.R., Chakrabarti,. D.J., Laughlin, D.E (Eds.), ASM International,



[1996Pau] Paufler, P., Faber, J., Zahn, G., “X-Ray Single Crystal Diffraction Investigation on

Ni1+xAl1-x”, Acta Crystallogr., Sect. A: Found. Crystallogr., A52, C319 (1996) (Crys.

Structure, Experimental, Abstract, 3)

[1996Vik] Viklund, P., Häußermann, U., Lidin, S., “NiAl3: A Structure Type of its Own”, Acta

Crystallogr., Sect. A: Found. Crystallogr., A52, C-321 (1996) (Crys. Structure,

Experimental, Abstract, 0)

[1997Bou] Bouche, K., Barbier, F., Coulet, A., “Phase Formation During Dissolution of Nickel in

Liquid Aluminium”, Z. Metallkd., 88(6), 446-451 (1997) (Thermodyn., Experimental, 15)



Experimental, #,*,25)[1998Pel] Pelosin, V., Riviere, A., “Structural and Mechanical Spectroscopy Study of the 1’

Martensite Decomposition in Cu-12% Al-3% Ni (wt.%) Alloy”, J. Alloys Compd., 268,

166-172 (1998) (Crys. Structure, Experimental, Mechan. Prop., 10)

[1998Rav] Ravelo, R., Aguilar, J., Baskes, M., Angelo, J.E., Fultz, B., Holian, B.L., “Free Energy and

Vibrational Entropy Difference between Ordered and Disordered Ni3Al”, Phys. Rev. B,

57(2), 862-869 (1998) (Thermodyn., Theory, Calculation, 43)

[2000Wit] Witusiewicz, V.T., Arpshofen, I., Seifert, H.-J., Sommer, F., Aldinger, F.,

“Thermodynanmics of Liquid and Undercooled Liquid Al-Cu-Ni-Si Alloys”, Thermochim.

Acta, 356, 39-57 (2000) (Calculation, Experimental, Thermodyn., 41)


(A1), (A2) and (D83) Phases in the Cu-Al-X System”, J. Phase Equilib., 22, 431-438


[2001Mot] Motoyasu, G., Kaneko, M., Soda, H., McLean, A., “Continuously Cast Cu-Al-Ni Shape

Memory Wires with a Unidirectinal Morphology”, Metall. Mater. Trans., 32A, 585-593

(2001) (Crys. Structure, Equi. Diagram, Experimental, Phys. Prop., 15)


System”, Abstr. VIII Int. Conf. “Crystal Chemistry of Intermetallic Compounds”,


[2002Leb] Lebrun, N., “Cu-Ni (Copper-Nickel)”, MSIT Binary Evaluation Program,in MSIT



Assessment, 51)

113


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Al–Cu–Ni




[2003Sal] Saltykov, P., Cornish, L., Cacciamani, G., “Al-Ni (Aluminium-Nickel)”, MSIT Binary

Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science

International Services GmbH, Stuttgart; to be published, (2003) (Crys. Structure, Equi.


[2003Wan] Wang, C-H., Chen, S-W., Chang, C-H., Wu, J-C., “Phase Equilibria of the Ternary

Al-Cu-Ni System and Interfacial Reactions of Related System at 800°C”, Metall. Mater.

Trans. A, 34A, 199-209 (2003) (Equi. Diagram, Experimental, 30)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Ni1-x,Cux)

Ni

< 1455

Cu

< 1084.62

cF4

Fm3m

Cu

a = 352.40

a = 361.46

0 < x < 1

at 25°C [Mas2]

at 25°C [Mas2]


(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

NiAl3< 856

oP16

Pnma

NiAl3oP16

Pnma

Fe3C

a = 661.3 ± 0.1

b = 736.7 ± 0.1

c = 481.1 ± 0.1

a = 659.8

b = 735.1

c = 480.2

[1996Vik]

[1997Bou, V-C]

Ni2Al3< 1138

hP5

P3m1

Ni2Al3

a = 402.8

c = 489.1

59.5 to 63.2 at.% Al [Mas]

[1997Bou, V-C]

Ni3Al4< 702

cI112

Ia3d

Ni3Ga4

a = 1140.8 ± 0.1 [1989Ell, V-C]

( ,NiAl)

< 1651

cP2

Pm3m

CsCl

a = 288.72 ± 0.02 at 50 at.% Ni [1996Pau].

In the ternary this phase forms a

continuous series of solid solution with

,Cu3Al above 800°C.

[1938Ale, 1941Tur]

Ni5Al3< 723

oC16

Cmmm

Pt5Ga3

a = 744

b = 668

c = 372

32 to 36 at.% Al [Mas] [V-C]

Ni3Al

< 1372

cP4

Pm3m

Cu3Au

a = 357.92

24 to 27 at.% Al [Mas2]

[1998Rav]

114


MSIT®

Al–Cu–Ni

, ( , Cu3Al)

1049-559

cI2

Im3m

W

a = 295.64

70.6 to 82 at.% Cu, [1985Mur, 1998Liu]

at 672°C in +(Cu) alloy.

In the ternary this phase forms a

continuous series of solid solution with

( ,NiAl) above 800°C.

[1938Ale, 1941Tur]

2, Cu1-xAlx< 363

~TiAl3long period

superlattice

a = 366.8

c = 368.0

0.22 x 0.235 [Mas, 1985Mur]

at 76.4 at.% Cu

(subcell only)

0, Cu1-xAlx1037-800

cI52

I43m

Cu5Zn8

- 0.31 x 0.402 [Mas2]

32 to 38 at.%Al, [1998Liu]

1, Cu9Al4< 890

cP52

P43m

Cu9Al4

a = 870.68

a = 871.32

at 33.8 at.% Al, [V-C] from single

crystal [V-C]

, Cu1-xAlx< 686

hR*

R3m a = 1226

c = 1511

0.38.1 x 0.407 [Mas2, 1985Mur]

at x = 38.9 [V-C]

1, Cu1-xAlx958-848

c**? - 0.379 x 0.406

[Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.47 x 0.78

55.0 to 61.1 at.% Cu

[Mas, 1985Mur, V-C2]


1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 59.8 at.% Cu, [Mas2, 1994Mur]


2, Cu11.5Al9(r)

< 570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu, [Mas2, 1985Mur]


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu

[V-C2, Mas2, 1985Mur]


2, CuAl(r)

< 560

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu

[V-C2]

, CuAl2< 591

tI12

I4/mcm

CuAl2

a = 606.3

c = 487.2

31.9 to 33.0 at.% Cu [1994Mur]

Single crystal

[V-C2, 1989Mee]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

115


MSIT®

Al–Cu–Ni

a) The i phases are stacking variants in the range assigned to a single phase by other authors. They are derived

from the CsCl structure with ordered vacancies (V) on the (Ni,Cu) sublattice (occupied sites designated by M).

i is the number of layers per unit cell.


* a5, (Ni,Cu)3Al5

11, (Ni,Cu)6Al11

6, (Ni,Cu)4Al6

13, (Ni,Cu)8Al13

7, (Ni,Cu)5Al7

15, (Ni,Cu)10Al15

8, (Ni,Cu)6Al8

17, (Ni,Cu)12Al17

hR8

(Ni,Cu)3Al5(pseudo?) cubic

hP51

(Ni,Cu)6Al11

hP30

(Ni,Cu)4Al6hR21

(Ni,Cu)8Al13

hP36

(Ni,Cu)5Al7hP75

(Ni,Cu)10Al15

hR14

(Ni,Cu)6Al8hP87

(Ni,Cu)12Al17

a = 411.19

c = 2512.5

a = 1460

a = 411.41

c = 5528.9

a = 411.32

c = 3013.5

a = 411.33

c = 6517.3

a = 410.62

c = 3493.8

a = 409.58

c = 7464.5

a = 410.45

c = 3985.0

a = 410.5 ± 0.01

c = 3997 ± 0.01

a = 410.14

c = 8449.9

stacking sequence VMMMV [1957Lu2]

[1955Bow, 1956Bow]

stacking sequence

VMMMVVVMMMV [1957Lu2]

stacking sequence VMMMMV

[1957Lu2]

stacking sequence

VMMMMVVVMMMMV [1957Lu2]

stacking sequence VMMMMMV

[1957Lu2]

stacking sequence

VMMMMMVVVMMMMMV

[1957Lu2]

stacking sequence VMMMMMMV

[1957Lu2] [1955Bow, 1956Bow]

stacking sequence VMMMMMMVVV-

MMMMMMV [1957Lu2]


Al Cu Ni

L + Ni3Al (Ni,Cu) + 1250 U1 L 20 40 40

L+ 0 1 + a) ~ 880 U2 L

0

1

48

37

48

40

50

58

40

59

2

5

12

1

L + 1 2 + ? U3

L + + Ni2Al3 ~ 820 P L

Ni2Al3

64

57

60

62

32

24

23

28

4

19

17

10

L + 2 + b) ~ 650 U4 L

2

63

30

49

59

36

40

50

34

1

30

1

7

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

116


MSIT®

Al–Cu–Ni

a) L + + NiAl according to [1948Koe] b) L + NiAl + according to [1948Koe]

L + NiAl3 (Al) + Ni2Al3 630 U5 L

NiAl3(Al)

Ni2Al3

90

74

99.6

62

8

1

0.2

14

2

25

0.2

24

L + 2 + ? U6

L + Ni2Al3 (Al) + ~ 590 U7 L

Ni2Al3(Al)

88

62

98.7

62

11

21

1.1

27

1

17

0.2

11

L + + 585 U8 L 67

50.2

66.5

59

32

49

33

37

1

0.8

0.3

4

L (Al) + + 546 E L

(Al)

82.3

98.3

67.6

64

17.1

1.5

32.1

29

0.6

0.2

0.3

7


Al Cu Ni

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

e2

p3

p4

p5

e

p7

p6

e4

e3

p2

e1p1

U1

U2

U3

U4

U8

P

E

U5

U6

(Al)NiAl3

Ni2Al3

β

(Ni,Cu)

β,NiAl

β,Cu3Al

γ0

ε2

η1

1400

1300 12001100

1600

1500

1400

1300

800

9001000

700

U7

ε1

11001200

Ni3Al

τθ

Fig. 1: Al-Cu-Ni.

Liquidus surface

117


MSIT®

Al–Cu–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

(β,NiAl)

(β,Cu3Al)

(Ni,Cu)

1050

11001200

1250

13001400

1200

1250

1400

1500

1600

Ni3Al

Fig. 2: Al-Cu-Ni.

Solidus surface for

Cu-Ni rich alloys

[1938Ale]

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

(Ni,Cu)

Ni3Al

Ni5Al3

(β,NiAl)

Ni2Al3

NiAl3

(Al)

η2

ζ2

γ1

τ

θNi3Al4

δ

Fig. 3: Al-Cu-Ni.

Constitution of slowly

cooled alloys, after

[1938Bra]

118


MSIT®

Al–Cu–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

(Ni,Cu)

Ni3Al

Ni5Al3

(β,NiAl)

Ni2Al3

(Al)

θ

η2

ζ2

δγ

1

τ

NiAl3

Ni3Al4

Fig. 4: Al-Cu-Ni.


500°C [1948Koe]

10

20

30 40

60

70

Ni 30.00Cu 20.00Al 50.00

Ni 0.00Cu 50.00Al 50.00

Ni 0.00Cu 20.00Al 80.00 Data / Grid: at.%

Axes: at.%

τ

τ5

τ11

τ6

τ13

τ7

τ15

x τ8

* τ17

xx

* **

Fig. 5: Al-Cu-Ni.

Extent of phase

region and

distribution of

stacking variants

[1957Lu1, 1957Lu2]

119


MSIT®

Al–Cu–Ni

Fig

. 6a:

A

l-C

u-N

i. T

he

reac

tion s

chem

e, p

art

1

Al-

Ni

Al-

Cu

Al-

Cu

-Ni

lβ

+ N

i 3A

l

13

69

e 1

L +

γε 1

+β

ca.

88

0U2

l +

(N

i)

Ni 3

Al

13

72

p1

L+

Ni 3

Al

(N

i,C

u)

+ β

12

50

U1

l +

Ni 2

Al 3

NiA

l 3

85

6p5

β +

Ni 3

Al

Ni 5

Al 3

72

3p

l (

Al)

+ N

iAl 3

64

4e 3

l +

β N

i 2A

l 3

11

38

p2

γ +

ε 1ε 2

85

0p

l +

γε 1

95

8p4

l (

Cu

) + β

10

32

e 2

l +

βγ

10

37

p3

γ +

ε2

δ6

86

p

ε 1l

+ ε2

84

8e

L +

βε 2

+ τ

ca.

65

0U4

L +

ε1

ε 2 +

βU3

L+

β +

Ni 2

Al 3

τca

. 8

20

P

L+

NiA

l 3(A

l)+

Ni 2

Al 3

63

0U5

ε 1ε 2

+ γ

+ β

E

L+

γ +

β

Ni 3

Al

+ (

Ni,

Cu)

+ β

γ +

ε 1+

βL

+ ε 1

+ β

L +

τ +

Ni 2

Al 3

β +

Ni 2A

l 3 +

τ

β +

Ni 3

Al

+ N

i 5A

l 3

L+

τ +

β

L+

ε 2+

βε 1

+ ε2 +

β

NiA

l 3 +

(A

l) +

Ni 2

Al 3

L +

(A

l) +

Ni 2

Al 3

L+

ε 2 +

τ

β +

ε 2+

τε 2 +

γ +

β

β,C

u3A

l+β,

NiA

l+(N

i,C

u)

β,C

u3A

l+β,

NiA

l+γ

ca.

80

0

γ +

ε 2 +

δ

120


MSIT®

Al–Cu–Ni

Fig

. 6b

:

Al-

Cu

-Ni.

The

reac

tion s

chem

e, p

art

2

Al-

Ni

Al-

Cu

Al-

Cu

-Ni

l +

ε2

η6

24

p6

L +

ε2

η +

τU6

L +

ητ

+ θ

58

5U8

L +

Ni 2

Al 3

(A

l) +

τ5

90

U7

β,C

u3A

l+β,

NiA

lγ+

(Ni,

Cu)

ca.

60

0U

ε 2 +

β

γ +

τ6

20

U

ε 2 +

ηζ

+ τ

U

τ +

β γ

+ N

i 2A

l 3ca

. 5

80

U

ε 2

τ +

ζ +

δE

L (

Al)

+ θ

+ τ

54

6E

ε 2

δ +

ζ5

60

e

ε 2+

ηζ

59

0p

l +

ηθ

59

1p7

β (

Cu)

+ γ

55

9e

l (

Al)

+ θ

548.2

e 4

γ +

ε 2

τ +

δU

L+

τ+N

i 2A

l

3L

+ ε 2

+ τ

ε 2 +

γ +

β

β +

ε 2 +

τ

L+

(Al)

+N

i 2A

l 3L+

η +

τβ,

Cu3A

l+β,

NiA

l+γ

β,C

u3A

l+β,

NiA

l+(N

i,C

u)

β,N

iAl+

γ+(N

i,C

u)

β +

γ +

τ

ε 2+

γ +

τ

β +

Ni 2

Al 3

+τ

γ +

ε 2+

δε 2

+ η

+ τ

γ +

τ +

δε 2

+ τ

+ δ

ε 2 +

ζ +

τη

+ ζ

+ τ

τ +

ζ +

δ

β +

γ +

Ni 2

Al 3

τ +

γ +

Ni 2

Al 3

L+

τ +

θ

η +

τ +

θN

i 2A

l 3+

(A

l) +

τ

L +

(A

l) +

τ

(Al)

+ θ

+ τ

121


MSIT®

Al–Cu–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

(Ni,Cu)

(β,Cu3Al)

γ1

δ

ε2

η1

L

(Al)

NiAl3

Ni2Al3

τ

(β,NiAl)

Ni3Al4

Ni3Al

Ni5Al3

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

(Ni,Cu)

β

γ1

ε2

L

NiAl3

Ni2Al3

(β,NiAl)

τ

Ni5Al3

Ni3Al

Ni3Al4

Fig. 7: Al-Cu-Ni.


approximately 600°C

[1948Koe]

Fig. 8: Al-Cu-Ni.


700°C [1948Koe]

122


MSIT®

Al–Cu–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

L

ε2

(Ni,Cu)

(β,Cu3Al)

γ1

Ni2Al3

NiAl3

(β,NiAl)

Ni3Al

τ

β

20

40

60

80

20 40 60 80

20

40

60

80

Ni Cu


Axes: at.%

L

ε1

(Ni,Cu)

(β,Cu3Al)

γ0

β(β,NiAl)

Ni2Al3

Ni3Al

Fig. 9: Al-Cu-Ni.


800°C

Fig. 10: Al-Cu-Ni.


900°C

123


MSIT®

Al–Cu–Ni

10

20

30

40

60 70 80 90

10

20

30

40

Ni 50.00Cu 50.00Al 0.00


Axes: at.%

γ1γ

1+(Ni,Cu)+(β,NiAl)

(Ni,Cu)+(β,NiAl)

(Ni,Cu)(Ni,Cu)+Ni3Al

Cu

10

20

30

40

60 70 80 90

10

20

30

40

Ni 50.00Cu 50.00Al 0.00


Axes: at.%

γ1

(β,Cu 3Al)

(Ni,Cu)+(NiAl)

(Ni,Cu)(Ni,Cu)+Ni3Al

γ1+(β,Cu3Al)

Cu

Fig. 11: Al-Cu-Ni.

Cu-Ni rich isothermal

section at 550°C

[1945Tur]

Fig. 12: Al-Cu-Ni.


section at 650°C

[1941Tur]

124


MSIT®

Al–Cu–Ni

10

20

30

40

60 70 80 90

10

20

30

40

Ni 50.00Cu 50.00Al 0.00


Axes: at.%

(Ni,Cu)

β

γ0

(Ni,Cu)+β

(Ni,Cu)+Ni3Al

Cu

40 20500

750

1000

1250

1500

Ni 50.00Cu 0.00Al 50.00

Ni 0.00Cu 75.00Al 25.00Ni, at.%

Tem

pera

ture

, °C

β

disorderedordered(β,Cu3Al)(β,NiAl)

(β,Cu3Al)

L

β+γ1

+(β,NiAl)

(Ni,Cu)+γ1

600

1049°C

1651°C

Fig. 13: Al-Cu-Ni.


section at 1000°C

[1941Tur]

Fig. 14: Al-Cu-Ni.

The NiAl-Cu3Al

section

125


MSIT®

Al–Cu–Ni

20 40 60 80500

750

1000

Ni 91.70Cu 0.00Al 8.30

Ni 0.00Cu 91.10Al 8.90Cu, at.%

Tem

pera

ture

, °C

(Ni,Cu)

Ni3Al+(Ni,Cu)

(β,NiAl)+(Ni,Cu)

(Ni,Cu)+Ni3Al+(β,NiAl)

20 40 60500

750

1000

1250

1500

Ni 80.50Cu 0.00Al 19.50

Ni 0.00Cu 79.30Al 20.70Cu, at.%

Tem

pera

ture

, °C

(Ni,Cu)

Ni3Al+(Ni,Cu)

(β,NiAl)(Ni,Cu)+(β,NiAl)

(Ni,Cu)+γ1

(Ni,Cu)

L+(β,NiAl)

L+(Ni,Cu) L

1250

600

+(β,NiAl)+Ni3Al

Fig. 15: Al-Cu-Ni.

Vertical section at 4

mass% Al

Fig. 16: Al-Cu-Ni.


mass% Al

126


MSIT®

Al–Cu–Ni

10 20400

500

600

700

800

900

1000

1100

Ni 6.50Cu 93.50Al 0.00

Ni 5.40Cu 65.40Al 29.20Al, at.%

Tem

pera

ture

, °C

(Ni,Cu) (β,Cu3Al)

(Ni,Cu)

(β,Cu3Al)+γ1

γ1+(Ni,Cu)+(β,NiAl)

(Ni,Cu)+Ni3Al

(Ni,Cu)+(β,Cu3Al)

+(β,Cu3Al)

+(β, NiAl)

(β,Cu3Al)+γ1+(β,AlNi)

10 20 30 40700

800

900

1000

1100

1200

1300

1400

1500

Ni 61.90Cu 38.10Al 0.00

Ni 46.80Cu 10.80Al 42.40Al, at.%

Tem

pera

ture

, °C

L+(Ni,Cu) L+(β,NiAl)

L+Ni3Al

(β,NiAl)(Ni,Cu)

Ni3Al+(Ni,Cu) Ni3Al+(β,NiAl)

1250

L

Fig. 17: Al-Cu-Ni.


mass% Ni

Fig. 18: Al-Cu-Ni.


mass% Ni

127


MSIT®

Al–Cu–Sc

Aluminium – Copper – Scandium

Alexander Pisch

Literature Data

The present evaluation updates and completes the evaluation made earlier by Q. Ran in the MSIT

Evaluation Program [1991Ran].

Two phases ScCuAl and ScCu2Al were early reported by [1965Tes] who prepared the ScCuAl alloy from

98.2% pure Sc and Cu and Al of higher purity, in an electric arc furnace and under helium atmosphere. The

powder X-ray diffraction pattern shows nearly a single phase of MgZn2 structure with traces of another

phase. For the ScCu2Al compound two possible structure types were considered by [1965Tes], the BiF3 and

the CsCl type structure. A later reinvestigation by [1965Tes] using single crystal method and a refinement

determined its structural type as MnCu2Al, although the authors explicitly did not exclude that it could

belong to the BiF3 type. The MgZn2 type structure of ScCuAl and the BiF3 type structure of ScCu2Al were

confirmed by [1968Dwi] and [1987Dwi], respectively, with considerable difference in the lattice

parameters reported for ScCuAl. [1996Nak] than reported a new ternary phase 2, ScCu0.6Al1.4 detected

from single crystal investigations.

[1988Kha] studied two polythermal sections at (a) constant 4 mass% Sc and up to 10 mass% Cu and (b) at

constant 20 mass% Cu up to 6 mass% Sc, by thermal analysis, metallography and X-ray phase analysis.

Samples were melted in an electric resistance furnace in corundum crucibles and cast into a thick-walled

copper mold. Besides some known elemental solid solution and binary compounds, a phase with unknown

composition was observed. [1988Kha] proposed that this phase, not reported earlier by [1965Tes], is a new

ternary compound. Later [1991Kha] could confirm this and determined its nominal composition as

ScCu4+xAl8–x where 0 x 2.6. [1997Sus] determined magnetic and electrical properties of this

compound.

[1991Kha] studied alloys in the Al-rich corner up to 40 mass% Cu and 6 mass% Sc at 450°C and 500°C by

optical microscopy, SEM coupled with EDX, microhardness and electrical resistivity measurements.

Samples have been prepared from the high purity metals (Al 99.99%, Sc 99.875%, Cu 99.996%) in an

electrical resistance furnace, for higher Sc contents in an electrical arc furnace under Ar atmosphere. The

liquidus surface in the Al-rich corner have been studied by [1992Yun, 1992Tor], with different results. As

the diagrams presented by [1992Yun] violate Gibbs phase rule and the results have not been considered.

The available data has been reviewed and compared to other Al-Sc-X systems by [1997Rok].

Binary Systems

The description of the binary Al-Sc system has been accepted from [1999Cac], Al-Cu from [2003Gro] and

Cu-Sc from [2002Wat].

Solid Phases

Four ternary compounds have been reported. Table 1 gives crystallographic data of these phases and all

binary phases from [1988Kha, 1991Kha, 1999Cac, 2003Gro, 2002Wat]. The ternary 4, ScCu4+xAl8–x

phase has a ThMn12 type structure with composition range from 0 < x < 2.6 [1991Kha].


Two four phase equilibria, L (Al)+ + 4 at 546°C and L+ScAl3 (Al)+ 4 at 572°C, were reported by

[1988Kha]. The compositions of the phases involved in the reactions were not determined.

Liquidus Surface

[1992Tor] established the liquidus surface in the Al-rich part of the diagram which is presented in Fig. 1.

128


MSIT®

Al–Cu–Sc

Isothermal Sections

The isothermal sections at 450 and 500°C, as determined by [1991Kha] are reproduced in Fig. 2a and 2b.

The maximum solubility for Al in the (Al)+CuAl2+ 4 three-phase equilibrium is 1.0 at.% Cu, 0.01 at.% Sc

at 450°C and 1.67 at.% Cu, 0.05 at.% Sc at 500°C. The maximum solubility for Al in the (Al)+ 4+ScAl3three phase equilibrium is 0.19 at.% Cu, 0.05 at.% Sc at 450°C and 0.21 at.% Cu, 0.05 at.% Sc at 500°C.


A partial vertical section at constant 20 mass% Cu with up to 6 mass% Sc, given in Fig. 3, was constructed

based on results of DTA, metallography and X-ray phase analysis [1988Kha]. The data given at constant 4

mass% Sc are not sufficient for constructing any diagram. [1992Tor] determined a partial vertical section

from 40 mass% Cu to 2 mass% Sc which is reproduced in Fig. 4.


4, ScCu4+xAl8-x phase shows paramagnetic behavior at low temperature and becomes diamagnetic above

about 70 K [1997Sus]. The electrical resistivity as a function of the temperature is linear from 50 K to 300

K and the RT/ 4.2K values are 1.61 (x = 2.15), 1.69 (x = 1.5), 1.64 (x = 0.85) and 1.82 (x = 0).

3, ScCu2Al phase is also paramagnetic [1996Nak], measured magnetic susceptibility showed very weak

temperature dependence.

Miscellaneous

[2003Kan] studied crystal structure of the ternary 4, ScCu4+xAl8-x phase theoretically. The properties

related to the lattice vibration, such as phonons, density of states, specific heat and vibrational entropy were

calculated.

References



[1965Tes] Teslyuk M.Yu., Protasov, V.S. “The Crystal Structure of Ternary Phases in the Sc-Cu-Al

System”, Sov. Phys. Crystallogr., 10, 470-471 (1966), translated from Kristallografiya, 10,


[1968Dwi] Dwight, A.E., Mueller, M.H., Conner, R.A., Downey Jr., J.W., Knott, H., “Ternary





[1987Dwi] Dwight, A.E., Kimball, C.W., “ScT2X and LnT2X Compounds with the MnCu2Al-Type

Structure”, J. Less-Common Met., 127, 179-182 (1987) (Crys. Structure, Experimental, 9)

[1988Kha] Kharakterova, N.L., Dobatkina, T.V., “Polythermal Sections of the Al-Cu-Sc System”,

Russ. Metall., (6), 175-178 (1988), translated from Izv. Akad. Nauk SSSR, Met., (6), 180-182

(1988) (Equi. Diagram, Experimental, #, 5)

[1988Sub] Subramanian, P.R., Laughlin, D.E., Chakrabarti, D.J., “The Cu - Sc (Copper - Scandium)

System”, Bull. Alloy Phase Diagrams, 9, 378-382 (1988) (Equi. Diagram, Thermodyn.,

Review, 20)

[1991Kha] Kharakterova, M.L., “Phase Composition of Al-Cu-Sc Alloys at Temperature of 450 and

500°C”, Russ. Metall. (Engl. Transl.), 2, 195-199 (1991), translated from Izv. Akad. Nauk

SSSR, Met., (4), 191-194 (1991) (Crys. Structure, Equi. Diagram, Experimental, Mechan.

Prop., 9)

129


MSIT®

Al–Cu–Sc

[1991Ran] Ran, Q., ”Aluminium - Copper - Scandium”, MSIT Ternary Evaluation Program, in MSIT


Stuttgart; Document ID: 10.10210.1.20, (1991) (Equi. Diagram, Assessment, 18)

[1992Yun] Yunusov, I., Ganiyev, I.N., Vakhobov, A.V., “The Al-CuAl2-ScAl2 System” (in Russian),

Metally, 6, 196-199 (1992) (Crys. Structure, Equi. Diagram, Experimental, 4)

[1992Tor] Toropova, L.S., Kharakterova, M.L., Eskin, D.G., “The Surface Solidification Projection

Al-Cu-Sc System in Aluminium-Rich Range” (in Russian), Metally, 3, 207-212 (1992)



Alloys”, Subramanian,. P.R., Chakrabarti,. D.J., Laughlin, D.E (Eds.), ASM International,


*, 226)

[1996Nak] Nakonechna, N.Z., Shpyrka, Z.M., “The Crystal Structure of the ScCu2Al and ScCu0.6Al1.4

Compounds”, Vestn. L’vov. Univ, Ser. Khim., 36, 29-33 (1996) (Crys. Structure,


[1997Rok] Rokhlin, L.L., Dobatkina, T.V., Kharakterova, M.L., “Structure of the Phase Equilibrium

Diagrams of Aluminum Alloys with Scnadium”, Powder Metall. Met. Cer., 36, 128-132


[1997Sus] Suski, W., Cichorek, T., Wochowski, K., Badurski, D., Kotur, B.Ya., Bodak, O.I.,

“Low-Temperature Electrical Resistance of the U(Cu,Ni)4Al8 System and Magnetic and

Electrical Properties of ScCu4+xAl8-x”, Physica B (Amsterdam), 230-232, 324-326 (1997)

(Crys. Structure, Experimental, Electr. Prop., 10)

[1999Cac] Cacciamani, G., Riani, P., Borzone, G., Parodi, N., Saccone, A., Ferro, R., Pisch, A.,

Schmid-Fetzer, R., “Thermodynamic Measurements and Assessment of the Al-Sc System”,

Intermetallics, 7, 101-108 (1999) (Experimental, Crys. Structure, Equi. Diagram,

Thermodyn., 26)




[2002Wat] Watson, A., Wagner, S., Lysova, E., Rokhlin, L., “Cu-Sc (Copper-Scandium)”, MSIT

Binary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials

Science International Services GmbH, Stuttgart; Document ID: 20.20091.1.20, (2002)

(Crys. Structure, Equi. Diagram, Assessment, 14).




[2003Kan] Kang, Y., Chen, N., “Site Preference and Vibrational Properties of ScCuxAl12-x”, J. Alloys

Compd., 349(1-2), 41-48 (2003) (Calculation, Crys. Structure, Experimental, Phys. Prop.,

29)

130


MSIT®

Al–Cu–Sc

Table 1: Crystallographic Data of Solid Phase

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Cu)

< 1084.62

Cu1-xAlx

cF4

Fm3m

Cu

a = 361.46

a = 361.52

a = 365.36

at 25°C [Mas2], melting point [1994Mur]

0 to 19.7 at.% Al, [Mas2]

x = 0, quenched from 600°C

x = 0.152, quenched from 600°C, linear

da/dx

dissolves ~ 0.5 at.% Sc (865°C)

[1988Sub]

(Al)

< 660.45

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2],

0 to 2.48 at.% Cu [2003Gro]

( Sc)

< 1337

hP2

P63/mmc

Mg

a = 330.88

c = 526.80

25°C [Mas2]

( Sc)

1541-1337

cI12

Im3m

W

a = 373 [2002Wat], negligible (?) solid solubility

of Cu in ( Sc)

, Cu3Al(h)

1049-559

cI2

Im3m

W

a = 295.64

70.6 to 82 at.% Cu, [2003Gro]

at 672°C in + (Cu) alloy

2, Cu100-xAlx< 363

-

TiAl3long period

super-lattice

-

a = 366.8

c = 368.0

22 x 23.5 [2003Gro]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu

(subcell only)

0, Cu100-xAlxCu 2Al

1037-800

cI52

I43m

Cu5Zn8

- 31 x 40.2 [Mas2],

62 to 68 at.% Cu [2003Gro]

1, Cu9Al4< 890

cP52

P3m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu [Mas2]

powder and single crystal, [V-C2]


, Cu100-xAlx< 686

hR*

R3m

a = 1226

c = 1511

38.1 x 40.7 [Mas2]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

1, Cu100-xAlx958-848

cubic? - 37.9 x 40.6

59.4 to 62.1 at.% Cu, [Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.47 x 0.78

55.0 to 61.1 at.% Cu, [Mas2, V-C2],

1, Cu47.8Al35.5(h)

590-530oF88 - 4.7

Fmm2Cu47.8Al35.5

a = 812

b = 1419.85c = 999.28


2, Cu11.5Al9(r)

< 570oI24 - 3.5

Imm2Cu11.5Al9

a = 409.72

b = 703.13c = 997.93


131


MSIT®

Al–Cu–Sc

1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200c = 863.5

49.8 to 52.4 at.% Cu


2, CuAl(r)

< 560

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu

[V-C2]

, CuAl2< 591

tI12

I4/mcm

CuAl2

a = 606.7

c = 487.7

31.9 to 33.0 at.% Cu, [2003Gro]

single crystal [V-C2]

ScCu

< 1125

cP2

Pm3m

CsCl

a = 324 to 326 [V-C2]

ScCu2

< 990

t16

I4/mmm

MoSi2

a = 329.0

c = 838.8

[2002Wat]

ScCu4

< 925

tI* a = 491

c = 698

[Mas2, 2002Wat]

ScAl3< 1320

cP4

Pm3m

AuCu3

a = 410.5 [Mas, V-C]

ScAl2< 1420

cF24

Fd3m

MgCu2

a = 757.8 [1999Cac]

ScAl

< 1240

cP2

Pm3m

CsCl

oP8

Cmcm

CrB

a = 354.0

a = 398.8

b = 988.2

c = 365.2

[V-C]

[V-C]

Sc2Al

< 1300

hP6

P63/mmc

Ni2In

a = 488.8

c = 617.3

[1999Cac]

* 1, ScCuAl hP12

P63/mmc

MgZn2

a = 504

c = 824

a = 523

c = 849

[1965Tes]

[1968Dwi]

* 2, ScCu0.6Al1.4 hP24

P63/mmc

MgNi2

a = 525.2

c = 1711.3

[1996Nak]

* 3, ScCu2Al cF16

Fm3m

MnCu2Al

a = 619.9

a = 620

a = 620.3

[1996Nak]

* 4, ScCu4+xAl8-x tI26

I4/mmm

ThMn12

a = 863 to 866

c = 510 to 443

[1991Kha, 1992Yun, 1997Sus]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

132


MSIT®

Al–Cu–Sc

(Al)

1.0·10-30.75·10-30.5·10-30.25·10-3 1.5·10-31.25·10-3Al

Sc, at.%

e2

5

10

20

15

ScAl3

(Al)

U, 572°C

e1

E, 546°C

Cu,at.%

q

t

Fig. 1: Al-Cu-Sc.

Partial liquidus

surface of the Al-rich

corner [1992Tor]

Sc 3.00Cu 0.00Al 97.00

Sc 0.00Cu 3.00Al 97.00


Axes: at.%

(Al)+ScAl3+τ4

(Al)

(Al)+τ

4

(Al)+

ScA

l 3

(Al)+θ+τ

4

(Al)+θ

Fig. 2a: Al-Cu-Sc.

Partial isothermal

section of the Al-rich

corner at 450°C

[1991Kha]

133


MSIT®

Al–Cu–Sc

Sc 4.00Cu 0.00Al 96.00

Sc 0.00Cu 4.00Al 96.00


Axes: at.%

(Al)+

ScA

l 3

(Al)

(Al)+ScAl3+τ4(A

l)+τ4

(Al)+θ

(Al)+θ+τ

4

Fig. 2b: Al-Cu-Sc.

Partial isothermal

section of the Al-rich

corner at 500°C

[1991Kha]

500

600

Sc 0.00Cu 9.60Al 90.40

Sc 4.18Cu 9.86Al 85.96Sc, at.%

Tem

pera

ture

, °C

(Al)+θ (Al)+θ+τ4

(Al)+τ4

(Al)+ScAl3+τ4

546°C

L+(Al)+τ4

572°CL+(Al)+ScAl3

L+ScAl3

L

L+(Al)

1.0 4.02.0 3.0

Fig. 3: Al-Cu-Sc.

Partial polythermal

section at 20

mass% Cu

134


MSIT®

Al–Cu–Sc

400

500

600

700

Sc 0.00Cu 22.06Al 77.94

Sc 1.21Cu 0.00Al 98.79Sc, at.%

Tem

pera

ture

, °C

(Al)+θ

L+(Al)+τ4

L

L+θ

L+τ4+ScAl3

L+ScAl3

(Al)+θ+τ4

(Al)+τ4

(Al)+ScAl3

(Al)+τ4+ScAl3

L+(Al)+ScAl3L+τ4

L+θ+τ4L+(Al)+θ

572°C

546°C

1.00.5

Fig. 4: Al-Cu-Sc.

Partial vertical section

of the Al-rich corner

from 40 mass% Cu to

2 mass% Sc

[1992Tor]

135


MSIT®

Al–Cu–Si

Aluminium – Copper – Silicon

Hans Leo Lukas, Nathalie Lebrun

Literature Data

In the early work the Al corner was investigated by thermal analysis, by optical micrographs [1923Wet,

1928Gwy, 1931Ura, 1953Phi, 1975Kuz] and by measuring the electric resistivity [1940Wie]. A ternary

eutectic L +(Al)+Si was found at 525°C [1923Wet, 1928Gwy, 1931Ura, 1975Kuz], at 524°C [1953Phi]

or 522°C [1936His]. The temperature given by [1984Oya], 512°C, deviates considerably. The growth of

this eutectic is complex due to the coarsening during solidification [1983Sch]. Liquidus as well as solidus

and solvus of the (Al) solid solution were determined in very detail by [1953Phi]. The papers agree well.

[1968Epi] gave three vertical sections at 5, 8 and 10 mass% Si up to 55 mass% Cu. The eutectic agrees well

with the previously mentioned papers, whereas the liquidus surface disagrees. In the section at 8 mass% Si

the boundary of L against L+Si in the interval 29 to 39 mass% Cu go from 580 to 590°C. L+Si tie lines go

from the points of this boundary to pure Si and pass the 10 mass% Si section between 30 and 40 mass% Cu.

In the 10 mass% Si section, however, for this whole range of Cu contents above 580°C single phase liquid

is shown. This is a severe contradiction exceeding by far the limits of accuracy of the drawings. The whole

ternary system was investigated by thermal analysis and by interpretation of microstructures recorded in

micrographs [1934Mat] and [1936His]. Matsuyama [1934Mat] presented 12 vertical sections, a projection

of the liquidus surface with the Cu corner enlarged in an extra diagram, and an isothermal section at room

temperature. Hisatsune [1936His] reported 16 vertical and four isothermal sections as well as the lines of

double saturation of the liquidus. No ternary phase exists in the system. The later detected phase of the

binary Cu-Si system in both papers was not distinguished from the (Cu) solid solution. Between the

phases of Cu-Al and Cu-Si, continuous solid solubility was found. [1934Mat] assumed complete solid

solubilities between the 0 (CuAl) and (CuSi) phase, whereas [1936His] reported it between in CuSi

and 1 in CuAl. However, these three phases have different crystal structures [V-C], which makes complete

miscibility unlikely. The two papers disagree in the 70 to 90 mass% Cu region of the liquidus surface.

[1934Mat] shows a large field of primary crystallization of 0- and a separate one for 1. [1936His] shows

smaller fields of primary crystallization for the 0 and 1 phases, but a large one for 1- . Both papers agree

that all binary Al-Cu phases containing more Al than 1 dissolve less than 1 mass% Si. The Cu-Si phase

dissolves about 1 mass% Al, whereas , ' and " dissolve between 2 and 3 mass% Al. Part of the Cu-rich

corner was investigated by [1948Wil]. The phase is stabilized by Al and seems to be stable to room

temperature inside the ternary system. This was confirmed by [1974Llo]. The phase is also stabilized, but

decomposes eutectoidally at 545°C [1974Llo] into (Cu), and 1 (named 2 by [1974Llo]) below both

binary eutectoids.

Literature published until 1986 is carefully reviewed by [1992Luk] and further updated by the present

evaluation.

Binary Systems

Assessments of the Al-Cu system by [2003Gro], of the Al-Si system by [2003Luk] and of the Cu-Si system

by [2002Leb] form the binary edge boundary consistent with the ternary data. They are based on [1994Mur,

1998Liu] for Al-Cu, [1984Mur] for Al-Si and [1994Ole, 2000Yan] for Cu-Si, respectively. For the Al-Cu

system recent crystal structure investigations of the 1 and 2 phases [2002Gul] are taken into account. For

the solubilities of Cu and Si in Al the thermodynamic calculations of the COST 507 action [1998Ans] are

accepted, as they provide numerically a much better resolution than the above mentioned graphic

assessments can do.

136


MSIT®

Al–Cu–Si

Solid Phases

No ternary phase was found. The stable binary phases are listed in Table 1. The Greek letters for

abbreviation of the phases are those used by the accepted binary diagrams, except 1, to distinguish it from

of the Cu-Si system. All phases except of the binary Al-Cu system have a numerical subscript; the

phases of the Cu-Si system are indexed by a prime or double prime instead of a subscript.


A tentative reaction scheme is shown in Fig. 1a and Fig. 1b. The non-dashed four-phase equilibria

containing liquid are taken from [1936His]. The eutectic E5 is more accurately given by [1953Phi], it agrees

with that of [1936His]. The equilibrium E4 is taken from [1974Llo]. The dashed equilibria are attempts to

complete the reaction scheme. P2 and U3 are introduced to distinguish from 1. As the phase may be

stable down to room temperature [1974Llo], the three phase equilibria reported by [1936His] to contain the

(Cu) solid solution at 400°C are assumed to contain instead of (Cu). Of the three phase equilibria at room

temperature, Si+(Al)+ is well-established [1928Gwy, 1936His, 1953Phi, 1986Che]. + 2+Si, 2+ 2+Si,

2+ 1+Si, 1+ 1+Si, and 1+ "+Si are reported by [1936His]. The transformations 1 2, 1 2 of Al-Cu

and ' " of the Cu-Si binary system are neglected in Fig. 1 for clarity. The compositions of the liquid

in the invariant equilibria, given by [1936His], are summarized in Table 2.

Liquidus Surface, Solidus and Solvus Surfaces

The liquidus surface of the whole system is shown in Fig. 2. The lines of double saturation of liquid are

taken from [1936His], except those between and 1. The isotherms in the Cu corner are derived from the

vertical sections given by [1936His]. The isotherms of the primary crystallization of Si are taken from

[1934Mat], except at 800°C and below, which are adjusted to fit with the isotherms derived from the data

of [1936His]. The liquidus surface of the Al corner in Fig. 3 is thermodynamically calculated using the

binary thermodynamic descriptions of Al-Cu and Al-Si from the COST 507 database [1998Ans] adding

ternary terms to the Gibbs energy description of liquid reproducing temperature and composition of liquid

of the eutectic L (Al)+Si+ as given by [1953Phi] the most detailed experimental investigation of the

Al-rich part. ternGliq = xAl xCu xSi (27000 xAl+100000 xCu+8000 xSi) J (mole of atoms)-1

This ternary term is tentative and must not be taken in the range with less than about 75 at.% Al. The

calculated liquidus agrees very well with the graph of [1953Phi] within the accuracy of the drawing.

The solidus and solvus surfaces of the (Al) solid solution in Figs. 4 and 5 are also thermodynamically

calculated using the same data set that was used to calculate the liquidus, yielding virtually identical results

as given by [1953Phi], whereas the solvus after [1940Wie] shows about 5 to 10% higher solubilities in (Al).

Isothermal Sections

In Fig. 6 the 400°C isothermal section of the Cu corner is given. The concentrations of the (Cu)+ + 1

equilibrium are taken from [1948Wil], those of the + 1+ ", 1+ "+Si, + "+ , and + + 1 equilibria

from [1936His], although [1936His] assumed the (Cu) phase at the concentrations ascribed to . The

remaining lines are interpolated between these concentrations and those taken from the accepted binary

systems. The isothermal section therefore must be taken as tentative. Although [1934Mat, 1936His] and

[1948Wil] gave more isothermal and vertical sections, too much speculation is needed to draw isothermal

sections at higher temperatures which agree with the three papers. At room temperature all phases with less

than 70 at.% Cu are in equilibrium with Si [1934Mat, 1936His].

137


MSIT®

Al–Cu–Si


Several polythermal sections were reported by [1936His]. They suffer from the non-distinguishing of the

(Cu) and phases and therefore are not reproduced here. [1986Gul] reported a polythermal section at 40

mass% Cu determined by thermal analysis and X-ray diffraction techniques. The point of double saturation

of liquid with respect to and Si deviates significantly from that shown in Fig. 2 based on [1936His,

1953Phi].

Thermodynamics

The heat of melting of the eutectic in the Al corner was measured by [1986Che] and [1984Mar] to be

364 J g-1 and 357 J g-1 respectively, which corresponds to 11.6 and 11.4 kJ mol-1. [1985Far] used an ideal

model to determine the heat of mixing at the eutectic composition. The calculated value found to be

422 J g-1 (13.5 kJ mol-1) is overestimated.

[1984Ber] reported from emf measurements the activities of Al in Al-Cu-Si alloys at 660, 700, 800 and

900°C.

[2000Wit] measured the partial and the integral enthalpies from liquid Al-Cu-Si alloys at 1302 ± 3°C using

a high temperature calorimeter only 3 vertical sections (xAl : xSi = 0.8 : 0.2, 0.5 : 0.5, 0.2 : 0.8 with

0 xCu 1). The thermodynamic functions of mixing were calculated from the partial measured enthalpies

using a regular association model. Minimum of enthalpy varies from -14.5 kJ mol-1 (Cu-25 Si (at.%)) to

-17.3 kJ mol-1 (Al - 60Cu (at.%)).


Using a grain and pore formation, [2002Chi] studied the micro-porosity in an 3Cu-Al-7Si (mass%) alloy

containing soluble hydrogen.

Si additions were found to lead to a very slight increase in corrosion resistance, while Cu additions were

found to lower the overall corrosion resistance significantly [1994Gri, 2001Tra]. This is probably due to the

large percentage of primary silicon phase in that alloys [2001Tra]. Moreover, Si accelerates the

age-hardening of the Al-Cu-Si alloys [1994Gri]. Corrosion can occur when alloys are exposed to

photolithographic processing [1990Wes].

[2000Zho] investigated the creep behavior in 0.5Cu-Al-1Si (mass%) alloys with thickness ranging from 10

to 500 m.

In compressed samples of high purity aluminium alloys, with hard precipitates 0.5Cu-Al-1Si (mass%), a

variety of deformation band patterns has been observed, including occasional exquisite detailed structuring

[1998Kul].

Miscellaneous

[1991Sta] studied the precipitation of Si and Cu in alloys 1.3Cu-Al-19.1Si (at.%). From liquid quenched of

this alloy composition, a transition ’ is observed ( ’ intermediate and equilibrium phase). For heating

rates less than 20°C/min, Cu precipitates as the ’, while for heating rates more than 40°C/min, Cu

precipitates mainly as the phase. In solid quenched samples, Guinier-Preston (GP) zone formation

occurred during annealing at room temperature with a rate of 104 time slower than in the corresponding

Al-Cu binary.

[1990Yam] studied the solid solubilities of Cu and Si in Al under high pressure to 3 Gpa using the diffusion

couple method. It was found an increase of the solubilities with high pressure.

[1985Oko] investigated the solidification structures of gasifiable pattern cast 4.25Cu-Al-1.03Si (at.%) alloy

to establish an influence of variations in casting conditions on such structure.

138


MSIT®

Al–Cu–Si

References

[1923Wet] Wetzel, E., “Progress in Aluminium Investigation, Copper and Silicon in Aluminium” (in

German), Metallboerse, 13, 936-938 (1923) (Equi. Diagram, Experimental, 5)

[1928Gwy] Gwyer, A.G.C., Philips, H.W.L., Mann, L., “The Constitution of the Alloys of Aluminium

with Copper, Silicon and Iron”, J. Inst. Met., 40, 297-358 (1928) (Equi. Diagram,

Experimental, 33)



[1931Ura] Urazov, G.G., Pogodin, S.A., Zomornev, G.M., “Physico-Chemical Investigations of

Ternary Alloys of Aluminium with Silicon and Copper” (in Russian), Izv. Inst.

Fiziko-Khimich. Analiza, 5, 157-200 (1931) (Equi. Diagram, Experimental, 30)

[1934Mat] Matsuyama, K., “Ternary Diagram of the Al-Cu-Si System” (in Japanese), Kinzoku no

Kenkyu, 11, 461-490 (1934) (Equi. Diagram, Experimental, #, *, 8)

[1936His] Hisatsune, C., “Constitution Diagram of the Copper-Silicon-Aluminium System” (in

Japanese), Mem. Coll. Eng. Kyoto Imp. Univ., 9(1), 18-47 (1935), translated from Tetsu to

Hagane, 22, 597-622 (1936) (Equi. Diagram, Experimental, #, *, 12)

[1940Wie] Wiehr, H., “Contribution to the Knowledge of the Aluminium-Copper-Silicon and

Aluminium-Copper-Iron Systems” (in German), Alum. Arch., 31, 5-14 (1940) (Equi.


[1948Wil] Wilson, F.H., “The Copper-Rich Corner of the Copper-Aluminium-Silicon Diagram”,

Trans. Amer. Inst. Met. Eng., Inst. Metals Div., 175, 262-282 (1948) (Equi. Diagram,

Experimental, 10)

[1953Phi] Philips, H.W.L., “The Constitution of Aluminium-Copper-Silicon Alloys”, J. Inst. Met., 82,


[1968Epi] Epikhin, M.A., Zaboleev-Zotov, V.V., Mishchenko, Yu.N., Tsymlov, A.I., Shashin, A.V.,

“Vertical Sections of the Equilibrium Diagram Aluminium-Copper-Silicon” (in Russian),

Metallovedenie Proch. Mater., Pashkov, (Ed.), Volgograd, (1968) (Equi. Diagram,

Experimental, 0)

[1974Llo] Lloyd, B.A., Pyemont, J.W., “Phase Equilibrium Diagram for 2% Silicon Isopleth in

Copper-Aluminium-Silicon Alloys in the Range 5 to 11 % Al”, Met. Tech., 534-537 (1974)


[1975Kuz] Kuznetsov, G.M., Smagulov, D.U., Vasenova, S.V., “Experimental Determination of the

Direction of Tie Lines in the Two Phase Fields (Al)+Liquid in the Al-Cu-Mg and Al-Cu-Si

System” (in Russian), Izv. V. U. Z. Tsvetn. Met., (4), 96-100 (1975) (Equi. Diagram,

Experimental, 14)

[1983Sch] Schnake, W., Abaud, S., “Solidification of the Al-Cu-Si Ternary Eutectic”, Uni. Chile,

Conf.: CONAMET 83, Santiago, A474-A482 (1983) (Experimental, 14)

[1984Ber] Berecz, E., Bader, I., Weberne, Kovaks, E., Horvath, J., Gabor, Z., “Thermodynamic

Examination of Aluminium Alloys by the Electrochemical Method”, Banyasz. Kohasz.

Lapok, Kohasz., 117(9), 413-417 (1984) (Experimental, Thermodyn., 10)

[1984Mar] Martynova, N.M., Rodionova, E.K., Tishura, T.A., Cherneeva, L.I., “Enthalpy of Melting

of Metallic Eutectics”, Russ. J. Phys. Chem. (Engl. Transl.), 58(4), 616-617 (1984),

translated from Zh. Fiz. Khim., 58(4), 1009-1010 (1984) (Thermodyn., 6)

[1984Mur] Murray, J.L., Mcalister, A.J., “The Al-Si (Aluminum-Silicon) System”, Bull. Alloy Phase

Diagrams, 5, 74-84 (1984) (Equi. Diagram, Review, #, 73)

[1984Oya] Oya, S., Fujii, T., Ohtaki, M., Baba, S., “Solidified Structure and Hot Tearing of Al-4.5%

Cu and Al-4.5% Cu-5% Si Alloys Containing Various Additives” (in Japanese), J. Japan

Inst. Light Metals, 34(9), 511-516 (1984) (Experimental, 18)

[1985Far] Farkas, D., Birchenall, C.E., “New Eutectic Alloys and Their Heats of Transformation”,

Met. Trans. A, 16A, 323-328 (1985) (Experimental, Thermodyn., 12)

139


MSIT®

Al–Cu–Si



[1985Oko] Okorafor, O.E., “Solidification Structures and Gasfiable Pattern Casting of

Al-4.25Cu-1.03Si”, Trans. Indian Inst. Met., 38(5), 415-422 (1985) (Experimental, 11)

[1986Che] Cherneeva, L.I., Martynova, N.M., Rodionova, E.K., “Energy Capacity of Metallic Alloys

as Promising Heat-Storing Materials” (in Russian), Izv. Vyss. Uchebn. Zaved., Energia, 12,

78-82 (1986) (Thermodyn., 7)

[1986Gul] Gul’din, I.T., Zakharov, A.M., Arnold, A.A., “The Effect of Iron and Silicon on the

Liquidus Temperature and Phase Composition of an Aluminium Alloy with 40% Copper”

(in Russian), Izv. V. U. Z. Tsvetn. Met., 4, 90-95 (1986) (Equi. Diagram, 8)




[1990Wes] Weston, D., Wilson, S. R., Kottke, M., “Microcorrosion of Al-Cu and Al-Cu-Si Alloys:

Interaction of the Metallization with Subsequent Aqueous Phototithographic Processing”,

J. Vac. Sci. Technol., A8(3), 2025-2032 (1990) (Experimental, Thermodyn., 0)

[1990Yam] Yamane, T., Minamino, Y., Sato, T., Itaya, E., Miyamoto, Y., Koizumi, M., “Solid

Solubility Chages in Aluminium Base Binary Alloys under High Pressure Measured by

Diffusion Couple Method”, Met. Abstr. Light Metals and Alloys, 23, 80 (1990) (Equi.

Diagram, Experimental,0)


Enthalpy of Aluminium in some Phases with Cu and Cu3Au Structures”, J. Less-Common

Metals, 170, 171-184 (1991) (Experimental, Crys. Struct., 57)

[1991Sta] Starink, M.J., Mourik, P.V., “A Calorimetric Study of Precipitation in an Al-Cu Alloy with

Silicon Particles”, Metall. Trans. A, 22A, 665-674 (1991) (Calculation, Crys. Structure,

Experimental, 40)

[1992Luk] Lukas, H.L., ”Aluminium - Copper - Silicon”, MSIT Ternary Evaluation Program, in MSIT



Assessment, 15)

[1994Gri] Griffin, A.J., Brotzen, F.R., Dunn, C.F., “Impedance-Spectroscopy Response of

Aluminium-Copper-Silicon Alloys”, J. Electrochem. Soc., 141(12), 3473-3479 (1994)

(Corrosion, Crys. Structure, Experimental, 19)

[1994Mur] Murray, J.L., “Al-Cu (Aluminium-Copper)” in “Phase Diagrams of Binary Copper Alloys”,

Subramanian, P.R., Chakrabarti D.J., Laughlin, D.E., (Eds.), ASM International, Materials

Park, OH, 18-42 (1994) (Equi. Diagram, Cryst. Struct., Thermodyn., Review, 226)

[1994Ole] Olesinski, R.W., Abbaschian, G.J., “Cu-Si (Copper-Silicon)” in “Phase Diagrams of Binary

Copper Alloys”, Subramanian, P.R., Chakrabarti D.J., Laughlin, D.E., (Eds.), ASM

International, Materials Park, OH, 398-405 (1994) (Review, Equi. Diagram, Cryst. Struct.,

Thermodyn., 60)

[1998Ans] Ansara, I., Dinsdale, A.T., Rand, M.H., COST507. Thermochemical Database for Light

Metal Alloys, Vol. 2, European Communities, Luxemburg, (1998) (Equi. Diagram,

Thermodyn., Calculation)

[1998Kul] Kulkarni, S.S., Starke, E.A., Kuhlmann-Wilsdorf, D., “Some Observation on Deformation

Banding and Correlated Microstructures of Two Aluminium Alloys Compressed at

Different Temperatures and Strain Rates”, Acta Mater., 46(15), 5283-5301 (1998) (Crys.


[1998Liu] Liu, X.J., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria in the Cu-Rich Portion of

the Al-Cu Binary System”, J. Alloys Comp., 264, 201-208 (1998) (Equi. Diagram,

Experimental, 25)

[2000Wit] Witusiewicz, V.T., Arpshofen, I., Seifert, H.-J., Aldinger, F., “Enthalpy of Mixing of Liquid

Al-Cu-Si Alloys”, J. Alloys Compd., 297, 176-184 (2000) (Experimental, Thermodyn., 11)

140


MSIT®

Al–Cu–Si

[2000Yan] Yan, X., Chang, Y.A., “A Thermodynamic Analysis of the Cu-Si System”, J. Alloys

Compd., 308(1-2), 221-229 (2000) (Equi. Diagram, Thermodyn., 41)

[2000Zho] Zhou, Q., Itoh, G., “Creep Behavior of Aluminum Alloy Foils for Microelectronic Circuits”,

Key Eng. Mater., 171-174, 633-638 (2000) (Experimental, Mechan. Prop., 12)

[2001Tra] Traldi, S.M., Costa, I., Rossi, J.L., “Corrosion of Spray Formed Al-Si-Cu Alloys in Ethanol

Automobile Fuel”, Key Eng. Mater., 189-191, 352-357 (2001) (Corrosion,

Experimental, 11)

[2002Chi] Chirazi, A., Atwood, R.C., Lee, P.D., “Micro-Macro Modelling of Microstructure and

Microporosity in Al-Si-Cu Alloys”, Mater. Sci. Forum, 396-402, 661-666 (2002) (Crys.


[2002Gul] Gulay, L.D., Harbrecht,B., “The Crystal Structures of the 1 and 2 Phases in the Al-Cu

System”, in “Crystal Chemistry of Intermetallic Compounds”, Abstr. VIII Int. Conf. Lviv,


[2002Leb] Lebrun, N., Dobatkina, T., Kuznetsov, V., “Cu-Si (Copper-Silicon)”, MSIT Binary


International Services GmbH, Stuttgart; Document ID: 20.12505.1.20, (2002) (Crys.

Structure, Equi. Diagram, Assessment, 23)








Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Cu)

< 1084.62

Cu1-xAlx

cF4

Fm3m

Cu

a = 361.46

a = 361.52

a = 365.36

at 25°C [Mas2], 0 to 19.7 at.% Al

[Mas2]


[1991Ell], x = 0, quenched from 600°C

[1991Ell], x = 0.152, quenched from

600°C, linear da/dx

(Al)

< 660.45

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

0 to 2.48 at.% Cu [Mas2]

(Si)

< 1414

cF8

Fd3m

C (diamond)

a = 543.06 0 to 0.003 at.% Cu [1994Ole]

, Cu1-x-yAlxSiy Cu3Al

1049-559

Cu6Si

853-787

cI2

Im3m

W

a = 295.64

a = 285.4

70.6 to 82 at.% Cu [1985Mur, 1998Liu]

at 672°C in + (Cu) alloy

14.2 to 16.2 at.% Si [1994Ole]

at 14.9 at.% Si [1994Ole]

141


MSIT®

Al–Cu–Si

2, Cu100-xAlx< 363

TiAl3long period

superlattice a = 366.8

c = 368.0

22 x 23.5 [Mas, 1985Mur]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu (subcell only)

0, Cu1-x-yAlxSiy Cu2Al

1037-800

cI52

I43m

Cu5Zn8

31 x 40.2 [Mas]

62 to 68 at.% Cu [1998Liu]

1, Cu9Al4< 890

cP52

P43m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu [Mas2, 1998Liu]



1, Cu100-xAlx< 686

hR*

R3m

a = 1226

c = 1511

38.1 x 40.7 [Mas2, 1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

1, Cu100-xAlx958-848

cubic ? - 37.9 x 40.6

[Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6 or hP4

P63/mmc

Ni2In or NiAs

a = 414.6

c = 506.3

0.47 x 0.78

55.0 to 61.1 at.% Cu

[Mas, 1985Mur, V-C2]

NiAs type in [Mas2, 1994Mur]

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2Cu47.8Al35.5

a = 812

b = 1419.85c = 999.28


2, Cu11.5Al9(r)

< 570

oI24 - 3.5

Imm2Cu11.5Al9

a = 409.72

b = 703.13c = 997.93


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu [Mas2, 1985Mur]


2, CuAl(r)

< 560

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu

[V-C2]

, CuAl2< 591

tI12

I4/mcm

CuAl2

a = 606.7

c = 487.7

31.9 to 33.0 at.% Cu [1994Mur]

Single crystal [V-C2, 1989Mee]

, Cu100-xSix

Cu7Si

842-552

hP2

P63/mmc

Mg

a = 256.05

c = 418.46

11.05 x 14.5 at.% Si [1994Ole]

at 14.9 at.% Si [1994Ole]

, Cu5Si(r)

< 729

cP20

P4132

Mn

a = 619.8 17.15 to 17.6 at.% Si [1994Ole]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

142


MSIT®

Al–Cu–Si


, Cu5Si (h)

824-711

t**

a = 881.5

c = 790.3

17.6 to 19.6 at.% Si [1994Ole]

sample was annealed at 700°C [V-C2]

, Cu15Si4< 800

cI76

I43d

Cu15Si4

a = 961.5 21.2 at.% Si [1994Ole, V-C2]

, Cu3Si(h2)

859-558

hR*

R3m

or t**

a = 247

= 109.74°

a = 726.7

c = 789.2

23.4 to 24.9 at.% Si [1994Ole]

[V-C2]

', Cu3Si(h1)

620-467

hR*

R3

a = 472

= 95.72°

23.2 to 25.2 at.% Si [1994Ole]

", Cu3Si(r)

< 570

o** a = 7676

b = 700

c = 2194

23.3 to 24.9 at.% Si [1994Ole]


Al Cu Si

L + + 0 1 980 P1 L 24.3 69.2 6.5

L + 0 1+ 1 910 U1 L 39.5 57.4 3.1

1 L + 1 840 E1 L 38.2 54.3 7.5

L + 1 2 + Si 760 U3 L 37 50.1 12.9

L + + Si 727 E2 L 10.6 68.1 21.3

L + 2 1 + Si 608 U8 L 60.1 31.7 8.2

L + 1 + Si 573 U9 L 68.2 25.1 6.7

L + (Al) + Si 524 E5 L

(Al)

80.6

96.8

13.4

2.1

6.0

1.1

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

143


MSIT®

Al–Cu–Si

Fig

. 1a:

Al-

Cu

-Si.

Rea

ctio

n s

chem

e, p

art

1

Al-

Cu

Cu

-Si

l +

βγ 0

10

37

p1

β +

(C

u)

κ8

42

p6

Lγ 1

+ (

Si)

ca.

80

0e 5

Al-

Cu

-Si

L +

β +

γ0

γ 19

80

P1

Al-

Si

l +

(C

u)

β8

52

p4

l +

γ0

ε 1

95

8p2

lβ

+ (

Cu)

10

32

e 1

ε 1 l

+ ε2

84

8e 2

γ 0γ 1

+ β

78

0e 7

ε 1 +

γ1

ε 2

85

0p5

γ 0 +

ε 1γ 1

87

3p3

ε 1 L

+ γ1 +

ε2

84

0E1

L +

β +

γ1 +

ε1

δca

. 9

00

P2

L +

γ0

γ 1 +

ε1

91

0U2

Lη

+δ

+ (

Si)

72

7E2

L +

γ1

δ +

(S

i)?

U3

L +

γ1

ε2 +

(S

i)7

60

U4

δ +

κγ

72

9p9

βδ

+κ

78

5e 6

η +

δε

80

0p8

l S

i +

η8

02

e 4

lδ

+ η

82

0e 3

l + β

δ8

24

p7

L +

γ0

+γ 1

L +

γ1

+ε 1

L +

β +

γ 1

L +

γ1 +

ε2

L +

γ1

+δ

β +

γ 1+

δ

γ 1 +

δ +

(S

i)

L +

δ +

(S

i)

β+(C

u)+

κ

δ+κ+

γ

β+δ+

κ

η+δ+

ε

η +

δ +

(S

i)L

+ ε2 +

(S

i)γ 1+

ε 2+

(S

i)

144


MSIT®

Al–Cu–Si

Fig

. 1b

: A

l-C

u-S

i. R

eact

ion s

chem

e, p

art

2

Al-

Cu

Cu

-Si

Al-

Cu

-Si

Al-

Si

ε 2+

γ 1δ 1

68

6p10

δ +

(Si)

γ 1 +

η?

U5

δ +

β γ

1 + κ

?U6

ε 2 +

γ1

δ 1+

(S

i)6

80

D1

δ +

γ 1

κ +

η?

U7

δ +

γκ

+ ε

67

5U8

δγ+

ε7

10

e 8

βγ 1

+ (

Cu)

55

9e 12

ζ 1+

µ 1ζ 2

57

0p

ε 2+

η 1ζ 1

59

0p12

lη 1

+ θ

59

1p

l +

ε2

η1

62

4p11

δκ

+ ε

+ η

?E3

L +

ε2

η 1 +

(S

i)6

08

U9

γ 1 +

(C

u)

α 2

36

3p13

ζ 1ζ 2

+δ

53

0e ?

lθ

+ (

Al)

548.2

e 14

ε 2ζ 1

+δ

56

0e 11

η 1+

θη 2

56

3p

L +

η1

θ +

(S

i)5

73

U10

ε 2+

η 1ζ 1

+ (

Si)

59

0D2

ε 2δ 1

+ζ 1

+(S

i)5

60

D3

β γ 1

+κ

+ (

Cu)

54

5E4

Lθ

+ (

Al)

+ (

Si)

52

4E5

γ 1+η

+(S

i)

l (

Al)

+ (

Si)

57

7e 10

η' (

Si)

+ η'

'

46

7e

κ γ+

(Cu)

55

2e 13

η (

Si)

+ η

'

55

8e

η' +

εη'

'

57

0p

η +

εη'

62

0p

γ 1+

κ +

η

γ 1+δ

1+

(Si)

κ+

ε +

η

η 1+ζ

1+

(Si)

δ 1+

ζ 1 +

(S

i)

θ+(A

l)+

(Si)

γ 1+

(C

u)

+ α2

γ 1+

κ +

(C

u)

κ +

γ +

(C

u)

η 1+

θ+(S

i)

η+δ+

(Si)

γ 1+

δ+(S

i)γ 1

+ε2+(

Si)

L+ε2+(

Si)

δ +

γ 1+

η

β +

γ 1+

δβ

+ δ

+ κ

δ+

κ +

γ

δ +

κ +

η

δ +

γ 1+

ηη+

δ+ε

δ +

κ +

ε

γ +

κ +

εε 2

+η1+

(Si)

L+

η 1+(S

i)

ε 2+

ζ 1+

(S

i)ε 2+δ

1+

(Si)

L+

θ+(S

i)

β +

(Cu

) +κ

β +

γ 1+

κ

145


MSIT®

Al–Cu–Si

10

20

80 90

10

20

Cu 25.00Al 75.00Si 0.00

Cu 0.00Al 75.00Si 25.00 Data / Grid: at.%

Axes: at.%

(Si)

(Al)

650

64063

062061

0600

590

57056

055054

0

550

560

570

740

720

680

660640

620

600

580

700

θ

580

E5

Al

20

40

60

80

20 40 60 80

20

40

60

80

Cu Al

Si Data / Grid: at.%

Axes: at.%

(Cu)

β P2

P1

δ

η E2 U2

γ1

E1

U1

U3

U8

U9E5

(Al)θ

η1ε2

ε1

1400

1300

1200

1100

1000

900

800

700

600

(Si)

γ0

e4

p7p4

e1 p1 p2 e2p12 p13 e14

e10

e3

Fig. 3: Al-Cu-Si.

Liquidus projection of

the Al-rich corner

Fig. 2: Al-Cu-Si.

Liquidus surface

146


MSIT®

Al–Cu–Si

Cu 4.00Al 96.00Si 0.00

Al


Axes: at.%

550

560

570

540

530

580

590

600

610

620

630

640

650

(Al)

Al

Cu 4.00Al 96.00Si 0.00

Al


Axes: at.%

550

525

500475450425 400

(Si)

θ300350

Al

Fig. 4: Al-Cu-Si.

Solidus surface of the

(Al) solid solution

Fig. 5: Al-Cu-Si.

Solvus surface of the

(Al) solid solution

147


MSIT®

Al–Cu–Si

80

20

20

Cu Cu 60.00Al 40.00Si 0.00


Axes: at.%

(Cu)

γ

κ

γ1

η" γ1+η"+(Si)

κ+η"+γ1

(Cu)+γ1

ε

κ+ε+

η"

δ1

η´´+ε

κ+γ1

(Cu)+κ

η´´+

(Si)

γ1+(Si)

Fig. 6: Al-Cu-Si.


400°C

148


MSIT®

Al–Cu–Tb

Aluminium – Copper – Terbium

Riccardo Ferro, Paola Riani

Literature Data

This evaluation is part of the MSIT Ternary Evaluation Program and incorporates and continues the critical

evaluation made by [1992Ran] considering a fast amount of new published data. Different compounds have

been identified and their crystal structures determined: TbCuAl [1968Dwi, 1973Oes, 1995Kuz] (the high

pressure modification of this compound and its structure were reported by [1987Tsv1, 1987Tsv2]),

TbCuAl3 [1988Kuz], TbCu4Al [1978Tak], Tb2Cu7Al10 [1982Pre, 1995Kuz], TbCu4Al8 [1979Fel,

1995Kuz], TbCu6Al6 [1980Fel] and TbCu0.9Al2.1 [1995Kuz].

The alloys were prepared under protective atmosphere by arc melting or induction melting followed by

homogenization heat treatments. High pressure modification of TbCuAl was made by rapid quenching from

the melt under a pressure of 7.7 GPa.

A partial isothermal section, from 0 to 50 at.% Tb, was built at 650°C or at 400°C in the Al-rich region by

[1995Kuz]. To this end 103 alloys were prepared by arc melting, under purified argon, from 99.5 mass%

Tb and 99.99 mass% Cu and Al. They were then annealed at 650 or 400°C for 1000h. Powder diffraction

techniques were used for phase and structure analysis. Lattice parameters trends for a number of solid

solutions have been reported. Differential thermal analysis was also used.

Binary Systems

The binary systems Al-Tb [2002Gro1], Al-Cu [2003Gro] and Cu-Tb [2002Gro2] are used as boundary

systems.

Solid Phases

Table 1 shows the crystal structure data of the solid phases. Following remarks may be useful.

In the determination of the isothermal section at 650°C of the Al-Cu-Tb system [1995Kuz] identified the

ThMn12 structure for a phase having a small range of compositions 1,Tb(CuxAl1–x)12 (0.4 x 0.43).

The ideal BaCd11 type structure corresponds to a tetragonal body-centered cell, in the space group I41/amd

with Ba in 4a and Cd in 4b, 8d and 32i. A co-ordination of 22 is observed around Ba, and from 10 to 14

around Cd. For Tb an orthorhombic variant of this structure was observed ( 2,TbCu6.4Al4.6 [1995Kuz])

with similar values of the co-ordination numbers.

[1995Kuz] discussing the structure of the Tb compounds proposed the structure La3Al11 type for the

4,Tb3Cu1.2Al9.8 composition, instead of the BaAl4 type previously proposed by [1988Kuz] for TbCuAl3.

For the 5 TbCu0.9Al2.1 phase the hR36 PuNi3 type (or NbBe3 type) was observed [1992Kuz, 1995Kuz]. In

a refinement of the structure of ~HoCuAl2 the following positions were observed [1992Kuz] in the space

group R3m: Ho in 3a + 6c, Cu in 6c, Al in 3b and (Al+Cu) in 18h. The large atoms have co-ordination

number 16 and 20, and the others 12.

Isothermal Sections

A partial isothermal section (from 0 to 50 at.% Tb) was built by [1995Kuz] at 650°C but at 400°C in the

Al-rich region. These are reported in Figs. 1 and 2. Note that in the Cu-Tb edge the Tb2Cu9 compound,

assumed by analogy with the other heavy rare earths, is missing; moreover the TbCu5 compound dissolves

up to ~45 at.% Al. Several ternary phases have been identified; the 2,TbCu6.4Al4.6, 5,TbCu0.9Al2.1 and

4,Tb3Cu1.2Al9.8 (La3Al11 type) phases have been described as point compounds [1995Kuz, 1996Ste]. For

the other phases the following composition ranges have been proposed: 1,Tb(CuxAl1–x)12 with

0.40 x 0.43 (ThMn12 type); 3,Tb2Cu17–xAlx with 5.5 x 9.4 (Th2Zn17 type) and 6,TbCu2–xAlx with

0.85 x 1.15 (Fe2P or ZrNiAl type) [1995Kuz]. Subsequently [1996Ste], using single crystal X-ray

149


MSIT®

Al–Cu–Tb

diffraction, determined the crystal structure of 3 Tb2Cu8Al9 as pertaining to Th2Zn17 type and refined by

the Rietveld method the atomic parameters of 2 TbCu6.4Al4.6, a new structural type related to the BaCd11

type. This phase was previously identified by [1995Kuz].


[1977Bas] found that Neel temperature of the solid solution of the binary compound TbCu with Al

decreases and the Curie temperature reverses sign at 16 at.% Al, i.e. at this composition a transformation

from anti-ferromagnetic to ferromagnetic occurs.

[1998Jav] studied the magnetic properties of the RCuAl (R = Y, Ce to Sm, Gd to Tm and Lu) intermetallic

compounds by means of susceptibility, magnetization and specific heat measurements and observed a

magnetic ordering at low temperatures in most of these materials: PrCuAl and NdCuAl showed an

antiferromagnetic behavior while in the heavy rare-earth compounds (R=Gd-Er) a ferromagnetic coupling

was found.

Magnetization and neutron diffraction measurements conducted by [1996Ehl] showed that TbCuAl orders

ferromagnetically with a Curie temperature of TC = 51K.

References



[1968Dwi] Dwight, A.E., Mueller, M.H., Conner, R.A.Jr., Downey, J.W., Knott, H., “Ternary




RCuAl”, J. Less-Common Met., 30, 225-236 (1973) (Crys. Structure, Experimental, Magn.

Prop., 21)

[1977Bas] Basha, A.F., Chechernikov, V.I., Sinanyan, L.G., Tavansi, A., “Magnetic Properties of

Certain Terbium Alloys with CsCl Structure”, Sov. Phys. - JETP, 45(4), 808-809 (1977)

(Crys. Structure, Experimental, Magn. Prop., 5)

[1978Tak] Takeshita, T., Malik, S.K., Wallace, W.E., “Crystal Structure of RCu4Ag and RCu4Al (R =

Rare Earth) Intermetallic Compounds”, J. Solid State Chem., 23, 225-229 (1978) (Crys.


[1979Fel] Felner, I., Nowik, I., “Magnetism and Hyperfine Interactions of 57Fe, 151Eu, 155Gd, 161Dy,166Er and 170Yb in RM4Al8 Compounds (R = Rare Earth or Y, M = Cr, Mn, Fe, Cu), J. Phys.

Chem. Solids, 40, 1035-1044 (1979) (Crys. Structure, Experimental, Magn. Prop., 8)

[1980Fel] Felner, I., “Crystal Structure of Ternary Rare Earth - 3d Transition Metal Compounds of the


10)

[1982Pre] Prevarskiy, A.P., Kuz'ma, Yu.B., “New Compounds with Th2Sn17 Type Structure in

REM-Al-Cu Systems”, Russ. Metall., (6), 155-156 (1982) (Crys. Structure, Experimental,

5)

[1985Mur] Murray, J.L., “The Aluminum-Copper System”, Int. Met. Rev., 30(5), 211-233 (1985) (Equi


[1987Tsv1] Tsvyashchenko, A.V., Fomicheva, L.N., “High Pressure Synthesis and Structural Studies of

Rare Earth (R) Compounds RCuAl”, J. Less-Common Met., 134, L13-L15 (1987) (Crys.




from Izv. Akad. Nauk SSSR, Neorg. Mater., 23, 1148-1152 (1987) (Crys. Structure,

Experimental, 15)

150


MSIT®

Al–Cu–Tb

[1988Kuz] Kuz'ma, Yu.B., Stel'makhovich, B.M., “New RCuAl3 Compounds (R = Tb, Dy, Ho, Er, Tm,

Yb) and Their Crystal Structure” (in Russian), Dop. Akad. Nauk Ukr. SSR B, Geol. Khim.

Biol., (11), 40-43 (1988) (Crys. Structure, Experimental, 4)

[1989Mee] Meetsma, A., de Boer, J.L., van Smaalen S., “Refinement of the Crystal Structure of

Tetragonal Al2Cu”, J. Solid State Chem., 83(2), 370-372 (1989) (Crys. Structure,

Experimental, 17)

[1992Kuz] Kuz’ma, Yu.B., Stel’makhovych, B.M., Babizhetsky, V.S., “New Compounds with

PuNi3-Type Structure in REM-Cu-Al Systems”, Russ. Metall., (2), 196-199 (1992),

translated from Izv. Ross. Akad. Nauk, Metally, (2), 227-230 (1992) (Experimental, Crys.

Structure, 4)

[1992Ran] Ran, Q., ”Aluminium-Copper-Terbium”, MSIT Ternary Evaluation Program, in MSIT

Workplace, Effenberg, G. (Ed.), Materials Science International Services GmbH, Stuttgart;

Document ID: 10.12789.1.20 (1992) (Equi. Diagram, Assessment, 10)


Subramanian, P.R., Chakrabarti, D.T., Laughlin, D.E. (Eds.), ASM International, Materials

Park, OH, 18-42 (1994) (Equi. Diagram, Review, 226)

[1994Sub] Subramanian, P.R., Laughlin, D.E., “The Cu-Tb (Copper-Terbium) System”, in “Phase

Diagrams of Binary Copper Alloys”, Subramanian, P.R., Chakrabarti, D.T., Laughlin, D.E.

(Eds.), ASM International, Vol. 10, 428-431 (1994) (Equi. Diagram, Review, 23)

[1995Kuz] Kuz’ma, Yu.B., Stel’makhovych, B.M., Vasyunyk, M.I., “Phase Equilibria and Crystal

Structure of Tb-Cu-Al Compounds in the Region up to 50 at.% Tb” (in Russian), Russ.

Metal., (5) 130-136 (1995), translated from Izv. Ross. Akad. Nauk, Metally, (5), 162-169

(1995) (Equi. Diagram, Crys. Structure, Experimental, *, #, 13)

[1996Ehl] Ehlers, G., Maletta, H., “Magnetic Order in TbNiAl and TbCuAl Intermetallic

Compounds”, Z. Phys. B: Condens. Matter, 99(2), 145-150 (1996) (Experimental, Magn.

Prop., 8)

[1996Goe] Goedecke, T., Sommer, F., “Solidification Behaviour of the Al2Cu Phase”, Z. Metallkd.,

87(7), 581-586 (1996) (Experimental, Crys. Structure, 8)

[1996Ste] Stel’makhovych, B.M., Aksel’rud, L.G., Kuz’ma, Yu.B., “The Tb2(Cu0.47Al053)17 and

Tb(Cu0.58Al0.42)11 Aluminides and Their Crystal Structures”, J. Alloys Compd., 234,


[1998Jav] Javorský, P., Havela, L., Sechovský, V., Michor, H., Jurek, K., “Magnetic Behaviour of

RCuAl Compounds”, J. Alloys Compd., 264, 38-42 (1998) (Experimental, Crys. Structure,

15)


the Cu-Al Binary System”, J. Alloys Compd., 264(1-2), 201-208 (1998) (Experimental,

Equi. Diagram, 25)

[2002Gro1] Gröbner, J., Matusch, D., Turkevich, V., “Al-Tb (Aluminium - Terbium)” MSIT Binary

Evaluation Program, in MSIT Workplace, MSI, Stuttgart, Document ID: 20.12179.1.20,

MSI, Stuttgart, (2002) (Equi. Diagram, Assessment, 5)

[2002Gro2] Gröbner, J., Matusch, D., Turkevich, V., “Cu-Tb (Copper - Terbium)” MSIT Binary


International Services GmbH, Stuttgart; Document ID: 20.13888.1.20 (2002) (Equi.





[2003Gro] Gröbner, J, “Al-Cu (Aluminium-Copper)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart, to be published, (2003) (Equi. Diagram, Assessment, 68)

151


MSIT®

Al–Cu–Tb


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

< 660.45

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2],

0 to 2.48 at.% Cu [Mas2]

(Cu)

< 1084.62

Cu1–xAlx

cF4

Fm3m

Cu

a = 361.46

a = 361.52

a = 365.36

at 25°C [Mas2],

0 to 19.7 at.% Al [Mas2]

no appreciable solubility of Tb [1994Sub]

x = 0, quenched from 600°C [2003Gro]

x = 0.152, quenched from 600°C [2003Gro]

( Tb)

1356-1289

cI2

Im3m

W

a = 402 [Mas2]

copper solubility in the different terbium

form is very small or negligible

( Tb)

1289-(–53)

hP2

P63/mmc

Mg

a = 360.55

c = 569.66

at 25°C [Mas2]

the and ’ designations have been

interchanged in some compilations

( ’Tb)

< –53

oC4

Cmcm

’Dy

a = 360.5

b = 624.4

c = 570.6

[Mas2]

, Cu3Al(h)

1049-559

cI2

Im3m

W a = 295.64

70.6 to 82 at.% Cu [1985Mur], [1998Liu]

at 672°C

2, Cu100–xAlx< 363

t**

TiAl3long period

super-lattice

a = 366.8

c = 368.0

22 x 23.5 [1985Mur]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu

(subcell only)

0, Cu100–xAlx Cu~2Al

1037-800

cI52

I43m

Cu5Zn8

37 x 31.5 [Mas2],

38 x 32 [1998Liu]

1, Cu9Al4< 890

cP52

P4m

Cu9Al4 a = 870.23

a = 870.68

62 to 68 at.% Cu

[Mas2, 1998Liu];

from single crystal [V-C2] at 68 at.% Cu


, Cu100–xAlx< 686

hR*

R3m

a = 1226

c = 1511

40.7 x 38.1 [1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

1, Cu100–xAlx958-848

cubic? 40.6 x 37.9

59.4 to 62.1 at.% Cu [Mas2, 1985Mur]

2, Cu2–xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.78 x 0.45

55 to 61 at.% Cu [Mas2, 1985Mur, V-C2],

NiAs in [Mas2,1994Mur]

152


MSIT®

Al–Cu–Tb

1, Cu47.8Al35.5 (h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 59.8 at.% Cu [Mas2, 1994Mur]


2, Cu11.5Al9 (r)

< 570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu

[Mas2, 1985Mur]


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu

[Mas2, 1985Mur]


2, CuAl(r)

< 560

mC20

C2/m

CuAl

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu [V-C2]

, CuAl2< 591

tI12

I4/mcm

CuAl2 a = 606.7

c = 487.7

31.9 to 33.0 at.% Cu [12994Mur]

32.4 to 32.8 at.% Cu at 250°C [1996Goe]

single crystal [V-C2,1989Mee]

TbAl4<420

oI20

Imma

Al4U

a = 443.0

b = 626.1

c = 1370.6

[V-C2]

not confirmed, possibly impurity stabilized

phase

TbAl3<1108

hR36

R3m

BaPb3

a = 617.6

c = 2116.5

[Mas2]

TbAl3(HP) hR60

R3m

Al3Ho

a = 609.5

c = 3596

High-pressure phase

[V-C2]

Tb(CuxAl1–x)2

TbAl2< 1514

cF24

Fd3m

Cu2Mg

a = 778.9

a = 785.9

0 x 0.2 at 650°C [1995Kuz]

at x = 0.2 [1995Kuz]

at x = 0 [Mas2]

TbAl

< 1079

oP16

Pmma

AlEr

a = 583

b = 1137

c = 562

[V-C2]

Tb3Al2< 986

tP20

P42/mnm

Al2Zr3

a = 825.5

c = 756.8

[V-C2]

Tb2Al

< 960

oP12

Pnma

Co2Si

a = 659.2

b = 511.3

c = 944.0

[Mas2]

Tb3Al cP4

Pm3m

AuCu3

a = 479.4 [V-C2]

not confirmed, possibly impurity stabilized

phase

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

153


MSIT®

Al–Cu–Tb

TbCu1–xAlxTbCu

900-(–157)

cP2

Pm3m

CsCl

a = 347.8 to 348.4

a = 348.0

a = 349.9

a = 351.8

a = 354.0

a = 354.7

a = 354.9

a = 356.8

at x = 0 [1994Sub]

0 x 0.35? (annealing temperature not

specified) [1977Bas]

at x = 0

at x = 0.1

at x = 0.2

at x = 0.3

at x = 0.4

at x = 0.5 [1977Bas]

0 x 0.5 at 650°C [1995Kuz]

at x = 0.5

TbCu

< –157

tP2

P4/mmm

MnHg

a = 345.7

c = 349.8

[V-C2]

Tb(Cu1–xAlx)2

TbCu2

< 870

oI12

Imma

CeCu2

a = 433.2

b = 683.0

c = 732.7

a = 431.0

b = 682.5

c = 732.0

0 x 0.075 at 650°C [1995Kuz]

at x = 0.075 [1995Kuz]

at x = 0 [1994Sub]

Tb2Cu7

890-850

? high temperature phase [1994Sub]

Tb2Cu9

< 950

? [1994Sub]

TbCu5(h)

940-895

TbCu5–xAlx

TbCu4Al

hP6

P6/mmm

CaCu5

a = 496 to 503

c = 409 to 415

a = 529.1

c = 409.3

a = 507.3

c = 414.9

[1994Sub] [V-C2]

A homogeneity range of 0 x 2.8

reported by [1995Kuz] and presented in his

isothermal section at 650°C. However, at

650°C, TbCu5, should be metastable

according to [2002Gro2]

at x = 2.8 [1995Kuz]

at x = 1 [1978Tak]

TbCu5

< 895

cF24

F43m

AuBe5

a = 704.1 [1994Sub] [V-C2]

TbCu7

?–~700

hP8

P6/mmm

TbCu7

(closely related to

CaCu5)

a = 494.2

c = 416.4

high temperature phase

[1994Sub]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

154


MSIT®

Al–Cu–Tb

Tb6Cu23 cF116

Fm3m

Th6Mn23

a = 1220 high pressure phase, prepared at 7.7 GPa

[1994Sub]

* 1, Tb(CuxAl1–x)12

TbCu4Al8

TbCu6Al6

tI26

I4/mmm

ThMn12

a = 868.8

c = 511.9

a = 874.2

c = 514.2

a = 875.2

c = 513.4

a = 865.7

c = 505.3

0.40 x 0.43 [1995Kuz] at 650°C

at x = 0.40 [1995Kuz]

at x = 0.43 [1995Kuz]

observed on a sample at x = 0.33 [1979Fel]

observed on a sample at x = 0.5 annealed at

~800°C [1980Fel]

* 2, TbCu6.4Al4.6 oF*

Fddd

Tb(Cu0.58Al0.42)1

1

a =1427.9

b =1489.2

c = 656.44

[1995Kuz]

* 3, Tb2(CuxAl1–x)17 hR57

R3m

Th2Zn17

a = 871.7

c = 1271

a = 885.2

c = 1289

a = 882.6

c = 1286

0.45 x 0.676 at 650°C [1995Kuz]

at x = 0.676 [1995Kuz]

at x = 0.45 [1995Kuz]

observed on a sample at x = 0.41 annealed

at 500°C [1982Pre]

* 4 Tb3Cu1.2Al9.8 oI12

Immm

La3Al11

a = 422.9

b = 1252.8

c = 994.0

[1995Kuz]

* 5 TbCu0.9Al2.1 hR36

R3m

PuNi3

a = 547.5

c = 2539.3

[1995Kuz]

* 6 TbCu2–xAlx hP9

P62m

Fe2P or ZrNiAl

a = 701.0 to 704.1

c = 405.0 to 405.4

a = 704.06

c = 404.39

0.85 x 1.15 [1995Kuz]

at x = 1 [1968Dwi]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

155


MSIT®

Al–Cu–Tb

20

40

60

80

20 40 60 80

20

40

60

80

Tb Cu


Axes: at.%

τ1

ε2

δγ1

β

τ4

τ5

τ2

τ3

TbAl3

TbAl2

TbAl

τ6

TbCu TbCu2 TbCu5

(Cu)

L

(Al)

?

Fig. 1: Al-Cu-Tb.

Partial isothermal

section at 650°C

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Tb 60.00Cu 0.00Al 40.00

Tb 0.00Cu 60.00Al 40.00


Axes: at.%

η

τ1

θτ4

TbAl3

(Al)Fig. 2: Al-Cu-Tb.

Partial isothermal

section at 400°C

156


MSIT®

Al–Cu–Ti

Aluminium – Copper – Titanium

Rainer Schmid-Fetzer

Literature Data

Phase equilibria in the entire ternary system have been studied by [1971Vir] and [1973Mar]. [1971Vir]

prepared the samples either from the metallic elements (99.9% Cu, 99.99% Al, Ti purity not given) or from

a Cu50Ti50 master alloy. About 100 alloys were melted in an electric arc furnace under pure Ar. Most of the

samples weighed 10 g, but 7 in the Ti corner and 11 in the Cu corner were prepared as 100 g bars. The

Cu-rich bars were homogenized at 850°C for 21 h, quenched in water, rolled or hammered and annealed at

different temperatures. The Ti-rich samples were hot rolled at 950°C and heat treated (950°C/15 min or

900°C/30 min or 850°C/1 h or 800°C/2 h). About 10 of the other samples were examined in the as-cast state.

Samples were examined by metallography for constructing the partial isothermal sections at 950, 900, 850

and 800°C, by X-ray diffraction for determining the crystal structures of the ternary compounds, and by

direct observation of the melting for the determination of the liquidus surface. [1973Mar] homogenized

more than 200 samples at 800°C for 600 to 900 h and at 500°C for 1000 h, and determined the 800 and

500°C isothermal sections by microstructural and X-ray analysis. Phase regions of controversy between

[1971Vir] and [1973Mar] were studied by [1997Dur] with 1 g samples arc melted from high purity metals

(Ti 99.9%, Cu and Al 99.999%), heat treated in evacuated silica tubes at 850°C for 120 h or even 430 h and

water quenched. Phase analysis was done by XRD, optical microscopy and SEM/EDX and electron

microprobe. Similar experiments were reported by [1994Lug] with 35 samples equally distributed in the

range > 50 mass% Ti, heated at 600 and 800°C for 6 h and 12 h. Many investigators give information on

phase equilibria in limited regions [1936Nis, 1943Mon, 1958Vig1, 1958Vig2, 1958Vig3, 1966Zwi,

1960Emo, 1962Pan, 1963Luz, 1965Ram2, 1966Zwi, 1969Hor, 1979Sei, 1981Sei, 1983Bru, 1984Guz,

1985Guz, 2000Kai, 2001Liu]. From differential thermal and microstructural analysis [1936Nis] derived

two partial polythermal sections at 6 and 10 mass% Cu with up to 1 mass% Ti. A ternary eutectic was

concluded. Phase equilibria were reported by [1958Vig1] at 850 and 500°C in the Cu corner from

microhardness measurements and by [1958Vig2] for some more temperatures by metallography. Including

the results of [1958Vig1] and [1958Vig2], [1958Vig3] reported details on their studies. 30 alloy

compositions with up to 7 mass% Ti and 14 mass% Al were studied by metallography and microhardness

measurements. The samples were heat treated at different temperatures: 300°C/360 h, 400°C/240 h, 500°C/

200 h, 600°C/100 h, 700°C/50 h, 800°C/20 h, 850°C/16 h, 900°C/10 h, 950 and 980°C/7 h. From the results,

phase relationships were established for the examined composition range for 980, 700, 600 and 500°C and

reported as isothermal sections, 1, 2 and 3 mass% Ti vertical sections and a diagram of joint solubility of Ti

and Al in (Cu) from 500 to 980°C. From microradiography and microhardness determinations, [1960Emo]

plotted sketches for the Cu corner which do not agree everywhere with the phase rule. [1962Pan] studied

the microstructure of 15 alloy compositions at different temperatures and constructed the partial (up to 3

mass% Ti) polythermal sections at 5 and 10 mass% Al. [1963Luz] determined the solubility of Cu in a

Ti-6Al (mass%) alloy by electrical resistance measurements. Samples with 0.5, 0.8, 1.2, 1.6, 2.0, 2.4, 3.4

and 5% Cu were vacuum melted, homogenized 125 h at 930°C, furnace cooled, annealed at 600°C/105 h,

700°C/100 h, 800°C/75 h and finally quenched. [1969Hor] studied the effect of Ti on the temperature of the

1+(Cu) eutectoid reaction in the Al-Cu system by differential dilatometry, differential thermal analysis

and metallography. [1979Sei] determined the liquidus surface of the Ti-CuAl-FeAl partial system by

microstructure and melting observation. [1981Sei] studied the composition of platelet precipitates in a

91.2Ti-6.9Al-1.9Cu (at.%) alloy after annealing at 475°C/8 h or 600°C/140 h using TEM with EDX and

found the Al-content much reduced (< 2.5 at.% Al with 24.5 at.% Cu) compared to the Ti-matrix (7.5 to 8.5

at.% Al with 0.8 at.% Cu). [2000Kai] prepared arc melted samples in the range Ti-(35-47)Al -(0.5-12)Cu

(at.%), checked for low levels of O (250 ppm) and N (50 ppm), wrapped in Mo foil and heated in evacuated

silica capsules at 1000°C for 168 or 504 h, at 1200°C for 168 h, and at 1300°C for 24 h. Microstructural and

electron microprobe analysis of the two- and three-phase samples was performed.

157


MSIT®

Al–Cu–Ti

Equilibrium relations in the Cu corner were studied by metallography, electron microprobe analysis, X-ray

diffraction, electron diffraction and electrical resistivity measurements for four temperatures between 600

and 850°C [1983Bru]. Samples were prepared from metals of 99.5% purity by induction melting under Ar

in a water-cooled Cu boat, holding the melt in levitation for several minutes, casting in a Cu mold, and

annealing 2 h at 900°C. The samples were then further annealed 25 h at 850°C, or 50 h at 800°C, or 30 days

at 700°C, or 30 days at 600°C. [2001Liu] studied Al-Cu-rich two-phase equilibria with Ti addition of 0.5

and 1 at.%, heated at 700 and 800°C for 48 to 100 h in two Cu-Ti / Cu-Al-Ti diffusion couples using SEM/

EDX.

[1984Guz] and [1985Guz] reported the determination of the solubility of Ti and Cu in (Al) at 500°C by

microstructural and X-ray analysis and electrical resistance measurements, on samples of 40 alloy

compositions ranging from 0 to 0.35 Ti and from 0 to 3.5 mass% Cu. All other works are on ternary

compounds and their crystal structures. The first work in this ternary system at all, [1935Bac1, 1935Bac2],

reports studies of crystal structure of two single-crystal ternary compounds by Laue and rotating single

crystal diffraction. For the two phases, cubic and hexagonal unit cells were revealed, respectively, and

lattice spacing parameters were given. [1957Gru] claimed to have found a body-centered tetragonal phase

in a copper base alloy with 1.13Ti-0.69Al (mass%) by Debye-Scherrer X-ray diffraction. The sample was

prepared from electrolytic Cu and a master alloy by melting and holding at 1200°C and annealing 1000 h

at 500°C after casting. [1958Vig3] at 600°C observed a phase called containing >12.8 mass% Al and >3.5

mass% Ti and suggested it to be a ternary phase. Several ternary compounds and their structures were

reported by [1960Moe] and [1962Hei] (TiCu2Al) and [1964Sch] (TiCuAl, Ti2CuAl5, Ti25Cu4Al71,

Ti25Cu2Al73) without giving information on the experimental procedures. The crystal structure of the

compound TiCuAl was completely determined by [1964Kry] and [1964Rie] using powder X-ray

diffraction. [1964Mar] arc melted the component metals of 99.9% purity under He, annealed the sample

20 days at 800°C, followed by water quenching. The existence of the compound TiCu2Al was confirmed

by X-ray and microstructural analysis. [1965Ram1] made X-ray analysis of a sample Ti25Cu3Al72 after

annealing for 7.5 days at 700°C. This work was continued and extended to several other compositions with

different heat treatment. [1967Hof] prepared TiCu2Al by melting in evacuated silica ampoules and

determined the structure in the as-cast state. Both [1971Vir] and [1973Mar] observed three ternary

compounds, TiCuAl, TiCu2Al and Ti2CuAl5 with lattice parameters determined for TiCuAl [1973Mar] and

structures determined for all the three compounds [1971Vir]. [1973Mar] concluded homogeneity along a

line only, whereas [1971Vir] suggested remarkable homogeneity regions for all the three phases. The

homogeneity range of 1, TiCu2Al, was studied with XRD on arc melted samples, annealed at 800°C for

>72 h and finally at 600°C for only 48 h [1990Mey]. [1989Miz] found Ti(Cu1-xAlx)2 alloys annealed at

800°C for 24 h to be single phase 2 with C14 structure for 0.45 < x < 0.7 and measured the lattice

parameters, increasing slightly and linearly with x, the magnetic susceptibility and, for stoichiometric

TiCuAl, the specific heat at 1.5-6 K. Earlier reviews of the ternary system [1979Cha, 1979Dri] are mostly

based on the work of [1971Vir]. The extensive review by [1992Ran] forms an important basis for the

present assessment even though the conclusions had to be revised in view of more recent data.

Much of the more recent work in the Al-Cu-Ti system is devoted to the L12 type phase 3 [1989Maz,

1991Fra, 1991Hon, 1991Mab, 1991Nic, 1991Win, 1992Dur, 1992Ma, 1992Mor, 1992Pot, 1992Win,

1993Nak, 1997Fan], which is considered as an interesting low density intermetallic compound [1990Kum].

Improved mechanical properties of 3 as compared to TiAl3 are expected since the L12 structure has the

required five independent slip systems [1992Win].

A sample Ti23.8-Cu13.4-Al62.8 (all at.%) was found single phase 3 [1992Ma], and Ti25-Cu12.5-Al62.5

shows nearly no second phase after 48 h at 1150°C but about 5% CuAl2 in as-cast state [1993Nak].

Mechanical alloying of Ti25-Cu8-Al67 produced nanocrystalline disordered (Al) solid solution in which

simultaneously grain growth and transformation to L12 was observed upon tempering in the range

400-700°C [1997Fan]. Further studies on the L12 type phase 3 regard the solubility range at 1200°C

[1989Maz], lattice parameter variations [1991Fra], atomic locations and ordering behavior [1992Ma,

1992Mor, 1992Win], TiAl2 precipitates forming in L12 matrix [1992Pot], theoretical stability calculations

[1991Hon, 1991Fre], and mechanical properties [1991Nic, 1991Win].

158


MSIT®

Al–Cu–Ti

Binary Systems

The three binary systems are accepted in the recently revised versions given in [2002Ans, 2003Gro,

2003Sch].

Solid Phases

Crystallographic data for all solid phases are given in Table 1. [1935Bac1] first reported two ternary

compounds, a cubic one and a hexagonal one. Neither composition was identified. From the structure type

and lattice parameters reported, however, these phases can be specified as TiCuAl [1964Kry, 1964Rie,

1964Sch, 1965Ram2] and Ti2CuAl5 [1964Sch, 1965Ram2, 1971Vir]. After the report of a CsCl type

structure for TiCu2Al [1960Moe], its crystallographic data have been determined further by [1962Hei,

1964Mar, 1965Ram2, 1967Hof]. Whereas [1960Moe, 1962Hei] and [1964Mar] gave the structure type as

CsCl, [1965Ram2] and [1967Hof] established the MnCu2Al structure and suggested that incomplete

ordering was the reason for reporting CsCl structure in earlier works. All three phases were also found by

[1971Vir] and [1973Mar] while constructing the isothermal sections at 800, 540 and 500°C. [1973Mar]

gave line-compound homogeneity ranges for TiCuAl and Ti2CuAl5 and a nearly linear range for TiCu2Al,

all with constant Ti content, whereas [1971Vir] also proposed considerable homogeneity regions for Ti for

all three phases. For Ti2CuAl5, the result of [1973Mar] is preferred, because 1) [1973Mar] investigated

more samples; 2) [1973Mar] was aware of the work of [1971Vir]; and 3) the homogeneity “areas” drawn

by [1971Vir] are not necessarily conclusions from experimental results. The homogeneity range for TiCuAl

from [1971Vir] is extended to include the composition after [1973Mar]. This is appropriate because the

structure determination of this phase was reported for the stoichiometric composition very close to the

Al-poor end of the range given by [1973Mar]. According to [1971Vir], the Ti2CuAl5 and TiCuAl phases

are formed by ternary peritectic reactions at 1280 and 1150°C, respectively. The compositions of the phases

taking part in the reactions make the peritectics improbable, but the stability of these two phases at these

temperatures, reflected in the assessed transition type reactions U1 and U3, is quite sure. As a consequence

a congruent melting is assumed to be likely for 3, Ti2CuAl5 (1350°C actually given by [1971Vir]) and 2,

TiCuAl ( 1160°C, slightly above max2). The congruent melting point for 1, TiCu2Al ( 1125°C) is from

[1971Vir], it must be above 1100°C.

The compound “Ti25Cu4Al71” has the ZrAl3 structure and is most probably a solid solution of Ti5Al11(h)

[1965Ram2]. The alloys Ti25Cu2Al73 [1964Sch] and Ti8CuAl23 [1965Ram1, 1965Ram2] have

compositions very close to the binary phase Ti9Al23 and an identical structure. They are therefore

considered to be solid solutions of this phase. [1957Gru] proposed the existence of another ternary phase of

a tetragonal body-centered lattice structure (a = 356, c = 463 pm) for which there is no further evidence.

The sample conditions suggest that this phase is most likely the binary TiCu4 phase.

The ternary phase called X, proposed by [1958Vig3], is considered not to be an additional phase, but to be

the TiCu2Al compound as indicated by the isothermal section of [1971Vir] and [1973Mar].

The (Ti,Al) phase referred to as 2 by [1971Vir] was not recognized as Ti3Al because the strong X-ray

reflections coincide with those of ( Ti). As a consequence “ 2” is Ti3Al in the low temperature isotherms,

but it has to be interpreted as ( Ti) in the liquidus projection.

The , Cu3Al(h) phase is claimed to be stabilized by solution of 5 at.% Ti (“Ti0.2Cu2.8Al”) and shown in

the “540°C” section of [1971Vir], whereas [1962Pan] have it decomposed at 560°C. The latter is accepted

since a large Ti-solubility of would be in conflict with the experimental partition ratio of Ti in the +(Cu)

equilibrium, which has an atomic value of about unity [2001Liu].

A high solubility of Al in a metastable ” ’ TiCu4” phase is suggested from a TEM study [1980Psh].


[1936Nis] suggested a ternary eutectic reaction in the Al-rich corner at 540°C: L (Al)+ +TiAl3 based on

his study of the partial vertical sections with 6 and 10 mass% Cu up to 10 mass% Ti

The vertical section at 1 mass% Ti of [1960Emo] demands a ternary reaction in the solid state at 570°C

where the phases (Cu), , 1 and TiCu4 participate, but the reaction type cannot be identified. This is in

159


MSIT®

Al–Cu–Ti

agreement with the 10 mass% Al partial vertical section of [1962Pan]. The extensive investigations of

[1971Vir] revealed two maxima, one eutectic, two peritectic and 18 transition reactions. Contrary to

[1936Nis], [1971Vir] gave the last reaction with liquid as a transition type, L+TiAl3 (Al)+ , at 555°C. The

result of [1936Nis] is more reliable since [1936Nis] used more samples (11) than [1971Vir] (2), and

[1936Nis] made both DTA and metallographic examinations. The new interpretation of the 2Ti phase and

its region of primary solidification as that of ( Ti) (see also”Solid Phases”), as well as the acceptance of the

new binary systems make the modification and introduction of several ternary reactions necessary, though

the work of [1971Vir] remains essential.

Two additional major changes made to the interpretation of [1971Vir] will be highlighted below. Firstly,

they plotted the liquidus surface with a small intersection of Ti2Cu and 2 primary phase fields. This is in

conflict with the recent experimental data on 1+Ti3Al equilibrium at 850°C [1997Dur]. This is resolved by

the modified reactions U8 and U9 in Table 2 and also an intersection of the 1 and Ti3Al primary phase fields

in Fig. 1, following essentially the interpretation of [1997Dur]. This modification is still in accord with the

actual data points of [1971Vir]. The second major point is that both [1971Vir] and [1997Dur] show an

intersection of the ( 0, 2) and the 2 primary fields from 930 to 830°C [1971Vir]. This is in conflict with

the fact that none of the Al-Cu solid phases is in equilibrium with 2 but rather the 1+ 3 equilibrium is

firmly established at 850°C [1997Dur] and also at lower temperature [1973Mar, 1971Vir]. This requires the

intersection of 1 and 3 fields shown in Fig. 2 and the reaction U15, above 850°C. Reflecting the above

comments and the additional influence of the generally not well known solid solution ranges in this ternary

it must be stated that there are still substantial uncertainties in the invariant equilibria. It is therefore

refrained from updating and reproducing the bulky Scheil reaction scheme of [1971Vir]. The reactions

which are at least partially experimentally verified are listed in Table 2 with the compositions of the liquid

taken from the modified liquidus surface of [1971Vir] shown in Fig. 1.

Liquidus Surface

The liquidus surface given in Fig. 1 is mainly based on the work of [1971Vir], but, as discussed in the

section “Invariant Equilibria”, it is changed in some areas and adapted to the accepted binary systems and

the primary solidification of ( Ti) instead of Ti3Al. Large regions of primary crystallization were observed

for the ternary compounds TiCu2Al ( 1), TiCuAl ( 2) and Ti2CuAl5 ( 3). [1979Sei] confirms the liquidus

surface of [1971Vir] on the Ti - CuAl section.

A possible inconsistency around the reaction U5 should be noted. This U5-liquid may well be located

relative to the composition of the solid phases in a manner to flip the reaction to L+ 3 TiAl+ 2, reversing

the temperature levels of U3 and U5. Also an additional maximum in the line L+ 3+ 2 is well conceivable.

This cannot be resolved without better experimental data on the solid phase compositions of 3+ 2+TiAl.

Isothermal Sections

Partial isothermal sections at 1300, 1200 and 1000°C in Figs. 2, 3, 4 show the ( Ti)+( Ti)+TiAl equilibria

and also with 2, measured by microprobe [2000Kai]. It is established that the Cu-solubility in the

( Ti)+TiAl+( Ti) phases decreases in that sequence. The extension of the 3 phase is much larger at

1200°C (25-29 at.% Ti taken from graph, but 11.5 at.% width along a constant line of 27 at.% Ti in text)

[1989Maz] compared to the 800°C data of [1973Mar].

The isothermal section at 800°C is constructed in Fig. 5, mainly based on [1973Mar]. The composition

ranges of the ternary compounds are estimated from different works, as discussed in the section “Solid

Phases”. The Ti3Al+ 1 equilibrium is firmly established by [1973Mar, 1994Lug] and also at 850°C by

[1997Dur]. Therefore the conflicting Ti2Cu+ 2 equilibrium, deduced by [1971Vir] from their liquidus

surface, is not accepted. This is corroborated by the Ti2Cu+ 1+Ti3Al equilibrium found at 800°C

[1994Lug]. The 1+ 2+ 3 equilibrium is also confirmed at 850°C [1997Dur] and the fact that the

stoichiometric TiCuAl composition of 2 is not single phase but 2+ 1. By contrast, [1989Miz] found a

larger single phase region of 2 ranging from at least 30 to 47 at.% Al at constant 33.3 at.% Ti. The 2+ 1+ 3

160


MSIT®

Al–Cu–Ti

equilibrium is from [1965Ram2], whereas [1997Dur] did find the 1+ 1+ 3 equilibrium at 850°C. They

could not detect the 1 or 2 phase in equilibrium with 1+ 3 (as shown in Fig. 5) and question the existence

of the binary 1/2 phase.

The isothermal section at 500°C, Fig. 6, is again mainly based on [1973Mar] and other data given in “Solid

Phases”, and it includes the accepted information from [1971Vir]. Their isothermal section at ”about

540°C” [1971Vir] is not reproduced here since it does not contain additional viable information. It was not

based on experiments at 540°C but was deduced from the liquidus surface and the solution ranges of solid

phases appear schematic and exaggerated. The appearance of phase well below the binary decomposition

temperature, as shown in the “540°C” section of [1971Vir], cannot be accepted since the partition ratio of

Ti in the (Cu)+ and + 1 equilibria is close to unity, as discussed above [2001Liu]. The extension of the

1 phase field given by [1990Mey] (50-53Cu, 24.5-25.25Ti, 25-22.2 Al (at.%)) is smaller than in both Fig.

6 and Fig.5, however, their annealing at 600°C was for only 48 h and their plotted ”phase diagram” violates

rules, for example the three-phase field (Cu) + TiCu4 + 1 does not touch the 1 phase field [1990Mey],

suggesting a possibly larger solution range. [1958Vig3] presented isothermal diagrams for the Cu-rich

corner in the temperature range 980 to 500°C with a three-phase equilibrium (Cu)+ + TiCu4. This is not

accepted because it contradicts other works [1971Vir, 1973Mar, 1983Bru, 1990Mey] which support each

other in the (Cu)+ 1 equilibrium. The precipitate found by [1981Sei] in a ( Ti) matrix is probably a

metastable “Ti3Cu” phase, also found by [1994Lug] at 600°C and initially at 800°C (6 h), but disappearing

after 12 h at 800°C. The low Cu-solubility in TiAl3 in equilibrium with (Al) is supported by TEM/EDX

analysis of precipitates, Ti24.5Al75.1Cu0.4, after annealing a Ti0.6-Al96.7-Cu2.7 (at.%) arc melted alloy

at 425°C up to 475 h [1997Mah].

Sections at 900 and 950°C in the Ti corner from [1971Vir] suffer from the uncertain identification of ( Ti)

vs Ti3Al and are not given here. Their section at 800°C is integrated into Fig. 5.


Several partial vertical sections were investigated. The 10 mass% Cu polythermal section with up to 1

mass% Ti drawn in Fig. 7 originates from [1936Nis]. The 6 mass% Cu partial section has the same phase

relation [1936Nis]. The isopleths given by [1958Vig3] and [1960Emo] are very tentative and do not agree

fully with the phase rule. Therefore, they are not considered as reliable. The 5 mass% Al vertical cut with

up to 3 mass% Ti of [1962Pan] shows simple extensions of phase regions from the binary edge. The 10

mass% Al vertical cut is given in Fig. 8.

Miscellaneous

Amorphous Ti40Cu50Al10 alloy was produced by rapid solidification and crystallizes to TiCu+ 1

[1994Myu], in accord with the assessed phase diagram. [1985Vas] studied age-hardening behavior in

Al-Cu-Ti alloys.

References



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(Equi. Diagram, Review, 1)

161


MSIT®

Al–Cu–Ti

[1957Gru] Gruhl, W., Codier, H., “On a Hardenable Copper-Titanium-Aluminium Alloy”

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162


MSIT®

Al–Cu–Ti

[1971Vir] Virdis P., Zwicker, U., “Phase Equilibria in the Copper-Titanium-Aluminium System”

(in German), Z. Metallkd., 62, 46-51 (1971) (Equi. Diagram, Crys. Structure, Experimental,

*, #, 18)

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Systems” (in Russian), Metallofizika, (46), 103-110 (1973) (Equi. Diagram, Experimental,

*, #, 24)

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(in Russian), Nauka, Moskow, 82-83 (1979) (Equi. Diagram, Review, 4)

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Technically Applicable Cast Alloys” (in German), Thesis, Univ. Erlangen-Nürnberg,

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in Cu-Ti Alloys”, Sov. Phys. J. (Engl. Trans.), 23(4), 293-299 (1980) (Experimental, 23)

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725-727 (1981) (Experimental, 14)

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Equilibria in the Cu-Rich Region”, Z. Metallkd., 74, 525-529 (1983) (Equi. Diagram,

Experimental, 24)

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[1985Guz] Guzyi, L.S., Kuzhecov, V.N., Orinbekov, S.B., Sokolovskaya, E.M., Makanov, U.M.,

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[1985Vas] Vassel, A., “The Age-Hardening Behaviour in Ti-Cu-Al Ternary Titanium Alloys”,

Conference: “Titanium-Science and Technology”, (DGM), 1481-1486 (1985)

(Experimental, Mechan. Prop., 7)

[1989Maz] Mazdiyasni, S., Miracle, D.B., Dimiduk, D.M., Mendiratta, M.G., Subramanian, P.R.,

“High Temperature Phase Equilibria of the Ll2 Composition in the Al-Ti-Ni, Al-Ti-Fe and

Al-Ti-Cu Systems”, Scr. Metall., 23(3), 327-331 (1989) (Equi. Diagram, Experimental,10)




[1989Miz] Mizutani, U., Hasegawa, M., Ohashi, S., “Enhanced Itinerant Paramegantism in C14-Type

Laves Ti(Cu1-xAlx)2Ti, x = 0.45-070, Alloys”, Solid State Commun., 69(4), 403-406 (1989)


[1990Kum] Kumar, K.S., “Ternary Intermetallics in Aluminium-Refractory Metal-X Systems (X = V,

Cr, Mn, Fe, Co, Ni, Cu, Zn)”, Int. Mater. Rev., 35(6), 293-327 (1990) (Crys. Structure, Equi.


[1990Mey] Meyer Zu Reckendorf, R., Schmidt, P.C., Weiss, A., “The Ternary Systems Cu-Ti-Al and

Cu-Zr-Al Around the Heusler Phase Composition Cu2XAl (X = Ti, Zr): Phase Diagrams

and Hydrogen Solubility”, J. Less-Common Met., 159, 277-289 (1990) (Equi. Diagram,

Experimental, 41)

[1990Sch] Schuster, J.C., Ipser, H., “Phases and Phase Relations in the Partial System TiAl3-TiAl”,


163


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Al–Cu–Ti




[1991Fra] Frazier, W. E., Benci, J. E., “Crystal Structure and Phase Relationships in As-Cast and Melt

Spun Titanium Aluminide (Al3Ti) and Al3Ti Plus Copper”, Scr. Metal. Mater., 25(10),


[1991Fre] Freeman, A.J., Hong, T., Lin, W., Xu, J.-H., “Phase Stability and Role of Ternary Additions

on Electronic and Mechanical Properties of Aluminum Intermetallics”, in ”High-Temp.

Ordered Intermetallic Alloys IV”, Mater. Res. Soc. Symp. Proc., 213, 3-18 (1991) (Theory,

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Electronic Structure of Intermetallic Compounds: Al3Ti+Cu”, J. Mater. Res., 6(2), 330-338

(1991) (Crys. Structure, Theory, 36)

[1991Mab] Mabuchi, H., Nakayama, Y., “Development of Al-Ti-X Ternary L12 Intermetallic

Compounds” (in Japanese), Bull. Jpn. Inst. Met., 30(1), 24-30 (1991) (Equi. Diagram,

Experimental)

[1991Nic] Nic, J.P., Zhang, S., Mikkola, D.E., “Alloying of Al3Ti with Mn and Cr to Form Cubic

L1(2) Phases”, in “High-Temp. Ordered Intermetallic Alloys IV”, Mater. Res. Soc. Symp.

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Ti-Fe-Cu System. Conditions of the Formation of Ti2Fe Compound”, Russ. Metall., 5,


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164


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Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E., (Eds.), ASM International,



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Equi. Diagram, Experimental, #, *, 34)




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165


MSIT®

Al–Cu–Ti

[2003Sch] Schmid-Fetzer, R., “Al-Ti (Aluminium-Titanium)”, MSIT Binary Evaluation Program, in


GmbH, Stuttgart; to be published, (2003) (Equi. Diagram, Crys. Structure, Assessment, 86)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]Comments/References

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 pure Al at 25°C [Mas2]

0 to 0.6 at.% Ti [1992Kat],

0 to 2.48 at.% Cu [Mas2]

(Cu)

< 1084.62

cF4

Fm3m

Cu

a = 361.46

a = 361.52 +

25.26xAl

a = 361.47 +

33.38xTi

at 25°C [Mas2],

0 to 19.7 at.% Al [Mas2]


[1991Ell], quenched from 600°C, xAl = 0

to 0.152

0 to 8 at.% Ti at 885°C [Mas2]

0 to 0.8 at.% Ti at 450°C [1999Nag]

( Ti)

1670 - 882

cI2

Im3m

W

a = 330.65 pure Ti [Mas2]

0 to 44.8 at.% Al [1992Kat] possible

ordering from A2 to B2 ( 2Ti) [2000Ohn]

dissolves 13.5 at.% Cu at 100°C [Mas2]

( Ti)

< 1490

hP2

P63/mmc

Mg

a = 295.06

c = 468.35

pure Ti(r) at 25°C [Mas2]

0 to 51.4 at.% Al [1992Kat]

dissolves 1.6 at.% Cu at 790°C [Mas2]

, Cu3Al(h)

1049 - 559

cI2

Im3m

W a = 295.64

70.6 to 82 at.% Cu [1985Mur]

at 672°C in +(Cu) alloy (Ti free)

[1998Liu]


1 cF16

Fm3m

BiF3

a = 585 Metastable [1994Mur]

supercell of

2, Cu1-xAlx< 363

-

TiAl3long period

super-lattice

-

a = 366.8

c = 368.0

0.22 x 0.235 [Mas, 1985Mur]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu

(subcell only)

0, Cu1-xAlx Cu-2Al

1037-800

cI52

I43m

Cu5Zn8

- 0.31 x 0.40 [Mas2]

0.32 x 0.38 [1998Liu]


1, Cu9Al4< 890

cP52

P3m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu [Mas2, 1998Liu];




, Cu1-xAlx< 686

hR*

R3m

a = 1226

c = 1511

0.38 x 0.407 [Mas2, 1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C]

166


MSIT®

Al–Cu–Ti

1, Cu1-xAlx958-848

cubic? - 0.379 x 0.406

59.4 to 62.1 at.% Cu [Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.47 x 0.78

55.0 to 61.1 at.% Cu, [Mas, 1985Mur,

V-C2], NiAs in [Mas2, 1994Mur]

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 59.8 at.% Cu [Mas2, 1994Mur]


2, Cu11.5Al9(r)

<570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu, [Mas2, 1985Mur]


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu

[V-C2, Mas2, 1985Mur]


2, CuAl(r)

< 560

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu

[V-C2]

Cu2Al3 hP5

P3m1

Ni2Al3

a = 410.6

c = 509.4


~40 to 50 at.% Cu

, CuAl2< 591

tI12

I4/mcm

CuAl2 a = 606.7

c = 487.7

31.9 to 33.0 at.% Cu

[1994Mur]

single crystal

[V-C2, 1989Mee]

’ tP6

distorted CaF2

a = 404.82

c = 581.17


Ti3Al

< 1164

(up to 10 GPa at RT)

hP8

P63/mmc

Ni3Sn

a = 580.6

c = 465.5

a = 574.6

c = 462.4

~20 to 38.2 at.% Al, [1992Kat]

DO19 ordered phase (” 2-Ti3Al”)

[1997Sah]

at 22 at.% Al [L-B]

at 38 at.% Al [L-B]

Ti3Al (I)

15 to > 41 GPa

hP16

P63/mmc

TiNi3

a = 531.2

c = 960.4

[1997Sah] at 16 GPa,

not confirmed by [2000Dub] (0-35 GPa,

25-2250°C)

TiAl

< 1463

tP4

P4/mmm

AuCu

a = 400.0

c = 407.5

a = 398.4

c = 406.0

46.7 to 66.5 at.% Al [1992Kat]

50 to 62 at.% Al at 1200°C [2001Bra]

L10 ordered phase (” -TiAl”)

at 50.0 at.% Al [2001Bra]

at 62.0 at.% Al [2001Bra]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters


167


MSIT®

Al–Cu–Ti

TiAl2< 1199

oC12

Cmmm

ZrGa2

tP4

P4/mmm

AuCu

tI24

I41/amd

HfGa2

tP32

P4/mbm

Ti3Al5

a = 1208.84

b = 394.61

c = 402.95

a = 403.0

c = 395.5

a = 397.0

c = 2497.0

a = 1129.3

c = 403.8

chosen stoichiometry, [1992Kat]

summarizing several phases:

metastable modification of TiAl2 , only

observed in as-cast alloys [2001Bra];

listed as TiAl2(h) by [1990Sch]

(66 to 67 at.% Al, 1433-1214°C)

Ti1-xAl1+x ; 63 to 65 at.%Al at 1250°C,

stable range 1445-1170°C [2001Bra];

listed as othorhombic, Pmmm, with

pseudotetragonal cell by [1990Sch]

(range ~1445-1424°C).

at 1300°C [2001Bra]

stable structure of TiAl2 <1216

[2001Bra];

listed as TiAl2(r) by [1990Sch]

Ti3Al5, stable below 810°C [2001Bra];

“Ti2Al5”

1416 - 990

tetragonal

superstructure of

AuCu-type

[2001Bra]

tI16

ZrAl3

tP28

P4/mmm

“Ti2Al5”

a* = 395.3

c* = 410.4

a* = 391.8

c* = 415.4

a = 391.7

c = 1652.4

a = 390.1

c = 1660

a = 390.53

c = 2919.63

chosen stoichiometry, [1992Kat]

summarizing several Al-Ti phases:

Ti5Al11

stable range 1416- 995°C [2001Bra]

66 to 71 at.% Al at 1300°C [2001Bra]

(including the stoichiometry Ti2Al5!);

[1990Sch] claimed: 68.5 to 70.9 at.% Al

and range 1416 - 1206°C;

at 66 at.% Al [2001Bra]

* AuCu subcell only

at 71 at.% Al [2001Bra]

* AuCu subcell only

Cu free [1965Ram2]

6 at.% Cu [1965Ram2]

“Ti4CuAl11”

“Ti2Al5”

~1215-985°C [1990Sch];

included in homogeneity region of

Ti5Al11 [2001Bra]!

TiAl3 (h)

< 1393

tI8

I4/mmm

TiAl3(h) a = 384.9

c = 860.9

74.2 to 75.0 at.% Al, [1992Kat]

74.5 to 75 at.% Al,

at 1200°C [2001Bra] DO22 ordered phase

stable above 735°C (Al-rich) [2001Bra]

TiAl3 (l)

< 950 (Ti-rich)

tI32

I4/mmm

TiAl3 (l)

a = 387.7

c = 3382.8

74.5 to 75 at.% Al [2001Bra]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters


168


MSIT®

Al–Cu–Ti

TiAl3 (m) cP4

Pm3m

AuCu3

a = 397.2 metastable, from splat cooling

obtained at 85 at.% Al [2001Bra]

Ti52Al48 cP20

P4132

Mn

a = 690 metastable phase precipitating in early

stage from amorphous thin film after

anneal 1 h, 525°C [1999Abe]

Ti2Cu

< 1012

tI6

I4/mmm

MoSi2

a = 295.3

c = 1073.4

[Mas2, V-C2, 1994Ali]

dissolves -8 at.% Al

(Ti,Al)2Cu [1971Vir]

TiCu

< 982

tP4

P4/nmm

TiCu

a = 310.8 to 311.8

c = 588.7 to 592.1

48 to 52 at.% Cu [Mas2, V-C2]

Ti3Cu4

< 925

tI14

I4/mmm

Ti3Cu4

a = 313.0

c = 1994

[Mas2, V-C2]

Ti2Cu3

< 875

tP10

P4/nmm

Ti2Cu3

a = 313

c = 1395

[Mas2, V-C2]

TiCu2

890-870

oC12

Amm2

VAu2

a = 436.3

b = 797.7

c = 447.8

[Mas2, V-C2]

TiCu4

885 - 400

oP20

Pnma

ZrAu4

a = 452.5

b = 434.1

c = 1295.3

~ 78 to ~ 80.9 at.% Cu [Mas2, V-C2]

TiCu4

500

tI10

I4/m

MoNi4

~ 78 to ~ 80.9 at.% Cu [Mas2]

* 1, TiCu2Al

1125

cF16

Fm3m

MnCu2Al

a = 601

a = 601.9

[1965Ram2]

[1997Dur]

with homogeneity range

[1971Vir, 1973Mar]

L21 ordered phase

* 2, TiCuAl

< 1200

hP12

P63/mmc

MgZn2

a = 502.6

c = 808.4

a = 503

c = 811

a = 506

c = 814

[1964Kry], with homogeneity range

[1971Vir, 1973Mar], stable at 1200°C

[2000Kai]

C14 type phase

Ti33Cu37Al30

[1989Miz]

Ti33Cu20Al47

[1989Miz]

* 3, Ti2CuAl51350

cP4

Pm3m

Cu3Al

a = 392.7 [1965Ram2], linear homogeneity range

with constant Ti [1973Mar]

melting [1971Vir]

L12 ordered phase

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters


169


MSIT®

Al–Cu–Ti



Al Cu Ti

L “Ti2Al5” + 3 ? max1 L 65 8 27

L + “Ti2Al5” TiAl3 + 3 1280 U1 L 70 8 22

L + “Ti2Al5” TiAl + 3 ? U2 L 61 9 30

L ( Ti) + 2 1155 max2 L 30 27 43

L + ( Ti) TiAl + 2 1150 U3 L 39 15 46

L 2 + 1 1100 max3 L 28 46 26

L (Cu) + 1 1020 max4 L 6 76 18

L + (Cu) + 1 1010 U4 L 25 68 7

L + TiAl 2 + 3 1000 U5 L 41 19 40

L + 0 + 1 1000 U6 L 36.94 57.83 5.23

L + ( Ti) Ti2Cu + ( Ti) 980 U7 L 10 27 63

L + 2 ( Ti) + 1 970 U8 L 18 41 41

L +( Ti) Ti2Cu + 1 965 U9 L 16 42 42

L + Ti2Cu TiCu + 1 940 U10 L 7 52 41

L + 0 1 + 1 920 U11

L + TiCu Ti3Cu4 + 1 910 U12 L 2 63 35

L + Ti3Cu4 TiCu2 + 1 900 U13

L + (Cu) TiCu4 + 1 870 U14 L 2 71 27

L TiCu2 + TiCu4 + 1 860 E1 L 2 66 32

L + 2 1 + 3 860 U15

L + 1 1 + 2 820 U16

L + 1 3 + 2 810 U17

L + 2 1 + 3 610 U18 L 64 34 2

L + 1 + 3 580 U19 L 68 30 2

L + 3 + TiAl3 570 U20 L 74 24 2

L (Al) + + TiAl3 540 E2 L 82 17 1

170


MSIT®

Al–Cu–Ti

20

40

60

80

20 40 60 80

20

40

60

80

Ti Cu


Axes: at.%

U3

max2

τ3

Ti3Al

τ2

max3

τ1

TiCu

Ti2Cu

(βTi)

"Ti2Al5"

(αTi)

TiAl

(Cu)

max4

e, 1032

p, 1037

p, 958

e, 848

p, 624

p, 591η

1

θ

e, 548.2

(Al)

p, 1393

p, 1416

p, 1463

p, 1490

e, 1005 e, 960p, p, e,p,

TiCu2Ti3Cu4 βTiCu4

E2

U20U1

U2

max1

U5

ε2

ε1U11

γ0U6

U4

β

U12 E1 U14

U10U9

U8

U7

U19

U18

U16

U15

U13

U17

925 890 875885

Fig. 1: Al-Cu-Ti.

Liquidus surface

40

50

60

10 20

40

50

60

Ti 65.00Cu 0.00Al 35.00

Ti 35.00Cu 30.00Al 35.00

Ti 35.00Cu 0.00Al 65.00 Data / Grid: at.%

Axes: at.%

TiAl

(βTi)

(αTi)

Fig. 2: Al-Cu-Ti.

Partial isothermal

section at 1300°C

171


MSIT®

Al–Cu–Ti

40

50

60

10 20

40

50

60

Ti 65.00Cu 0.00Al 35.00

Ti 35.00Cu 30.00Al 35.00


Axes: at.%

TiAl

(βTi)

(αTi) τ2

40

50

60

10 20

40

50

60

Ti 65.00Cu 0.00Al 35.00

Ti 35.00Cu 30.00Al 35.00


Axes: at.%

Ti3Al

TiAl

τ2

Fig. 3: Al-Cu-Ti.

Partial isothermal

section at 1200°C

Fig. 4: Al-Cu-Ti.

Partial isothermal

section at 1000°C

172


MSIT®

Al–Cu–Ti

20

40

60

80

20 40 60 80

20

40

60

80

Ti Cu


Axes: at.%

τ2

τ1

TiAl

β,TiCu4

(Cu)

γ1

δ

ζ2

η2

θTiAl2

TiAl3

(Al)

Ti3Al

(αTi)

Ti2CuTiCu

Ti3Cu4

Ti2Cu3

τ3

20

40

60

80

20 40 60 80

20

40

60

80

Ti Cu


Axes: at.%

τ2

TiAl

TiAl2

TiAl3

L

ε2

γ1

γ0

β

(Cu)

τ3

τ1

"Ti2Al5"

Ti3Al

(αTi)

TiCuTi3Cu4

Ti2Cu3Ti2Cu β,TiCu4(βTi)

Fig. 6: Al-Cu-Ti.


500°C

Fig. 5: Al-Cu-Ti.


800°C

173


MSIT®

Al–Cu–Ti

500

600

Ti 0.00Cu 4.50Al 95.50

Ti 0.60Cu 4.50Al 94.90Ti, at.%

Tem

pera

ture

, °C

540

L+(Al)L+TiAl3

L

L+(Al)+TiAl3

(Al)+θ+TiAl3

0.40.2

400

500

600

700

800

900

1000

1100

Ti 3.45Cu 76.00Al 20.55

Ti 0.00Cu 79.30Al 20.70Cu, at.%

Tem

pera

ture

, °C

L

β

(Cu)+β

(Cu)+γ1

(Cu)+γ1+TiCu2Al

(Cu)+β+TiCu2Al

β+TiCu2Al

570

7977 78

Fig. 7: Al-Cu-Ti.

Partial vertical

section with constant

10 mass% Cu

Fig. 8: Al-Cu-Ti.

Partial vertical

section with constant

10 mass% Al

174


MSIT®

Al–Cu–Yb

Aluminium – Copper – Ytterbium

Gabriele Cacciamani and Paola Riani

Literature Data

The Al-Cu-Yb system has been previously assessed by [1992Ran] and, recently, by [2003Ria], in the

framework of a general review of the R-Cu-Al (R = rare earth) systems.

At low Yb concentrations (< 33 at.% Yb) several ternary phases are present, which often show line

solubility due to substitution between Al and Cu. Phase equilibria at 600°C have been studied by

[1993Ste1].

Binary Systems

The binary systems Al-Cu, Al-Yb and Cu-Yb assessed by [2003Gro, 2003Ria], [2002Bod] and [2002Rog]

are accepted here as boundary sub-systems.

Solid Phases

Crystal structure data are reported in Table 1. Appreciable ternary extensions of the binary compounds and

seven ternary phases are present in the Al-Cu-Yb system for x(Yb) < 0.33.

YbCu5 (hexagonal, CaCu5 type) dissolves up to 35 at.% Al. A cubic structure, AuBe5 type, was also

obtained at high pressure in the Cu-Yb system [1996He, 2002Rog]. At room conditions substitution of Cu

by Al is reported to stabilize the hexagonal structure [1998He].

At nearly equiatomic composition 1 (ZrNiAl type, related to Fe2P type) [1968Dwi, 1973Oes, 1974Fer,

1993Ste1] shows a small solubility range. At high pressure it transforms to the cubic MgCu2 type structure

[1987Tsv1, 1987Tsv2].

2 (YbCu0.9Al2.1, PuNi3 type), nearly stoichiometric, has been identified by [1992Kuz] and confirmed by

[1993Ste1].

7 (Yb(CuxAl1-x)12, ThMn12 type) has been studied by [1976Bus, 1979Fel, 1993Ste1] at compositions close

to YbCu4Al8. The same structure was identified in a sample at the YbCu6Al6 composition investigated by

[1980Fel] after annealing at 800-1000°C.

An YbCuAl3 phase, tI10 BaAl4 type, has been reported by [1988Kuz] but not confirmed by [1993Ste1].

Isothermal Sections

The 600°C Al-Cu-Yb isothermal section has been studied by [1993Ste1]. It is reported in Fig. 1 according

to the modifications added by [2003Ria] in order to meet the accepted Al-Cu phase equilibria (in particular,

the presence of the liquid phase at this temperature was neglected in the original paper).


Properties related to the Yb mixed valence state in YbCuAl (the 1 phase) have been studied by several

authors: [1977Mat] (low temperature Cp and magnetization), [1979Ent] (symmetry properties, phonon

phenomena and anomalous features in the low temperature T/P phase diagram), [1980Mat] (thermal

expansion and magneto-volume effect), [1981Ble1, 1981Ble2] (low temperature Cp at high pressure up to

10 kbar), [1981Pot] (thermal expansion and Cp), [1982Mar, 1991Ell] (molar volume).

More recently, attention has been attracted by the YbCu5-based solid solution. Low temperature resistivity

and magnetic properties have been investigated in either CaCu5 type and AuBe5 type structures evidencing

Kondo behavior [1992Bau, 1998He, 1999Bon, 2001And, 2001He].

175


MSIT®

Al–Cu–Yb

References



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RCuAl”, J. Less-Common Met., 30, 225-236 (1973) (Crys. Structure, Magn. Prop.,

Experimental, 21)

[1974Fer] Ferro, R., Marazza, R., Rambaldi, G., “Equiatomic Ternary Phases in the Alloys of the Rare

Earth with In and Ni or Pd”, Z. Metallkd., 65, 37-39 (1974) (Crys. Structure, Experimental,

2)

[1976Bus] Buschow, K.H.J., van Vucht, J.H.N., van den Haagenhof, W.W., “Note on the Crystal

Structure of the Ternary Rare Earth 3d Transition Metal Compounds of the Type RT4Al8”,

J. Less-Common Met., 50(1), 145-150 (1976) (Crys. Structure, 2)

[1977Mat] Mattens, W.C.M., Elenbaas, R.A., de Boer, F.R., “Mixed-Valence Behaviour in the

Intermetallic Compound YbCuAl”, Commun. Phys., 2, 147-150 (1977) (Experimental,

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[1979Fel] Felner, I., Nowik, I., “Magnetism and Hyperfine Interactions of 57Fe, 151Eu, 155Gd, 161Dy,166Er and 170Yb in RM4Al8 Compounds (R=Rare Earth or Y, M=Cr, Mn, Fe, Cu)”,

J.Phys.Chem. Solids, 40, 1035-1044 (1979) (Crys. Structure, Experimental, 8)

[1980Fel] Felner, I. “Crystal Structure of Ternary Rare Earth - 3d Transition Metal Compounds of the

RT6Al6 Type ”, J. Less-Common Met., 72, 241-249 (1980) (Crys. Structure, Experimental,

10)

[1980Mat] Mattens, W.C.M., Hoelscher, H., Tuin, G.J.M., Moleman, A.C., de Boer, F.R., “Thermal

Expansion and Magneto-Volume Effects in the Mixed-Valent Compound YbCuAl”,

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[1981Ble2] Bleckwedel, A., Eichler, A., Pott, R., “Pressure Dependence of the Specific Heat of

YbCuAl”, Physica B/C, 107B, 93-94 (1981) (Experimental, Phys. Prop., 7)

[1981Pot] Pott, R., Schefzyk, R., Wohlleben, D.,Junod, A., “Thermal Expansion and Specific Heat of

Intermediate Valent YbCuAl”, Z. Phys. B: Condens. Matter, 44B, 17-24 (1981) (Electr.

Prop., Experimental, 20)

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[1985Mur] Murray, J.L., “The Aluminum-Copper System”, Internat. Met. Rev., 30(5), 211-233 (1985)

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YbXCu4 (X = Al, Ag and Ga)”, J. Phys. C: Solid State Physics, 20(15), L307-310 (1987)

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[1987Tsv1] Tsvyashchenko, A.V., Fomicheva, L.N., “High-Pressure Synthesis and Structural Studies of

Rare Earth (R) Compounds RCuAl”, J. Less-Common Met., 134, L13-L15 (1987) (Crys.


176


MSIT®

Al–Cu–Yb

[1987Tsv2] Tsvyashchenko, A.V., Fomicheva, L.N. “New Polymorphic Modifications of the


from Izv. Akad. Nauk SSSR, Neorg. Mater., 23, 1148-1152 (1987) (Crys. Structure,

Experimental, 15)

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Yb) and their Crystal Structure” (in Russian), Dop. Akad. Nauk Ukr. SSR, Ser. B: Geol.

Khim. Biol. Nauki, (11), 40-43 (1988) (Crys. Structure, Experimental, 4)

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Bull. Alloy Phase Diagrams, 10, 47-49 (1989) (Crys. Structure, Equi. Diagram, Review, 16)


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Experimental, 17)

[1990Ste] Stelmakhovich, V.M., Kuzma, Yu.B., “New Compounds Ln6(Cu,Al)23 and their Crystal

Structure” (in Russian), Dokl. Akad. Nauk SSSR, (6), 63-65 (1990) (Crys. Structure,

Experimental, 4)



Metals, 170, 171-184 (1991) (Experimental, Crys. Structure, 57)

[1991Ste] Stel'makhovich, B.M., Kuz'ma, Yu.B., “A New Aluminide Yb8Cu17Al49 and its Structure”,

Sov. Phys.-Crystallogr. (Engl. Transl.), 36(6), 808-810 (1991) (Crys. Structure, 4)

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Thermodynamical Properties of Ytterbium-Copper-Aluminum (Yb(Cu,Al)5) Compounds”,

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the Intermediate Valence Systems Yb(CuxAl1-x)5 (x=1, 0.8, 0.6)”, Mater. Sci. Forum,


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- Aluminum System”, J. Alloys Compd., 190, 161-164 (1993) (Crys. Structure, Equi.


[1993Ste2] Stel'makhovich, B.M., Kuz'ma, Yu.B., Akselrud, L.G., “New Intermetallic Compounds

with Structures of the YbMo2Al4 and Th2Zn17 Type”, Russ. Metall. (Engl. Transl.), (1),


[1994Mur] Murray, J.L., “Al-Cu (Aluminum-Copper)”, in “Phase Diagrams of Binary Copper Alloys”,

Subramanian, P.R., Chakrabati, D.T., Laughlin, D.E., (Eds.), ASM International, Materials

Park, OH, 18-42 (1994) (Equi. Diagram, Review, 226)

[1994Sub] Subramanian, P.R., Laughlin, D.E., “Cu-Yb (Copper-Ytterbium)” in “Phase Diagrams of

Binary Copper Alloys”, Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM

International, Materials Park, OH, 482-486 (1994) (Equi. Diagram, Review, 39)

[1996Cer1] Cerny, R., Francois, M., Yvon, K., Jaccard, D., Walker, E., Petricek, V., Cisarova, I.,

Nissen, H.-U., Wessicken, R., “A Single-Crystal X-ray and HRTEM Study of the

Heavy-Fermion Compounds YbCu4.5”, J. Phys.: Condens. Matter, 8, 4485-4493 (1996)

(Crys. Structure, 13)

[1996Cer2] Cerny, R., “YbCu4.5 - A Giant Structure Determined by Single-Crystal X-Ray Diffraction

and HRTEM”, Acta Crystallogr., A52, 323-324 (1996) (Crys. Structure, 1)

177


MSIT®

Al–Cu–Yb

[1996Goe] Gödecke, T., Sommer, F., “Solidification Behaviour of the Al2Cu Phase” Z. Metallkd.,

87(7), 581-6 (1996) (Equi. Diagram, Crys. Structure, 8)

[1996He] He, J., Tsujii, N., Nakanishi, M., Yoshimura, K., Kosuge, K., “A Cubic AuBe5-Type YbCu5

Phase with Trivalent Yb Ion”, J. Alloys Compd., 240, 261-265 (1996) (Crys. Structure, 18)

[1997Bel] Belan, B.D., Bodak, O.I., Cerny, R., Pacheko, J.V., Yvon, K., “Crystal Structure of YbCu”,

Z. Kristallogr. NCS, 212, 508 (1997) (Crys. Structure, 6)

[1998He] He, J., Tsujii, N., Yoshimura, K., Kosuge, K., “Preparation of Cubic AuBe5-type

YbCu5-xAlx (0 < x < 0.5) Under High Pressure and Their Kondo Behavior”, J. Alloys

Compd., 268, 221-225 (1998) (Crys. Structure, Experimental, Magn. Prop., 27)


the Cu-Al Binary System”, J. Alloys Compd., 264(1-2), 201-08 (1998) (Equi. Diagram,


[1999Bon] Bonville, P., Vincent, E., Bauer, E., “Low Temperature Kondo Reduction of Quadrupolar

and Magnetic Moments in the YbCu5-xAlx Series”, Eur. Phys. J. B, 8, 363-369 (1999)

(Experimental, Thermodyn., 13)

[2001And] Andreica, D., Amato, A., Gygax, F.N., Schenck, A., Wiesinger, G., Reichl, C., Bauer, E.,

“ SR Studies of the Nonmagnetic-Magnetic Transition in YbCu5-xAlx”, J. Magn. Magn.

Mater., 226-230, 129-131 (2001) (Experimental, Magn. Prop., 5)

[2001He] He, J., Ling, G., Ye, Z., “Magnetic Properties of Hexagonal YbCu5-xAlx Crossover from

Intermediate Valence to Trivalence of Yb Ion”, J. Alloys Compd., 325, 54-58 (2001) (Crys.


[2002Bod] Bodak, O., “Al-Yb (Aluminum-Ytterbium)”, MSIT Binary Evaluation Program, in MSIT



Assessment, 15)




[2002Rog] Rogl, P., van Rompaey, T., “Cu-Yb (Copper-Ytterbium)”, MSIT Binary Evaluation

Program,in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International

Services GmbH, Stuttgart; Document ID: 20.13889.1.20 (2002) (Crys. Structure, Equi.





[2003Ria] Riani, P., Arrighi, L., Marazza, R., Mazzone, D., Zanicchi, G., Ferro, R., “Ternary Rare

Earth Aluminum Systems with Copper: a Review and a Contribution to Their Assessment”

submitted to J. Phase Equilib. (Assessment, Review, 267)

178


MSIT®

Al–Cu–Yb


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

< 660.45

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2],

0 to 2.48 at.% Cu [Mas2]

(Cu)

< 1084.62

Cu1-xAlx

cF4

Fm3m

Cu

a = 361.46

a = 361.52

a = 365.36

at 25°C [Mas2],

0 to 19.7 at.% Al [Mas2]

0 to 0.1 at.% Ce at 876°C [1994Sub]

x=0, quenched from 600°C [1991Ell]

x=0.152, quenched from 600°C, linear

da/dx [1991Ell]

( Yb)

819-795

cI2

Im3m

W

a = 444 [Mas2]

( Yb)

795-(-3)

cF4

Fm3m

Cu

a = 548.48 at 25°C [Mas2]

( Yb)

<-3

hP2

P63/mmc

Mg

a = 387.99

c = 638.59

[Mas2]

, Cu3Al(h)

1049-559

cI2

Im3m

W a = 294.6

~70 to 82 at.% Cu [1985Mur],

[1998Liu]

at 672°C

2, Cu1-xAlx< 363

t**

TiAl3long period

super-lattice

a = 366.8

c = 368.0

0.22 x 0.235 [1985Mur]

76.5 to 78.0 at.% Cu

at 76.4 at.% Cu

(subcell only)

0, Cu1-xAlxCu~2Al

1037-800

cI52

I43m

Cu5Zn8

0.37 x 0.315 [Mas2],

63 to 68.5 at.% Cu [1998Liu]

1, Cu9Al4< 890

cP52

P43m

Cu9Al4

a = 870.23

a = 870.68

62 to 68 at.% Cu, [Mas2, 1998Liu];

single crystal [V-C2] at 68 at.% Cu


, AlxCu1-x

< 686

hR*

R3m

a = 1226

a = 1511

0.407 x 0.381 [1985Mur]

59.3 to 61.9 at.% Cu

at x = 38.9 [V-C2]

1, Cu1-xAlx958-848

cubic? 0.406 x 0.379

59.4 to 62.1 at.% Cu [Mas2, 1985Mur]

2, Cu2-xAl

850-560

hP6-x

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.78 x 0.45

55 to 61 at.% Cu

[Mas2, 1985Mur, V-C2],


179


MSIT®

Al–Cu–Yb

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2Cu47.8Al35.5

a = 812

b = 1419.85c = 999.28


2, Cu11.5Al9(r)

< 570oI24 - 3.5

Imm2Cu11.5Al9

a = 409.72

b = 703.13c = 997.93


1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200c = 863.5

49.8 to 52.4 at.% Cu


2, CuAl(r)

< 560

mC20

C2/m

CuAl

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.3 at.% Cu [V-C]

, CuAl2< 592

tI12

I4/mcm

CuAl2a = 606.7

c = 487.7

32.05 to 32.6 at.% Cu at 549°C

32.4 to 32.8 at.% Cu at 250°C

[1996Goe]

single crystal [V-C2,1989Mee]

YbAl3< 980

cP4

Pm3m

AuCu3

a = 420.2 [1989Gsc]

Yb(CuxAl1-x)2

YbAl2< 1360

cF24

Fd3m

MgCu2

a = 787.7

0 x 0.25 [1993Ste1]

[1989Gsc]

YbCu

< 628

oP8

Pnma

FeB

a = 756.8

b = 426.7

c = 577.6

a = 756.53

b = 425.53

c = 576.67

[1994Sub]

[1997Bel]

YbCu2

< 757

oI12

Imma

CeCu2

a = 428.6 to 429.1

b = 689.4 to 689.9

c = 738.2 to 738.6

[1994Sub, V-C2]

YbCu2 (HP) hP12

P63/mmc

MgZn2

a = 526.0 ± 0.05

c = 856.7 ± 0.08

[V-C2]

Yb2Cu7

< 825

? ? [1994Sub, 1996Cer2]

Yb2Cu9

< 937

mC7448

-

Yb2Cu9

a = 4896.1

b = 4899.4

c = 4564.3

= 91.24°

monoclinic superstructure deriving

from cubic AuBe5-type via the

introduction of anti-phase boundaries

and copper-deficient shear planes

[1996Cer1, 1996Cer2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

180


MSIT®

Al–Cu–Yb

Yb(CuxAl1-x)5 (I)

YbCu~6.5

< 879

hP6

P6/mmm

CaCu5

a = 510.6 to 500.8

c = 414.6 to 411.7

a = 504.4

c = 414.0

a = 499.2 to 500

c = 412.6 to 413

a = 498.6

c = 412.8

0.58 x 1 [1993Ste1]

at x = 0.6 to 0.9

[1992Bau, 1993Gra]

at x = 0.8 [1987Adr]

[1994Sub], the composition Yb2Cu13

was attributed to a structure described

with same lattice parameter with a

random substitution of 18% of

Yb-sites by Cu-pairs [1994Sub]

[1996He]

Yb(CuxAl1-x)5 (II) cF24

F43m

AuBe5

a = 700.0 to 697.3 0.5 x 1 HP phase

prepared at 1.5 GPa, 1000°C, but also

found in as-cast alloys prepared under

ambient pressure [1996He, 1998He]

Yb6Cu23 (HP) cF116

Fm3m

Th6Mn23

a = 1203 ± 1 [V-C2]

* 1, Yb(CuxAl1-x)2 hP9

P62m

ZrNiAl

a = 692.5 to 691.3

c = 399.0 to 398.3

0.50 x 0.55 [1993Ste1]

* 2, YbCu0.9Al2.1 hR36

R3m

PuNi3

a = 547.1

c = 2535.8

[1992Kuz,1993Ste1]

* 3, Yb6(CuxAl1-x)23 cF116

Fm3m

Th6Mn23

a = 1223.4 x = 0.74 (Yb6Cu16Al7) [1990Ste]

* 4, Yb(CuxAl1-x)6 tI14

I4/mmm

YbMo2Al4

a = 638.6

c = 492.6

x = 0.85 [1993Ste1, 1993Ste2]

* 5, Yb4(CuxAl1-x)33 tI*

I4/mmm

Yb8Cu17Al49

a = 856.5

c = 1625.5

x = 0.26 [1991Ste]

* 6, Yb2(CuxAl1-x)17 hR57

R3m

Th2Zn17

a = 887.7 to 865.3

c = 1273.4 to 1265.9

0.46 x 0.51 [1993Ste1]

* 7, Yb(CuxAl1-x)12 tI26

I4/mmm

ThMn12

a = 872.4 to 862.3

c = 511.8 to 505.7

a = 874.6

c = 512.2

a = 864.3

c = 504.3

0.33 x 0.50 [1993Ste1]

at x = 0.33 [1979Fel]

at x = 0.50 [1980Fel]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

181


MSIT®

Al–Cu–Yb

20

40

60

80

20 40 60 80

20

40

60

80

Yb Cu


Axes: at.%

τ1

τ3

τ2

τ5

τ7

τ6

τ4

YbCu5YbCu2YbCu

YbAl2

YbAl3

η1

ε2

δγ

1

β

L

(Al)

?

(Cu)(Yb)

Fig. 1: Al-Cu-Yb.


600°C

[1993Ste1, 2003Ria]

182


MSIT®

Al–Cu–Zn

Aluminium – Copper – Zinc

Gautam Ghosh and Jan van Humbeeck, updated by Pierre Perrot

Literature Data

This ternary system contains many technologically important alloys, present and future applications.

Accordingly, the phase equilibria of the system have been reviewed [1934Fus, 1943Mon, 1952Han,

1961Phi, 1969Gue, 1973Wil, 1976Mon, 1979Cha] from time to time. Köster [1941Koe3] was the first to

report the entire liquidus surface and it was subsequently modified by [1960Arn2]. Isothermal sections in

the temperature range of 200 to 700°C have been determined by several researchers [1932Bau1, 1932Bau2,

1932Bau3, 1940Geb, 1941Geb1, 1941Koe1, 1941Koe2, 1941Koe3, 1942Geb, 1942Koe, 1960Arn1,

1960Arn2]. After a gap of four decades, [1980Mur] reinvestigated the solid state equilibria, using 31 ternary

alloys containing about 40.8 mass% Cu, in the temperature range of 250 to 350°C by means of

metallography, X-ray diffraction and electron probe microanalysis. Thermodynamic descriptions of the

system were mainly carried out by [1998Lia, 2002Mie]. Except for the sequence of solid state phase

transformations, the basic features of the phase equilibria in all of the above investigations are consistent

with each other. The present evaluation continuous the detailed critical review made by [1992Gho], which

took into account the data published until the year 1988.

Al-Cu-Zn alloys exhibit high damping capacity, shape memory effects and super elasticity which allows a

wide variety of possible use. The physical properties are associated with the reversible thermo-elastic

martensitic transformation [1987Lon, 1987Sca, 1988Mun, 1988Yev, 1990Gui, 1992Gui, 1993Lex,

1994Bou, 1995Pri1, 1995Pri2, 1997Zha, 1998Buj, 1999Ago1, 1999Lon, 2000Pel, 2000Zel]. So, interest in

these materials is grown and a large amount of literature is devoted to their physical properties.

The enthalpy of formation of the ternary phase ’ has been measured by dissolution calorimetry [2000Leg].

Calphad assessment has been carried out by [1998Lia, 2002Che, 2002Mie]. [2000Kra] calculated

solidification maps below the solidus at different cooling rates.

Binary Systems

The edge binary systems were recently critically evaluated, Al-Cu by [2003Gro], Al-Zn by [2003Per] and

Cu-Zn by [2003Leb] in the MSIT Binary Evaluation Program. These works are accepted here.

Solid Phases

The maximum solid solubility of Cu in ( Al) is up to 5.5 mass% in absence of Zn, and that of Zn is up to

83.1 mass% in absence of Cu. In equilibrium with the Cu solubility in (Al) increases with addition of Zn,

whereas in the ( Al)+ two phase field it decreases with increasing Zn content. The solid solubility limits

of Cu and Zn in (Al) are shown in Fig. 1 [1961Phi]. Within the composition range covered in Fig. 1, the

locus of the apex of the ( Al)+ + three-phase field is also shown. The apex of the ( Al)+ +( Zn)

three-phase field was not given by [1961Phi]; it is estimated in Fig. 1 and given by a dashed line. The solid

solubilities of Cu in (Al), given by [1942Geb] at 350, 300 and 240°C agree reasonably well with those of

[1961Phi]. However, the solid solubility of Zn in (Al) given by [1942Geb] are systematically higher than

those of [1961Phi]. [1941Koe1] reported that (Al) contains 1.5 mass% Cu and 33.5 mass% Zn when it is in

equilibrium with and phases at 350°C (annealed for 336 h), whereas [1942Geb] reported the

composition of (Al) to be about 1.5 mass% Cu and 43.0 mass% Zn after annealing at the same temperature

for 1680 h. Hume-Rothery [1948Hum] discussed the solid solubility limits of Al and Zn in (Cu) in terms of

the electron concentration factor. He noticed that, when Al is added to Cu-Zn alloys, the solubility range of

the (Cu) phase against remains at a constant electron concentration over a wide range of composition,

whereas when Zn is added to Al-Cu alloys there is an immediate departure from the simple electron

concentration rule. The solid solubility of Al and Cu in (Zn) were reported by [1936Bur, 1940Geb,

1940Loe, 1941Geb1, 1942Geb, 1949Geb] and [1980Mur]. The maximum solubility are about 1.3 mass%

183


MSIT®

Al–Cu–Zn

Al and 2.8 mass% Cu at 375°C and 0.8 mass% Al and 1.7 mass% Cu at 275°C. The saturation

concentrations of Al and Cu in (Zn) [1940Loe], as a function of temperature, are listed in Table 3. It should

be noted that the solubility found by [1940Geb, 1940Loe, 1941Geb1] and [1942Geb] agree well. Those of

[1980Mur] indicate a higher Cu solubility. The phase shows a continuous series of solid solutions from

Cu3Al to CuZn; it has a disordered cI2, W type structure at high temperatures. The stability of the phase

alloys decreases with decreasing temperature, and centers around an electron concentration of 1.48 for both

the binary and ternary alloys. [1948Ray] predicted the lower temperature limit of the stability of the ternary

phase in terms of an effective size factor. At lower temperatures, the phase undergoes ordering to a CsCl

or Fe3Si type superlattice depending on the alloy composition. Comprehensive reviews of the stability of

the phase and the effect of ordering on the subsequent martensitic transformation can be found elsewhere

[1977Rap, 1978Sin, 1980Ahl, 1986Ahl1, 1986Ahl2, 1995Ahl]. Also the -brass phases form a continuous

series of solid solutions at high temperatures [1941Koe3] which shows a miscibility gap below about

400°C. The behavior of the binary and ternary phases has been investigated by a number of experimental

techniques, such as resistivity and thermo-emf [1972Kan1, 1973Ash], X-ray diffraction [1972Kan2,

1974Ash, 1988Kis], and thermo-graphymetry and dilatometry [1974Umu]. The solid solubilities of Al in

Cu5Zn8 at 20 and 350°C are about 3.5 and 7.0 mass% Al, respectively [1973Ash]. At the same temperatures,

the 1 phases of the Al-Cu binary system dissolve about 30 mass% Zn [1973Ash]. With the addition of Al

in Cu5Zn8, the lattice parameter is reported to decrease continuously [1928Bra]. [1941Koe2] and

[1941Koe3] assumed , and ' to have one common field of homogeneity at higher temperatures. The

same was assumed for the 2 and phases. The phases and were shown to be different phases at any

temperature by [1960Arn2]. The phases 2 and have such different unit cells that it is very improbable to

have one continuous series of solid solutions between them. The 2 phase of the Al-Cu binary system was

assumed to be completely soluble with the phase of the Cu-Zn binary system above about 680°C

[1941Koe3] and [1960Arn2]. Below this temperature, separation occurs through the intrusion of

equilibrium between the and phases. The phase of the Al-Cu binary system can dissolve up to 2 to 3

mass% Zn with little change in lattice parameter and properties [1941Koe3]. The phase of the Cu-Zn

binary system can dissolve up to about 12 mass% Al [1941Koe3] at about 600°C, and this solid solubility

decreases with decreasing temperature. The ternary phase, below 250°C has two separate ranges of

homogeneity and ' [1960Arn1] due to the maximum of the three-phase field + + 1 [1941Koe1] and

[1941Koe2]. The different structures do not exclude a single range of homogeneity at higher temperatures

since the hR9 structure of ' is a superstructure of the CsCl type with ordered vacancies. It may be formed

from a CsCl structure with random distribution of vacancies by a second order transformation. The possible

formulas of and ' phases can be represented as Cu5Zn2Al3 and Cu3ZnAl4, respectively. The phase is

formed by a univariant peritectic reaction between 2 and liquid at about 740°C. The ternary ' phase

appears between 600 and 550°C near the Al-rich end of the homogeneity range of the phase. At 550°C,

the phase has a wide range of homogeneity (Fig. 7). At 200°C, the phase has a relatively narrow range

of homogeneity surrounding 13 mass% Al, 56 mass% Cu and 31 mass% Zn and the ' phase also has a

narrow homogeneity range surrounding 32 mass% Al, 56 mass% Cu and 12 mass% Zn (Fig. 13). A

metastable X phase has been reported [1988DeG] in both Al-Cu and ternary phase alloys which were

quenched from 900 to 950°C to room temperature or in ice water, and subsequently annealed at 300 to

348°C. This X phase has a long period superlattice structure and can be described in terms of 18R or

monoclinic unit cell. The details of the crystal structures and the lattice parameters of all stable solid phases

are listed in Table 1.


Figures 2a and 2b show the reaction scheme based on the investigations of [1940Geb, 1941Geb1,

1941Geb2, 1941Koe3, 1942Geb, 1949Geb, 1960Arn1, 1960Arn2] and [1980Mur]. The univariant reaction,

p8, occurs at about 740°C and feeds both the invariant reactions U4 and U6. Some of the four-phase

equilibria involving the compositions of the phases are listed in Table 2 after [1940Geb, 1941Geb1,

1941Geb2, 1941Koe3, 1942Geb, 1942Wei, 1949Geb, 1960Arn1, 1960Arn2, 1967Coo] and [1980Mur]. For

most of the invariant reactions, both the temperatures and the compositions of the invariant points as

184


MSIT®

Al–Cu–Zn

reported by [1925Han] and [1927Nis] differ substantially from the above authors. The sequence of the solid

state reactions in the temperature range of 275 to 350°C is adopted from [1980Mur]. The solid state

reactions in the temperature range of 268 to 288°C proposed by [1941Geb1] and [1941Geb2] have been

experimentally verified by [1980Mur]. This involves three U type reactions instead of one U type and one

E type reaction proposed by [1960Arn2]. To comply with the accepted Al-Zn binary phase diagram, the

temperature of the four-phase reaction U12 is taken as 278°C instead of 276°C as proposed by [1980Mur].

In contrast to the results of [1941Koe3] and [1980Mur], [1969Cia] reported that the four-phase reaction

U14, (Al)+ '+(Zn), can take place at as low as 50°C. In the original papers the reaction scheme was

simplified, as the phases 0 and 1, 1, 2 and , 1 and 2, 1 and 2 were not distinguished and the

invariant equilibria evolving from solid state three-phase reactions containing 2 and phases of the Al-Cu

system were neglected. In Figs. 2a and 2b the phases 0 and 1, 1, 2 and are tentatively distinguished.

It must be emphasized that the reaction scheme in Figs. 2a and 2b is still incomplete as the participation of

some binary solid state invariant reactions has not been considered; 1 and 2 as well as 1 and 2, are not

distinguished and are called 1 and 1, respectively. Nevertheless, the assessed reaction scheme is

consistent with the experimental phase diagrams.

Liquidus Surface

Figure 3 shows the liquidus surface after [1941Koe2] and [1960Arn2] and the monovariant curves

separating different areas of primary crystallization. The valley projection not yet determined are given

tentatively by dashed lines. [1911Lev] and [1912Lev] reported the primary crystallization temperature of a

number of ternary alloys, but their results differ significantly from [1941Koe2] and [1960Arn2]. The partial

liquidus surface determined by the earlier workers [1912Car, 1919Jar, 1920Ros, 1921Hau, 1925Han,

1927Nis] agree only qualitatively with the results of [1941Koe2] and [1960Arn2]. Even though [1926Nis]

and [1927Nis] performed a thorough investigation of the Al-Cu-Zn phase equilibria, some of their results

concerning the liquidus surface could not be reproduced later by [1928Ham]. The liquidus surface of the

Zn-corner reported by [1957Wat] does not agree with those of [1941Koe1] and [1960Arn2]. Approximate

isotherms at 50 K intervals are also shown in Fig. 3. The Cu-rich part of the system was optimized by

[2002Mie]. The calculated liquidus surface (xZn < 0.5, xAl < 0.35) agrees well with the experimental one

represented in Fig. 1.

Isothermal Sections

The isothermal sections at 700°C [1941Koe2, 1960Arn2], 650°C [1960Arn2], 600°C [1941Koe2,

1960Arn2], 550°C [1941Koe2, 1960Arn2], 500°C [1941Koe2], 400°C [1941Koe2], 350°C [1941Koe1,

1941Koe2, 1942Geb, 1960Arn1], 300°C [1942Geb], 240°C [1942Geb] and 200°C [1942Koe, 1960Arn1]

are shown in Figs, 4, 5, 6, 7, 8, 9, 10, 11,12 and 13, respectively. The Cu-rich regions are particularly derived

from [1932Bau1, 1932Bau2, 1932Bau3, 1970Fle] and the Al- and Zn-rich regions are derived from

[1940Geb, 1941Geb1, 1942Geb, 1949Geb] and [1980Mur]. The partial isotherms at the Zn-corner reported

by [1920Ros] and [1921Hau] in the temperature range of 200 to 400°C and those for other alloys by

[1925Han] at 370 and 385°C agree only qualitatively with the results of the above authors. The isothermal

section at 700°C (Fig. 4) shows the continuous solid solutions (between of Al-Cu binary system and

of Cu-Zn binary system) and (between of Al-Cu binary system and of Cu-Zn binary system). In Fig. 4,

the phases 2 and are tentatively distinguished by dashed lines. Figure 7 shows the isothermal section at

550°C. Here, the ternary phase ' appears in the Al-rich region of the phase field. Even though two

different superstructures, for and ' phases, have been reported, no two-phase field has been detected

[1941Koe1, 1941Koe2]. The isothermal sections shown above are also consistent with the results of phase

decomposition studies by several authors [1934Ful, 1970Fle, 1984Man, 1986Myk, 1986Yan]. Below

350°C, the Cu-rich portion of the isothermal sections are still in doubt. In the isothermal sections, minor

adjustments have been made to comply with the accepted binary phase diagrams. The liquidus isotherms in

Figs. 4, 5, 6, 7, 8 and 9 are adjusted to those given in Fig. 3. (Al)’ and (Al)’’ correspond to the de-mixing

of ( Al) below 352°C.

185


MSIT®

Al–Cu–Zn


A large number of temperature-concentration diagrams, cutting vertically through the ternary phase

diagram are reported as isopleths or polythermal sections, e.g. by [1919Jar], and by [1919Sch] at constant

Cu contents of 2, 4, 6, 8 and 10 mass% Cu. [1921Hau] determined the isopleths at 1, 2, 3, 4, 5, 7, and 9

mass% Cu and also at 2, 4, 6, 8, 10, 12 and 15 mass% Al. [1925Han] determined the isopleths at 5, 10, 15,

20 and 25 mass% Cu. [1926Nis] reported the polythermal sections at 1, 2, 3, 5, 7.5 and 10 mass% Cu.

[1949Geb] reported three isopleths at 1, 2 and 3 mass% Cu. [1960Arn2] determined two isopleths at 10 and

20 at.% Zn. [1957Wat] determined three polythermal sections at 2.5, 5.0 and 10.0 mass% Cu. The earlier

results [1919Jar, 1919Sch, 1921Hau, 1925Han, 1926Nis] agree only qualitatively with each other. In

general, there is substantial disagreement between the earlier results [1919Jar, 1919Sch, 1921Hau,

1925Han, 1926Nis] and later investigations by [1949Geb, 1957Wat] and [1960Arn2] which are considered

to be accurate and reliable. However all data have been considered in the course of this critical evaluation.

Thermodynamics

Heat capacities of the 1 and ’1 phases has been measured on the Cu-13.9Zn-17.3Al (at.%) [1988Tsu].

[1993Ahl] evaluates the phase stabilities of martensitic and equilibrium phases and discusses the

contribution which controls the Gibbs energy of the different phases. The first expressions of the chemical

potentials changes were proposed by [1988Kuz] for the transition liquid and by [1994Hsu] for the

martensitic transformations of the phase. The thermodynamic properties of the ternary alloys containing

25 to 62 at.% Al have been determined in [1994Van] by emf measurements between 420 and 920°C by an

aluminum concentration cell. [1998Lia] presents a thermodynamic description of the Al-Cu-Zn system with

an emphasis on the Al-Zn binary. The descriptions of the binary systems accepted by [1998Lia] are those

of [1993Che] for Al-Zn and [1993Kow] for Cu-Zn. The liquid, fcc-(Cu), fcc-(Al), cph-(Zn), and

disordered solutions are modeled by a disordered solution with the introduction of a ternary interaction

parameter. The two binary phases: Al4Cu9 and Cu5Zn8, isomorphous and forming a continuous solid

solution are of a rather complex structure. Cu5Zn8 has a superlattice in which one unit cell corresponds to

27 unit cells of the W type; Al4Cu9 is an ordered variant of that structure in which every Zn position of

Cu5Zn8 splits into two positions, one occupied by Al, the other by Cu. Models with 4 to 6 sublattices have

been proposed for the solid solution [2000Ans, 2000Sat]. The model used by [1998Lia] is a simple

Redlich-Kister description with hypothetical lattice stabilities used for the phases and does not take into

account the ordering; it describes reasonably well the solubility range. The 0 phase was modeled as

Cu8(Cu,Zn,Al)1(Zn,Al)4 and the ternary Cu5Zn2Al3 as (Al,Cu)1Cu4ZnAl4 that is as formed by two

hypothetical stoichiometric compounds Cu4ZnAl5 and Cu5ZnAl4 Using the Pandat software, [2001Che,

2002Che] propose an isothermal section of the diagram at 277°C (550 K) showing a miscibility gap in the

fcc-(Cu) solid solution which does not appear in the experimental diagrams drawn between 200 and 300°C

(Figs. 11, 12 and 13).


Al-Cu-Zn based alloys are important materials with shape-memory effect, more economic than Ni-Ti alloys

[1997Zha]. In addition to the martensitic transformation ensuring shape-memory effect [1995Gue,

1999Lov], these alloys are characterized by ordering occurring in the phase after annealing at 450°C and

below. Before turning into martensite, the parent phase (austenite) undergoes an ordering reaction which

transforms the unit cell (A2) into ordered 1 (L21) or 2CsCl. During the direct martensitic

transformation, the above parent phases change respectively into ’1 (monoclinic) and ’2 (orthorhombic)

martensites [1995Cha, 1998Buj]. Between 300 and 600°C, the phase can decompose by the following

reaction: ( Cu)+ Cu5Zn8 [2000Zel]. The heat exchange associated with the martensitic transformation

has been recorded for three alloy compositions, Cu-24.8Zn-9.2Al at.% [1995Cha], Cu-16.49Zn-15.75Al

at.% (alloy R) [2000Pel] and Cu-8.83Zn-22.09Al at.% (alloy H) [2000Pel]. On cooling, the martensitic

transformation starts at MS and is completed at MF; on heating, the reverse transformation (austenitization),

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starts at AS and terminates at AF. The temperature intervals (MS - MF) and (AF - AS) for the phase

transformations depend on the martensitic structure, but not on the grain size. A similar dependence applies

for the width of the hysteresis (AF - MS).

The martensitic transformations has been investigated by various methods, recording the nuclear magnetic

resonance [1991Dim], measuring the associated caloric effects [1988Mun, 1995Cha, 1998Wei, 2000Pel]

and observing the response of the material’s structure in X-ray diffraction and electron microscopy

[1989Tol, 1998Buj, 2000Dor, 2000Zel]. One of the resulting conclusions is that the relative stabilities of

different martensitic phases are related to the lattice distortion [1992Ahl, 1992Pel, 1992Sau, 1995Sau,

1995Ahl].

Other important features such as the influence of quenching and aging on the transformation temperatures

were investigated by [1988Ara, 1989Cha, 1994Wu, 1998Man]. [1990Gui] and [1996Gar] studied the

influence of compositional changes on the transformation temperatures. Effects on the transformations

attributed to the stress-state of the material were studied by [1992Ame, 1995Isa, 1998Gal]. The work of

[2001Bek] investigates the influence of pressure, up to 1.5 GPa.

The Gibbs energy of the martensitic transformation of both thermal and mechanical origin has been

evaluated by [1988Ort, 1991Gui1, 1991Gui2]. [1999Ago2] developed a thermo-mechanical model

allowing the simulation of the shape-memory effect on Cu-14.1Zn-17.0Al (at.%). Point defects in

Cu-Zn-Al single crystals alloys have been investigated by means of positron lifetime spectroscopy

[1997Som, 1999Rom]. The formation and growth of 1 plates from a ’ matrix by a bainitic transformation

has been studied by [1992Tak, 1994Men]. The shape memory effect has also been observed in alloys with

dual phase - ’ structure, obtained by quenching from the equilibrium - [1999Lon]. Martensites in

shape-memory alloys often exhibit unusual pseudo-elasticity referred to as the rubber-like behavior which

has been investigated by [1987Sak, 1995Pri1, 1995Pri2, 1995Tsu, 2000Yaw] and thermodynamic models

[1993Lex, 1994Bou] as well as thermo-mechanical models [1999Ago2] has been proposed.

Small Cu-additions to as-cast Al-Zn alloys close to the eutectoid composition show a relatively low ductility

but also instabilities [1992Cia], which can be reduced by relatively simple heat treatments [1992Bob].

Miscellaneous

[1986Sug] reported the chemical activity of Zn in liquid Al-Cu-Zn alloys at 1150 and 1100°C in the

composition range xZn < 0.09 and xAl 0.08. [1964Day] determined the solid/liquid distribution

coefficients by centrifugal method in Al-rich and Zn-rich alloys. The partition coefficients are reported to

be consistent with the phase diagram features.

As early as in the beginning 20th century [1905Gui] and [1906Gui] performed systematic studies of

replacing Zn by Al, Fe, Mg, Mn, P, Pb, Sb, Si and Sn in a number of Cu-Zn brasses. They determined the

volume fraction of the and phases in Cu-Zn alloys and their mechanical properties with the addition of

these alloying elements. Comparable systematic studies were made by [1925Sma] replacing Zn by Al, Fe,

Ni and Sn in Cu-Zn brasses. Similar alloy development studies, regarding the effect of Si and Sb on the

microstructure of Al-Cu-Zn bronzes, were also performed by [1930Sev]. All these laborious alloy

development studies were performed by carefully examining the microstructure and determining the

mechanical properties.

[2001Liu] investigated the influence of zinc and other elements on the (fcc), (bcc) and (Cu) Cu9Al4equilibrium in the Al-Cu system and develop a quantitative method to determine the effect of the alloying

elements on the two-phase microstructure. [2001Zhu1] analyses by electron back-scatter diffraction the

microstructure of an alloy Zn85-Cu11-Al4 (mass%) in which both hexagonal phases ( Zn) and are

present. The microstructure evolution in Zn76-Al22-Cu2 and Zn86-Al11-Cu3 (mass%) alloys during

ageing between 100 and 200°C were followed respectively by [2000Dor] and [2001Zhu2]. The evidence of

a spinodal decomposition of the ( Zn) phase and the occurrence of a four phase reaction + + is shown.

Prolonged ageing causes the disordered phase to transform into an ordered ’, which confirms previous

observations made by [1999Zhu]. The measured composition of the ’ phase 57.7Al-34.9Cu-7.4Zn (at.%)

agrees with the composition given by [1975Mur] and is incorporated in the Figs. 7 to 13.

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Al–Cu–Zn

Mechanical alloying of Al-Cu-Zn alloys [1998Lop] allows to form metastable phases such as ternary

compounds, supersaturated solutions and also amorphous alloys; this opens another large spectrum of

possible applications for this ternary system.

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Centrifugal Methods”, J. Inst. Met., 93, 276-277 (1964-1965) (Experimental, 7)

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Systems Cd-Sn-(Pd, In, Tl), Al-Cu-(Mg, Zn, Ag) and Zn-Sn-Pb”, J. Inst. Met., 95(6),

183-187 (1967) (Experimental, 17)

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(i.e. A+B C+D) in Al-Zn 78 % Alloys Containing 1-3% of Cu”, Bull. Acad. Pol. Sci., Ser.

Sci. Chim., 17, 371-378 (1969) (Experimental, 13)

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Transformations and Thermodynamics of the Transformation in a Cu-14.4Al-3.6Ni Alloy”,

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36 (9), 2627-2638 (1988) (Mechan. Prop., Experimental, 21)

[1988DeG] de Graef, M., Delaey, L., Broddin, D., “High Resolution Electron Microscopic Study of the

X-Phase in Cu-Al and Cu-Al-Zn Alloys”, Phys. Status Solidi A, 107, 597-609 (1988)

(Experimental, 25)

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Powder and Single-Crystal Neutron Diffraction”, Mater. Sci. Forum, 27-28, 89-94 (1988)


[1988Kuz] Kuznetsov, G.M., Krivosheeva, G.B., Shaina, M.V., “Study of Alloys of the Al-Mg-Zn-Cu

System” (in russian) Izv. Vyssh. Uchebn. Zaved., Tsvetn. Metall., (5), 88-91 (1988) (Equi.

Diagram, 8)

[1988Mun] Muntasell, J., Tamarit, J.H., Guilemany, J.M., Gil, J., Cesari, E., “Martensitic

Transformation Differences on Poly and Single CuZnAl Crystals”, Mater. Res. Bull.,

23(11), 1585-1590 (1988) (Crys. Structure, Experimental, 11)

[1988Ort] Ortin, J., Planes, A., “Thermodynamic Analysis of Thermal Measurements in

Thermoelastic Martensitic Transformations”, Acta Metall., 26(8), 1875-1889 (1988)

(Thermodyn., 36)

[1988Tsu] Tsumura, R., Rios-Jara, D., Chavez, M., Rodriguez, L., Akachi, T., Escudero, R., “Specific

Heat Measurements of the 1 and ’1 Phases in a Copper-Zinc-Aluminium Alloy”, Phys.

Status Solidi A, A105 (2), 411-418 (1988) (Thermodyn., Experimental, 10)

[1988Yev] Yevsyukov, V.A., Garshina, M.N., Agapitova, N.V., “Amplitudinal Dependence of Internal

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(1988) (Experimental, Mechan. Prop., 3)

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[1989Cha] Chandrasekaran, M., Cooreman, L., Van Humbeeck, J., Delaey, L., “Martensitic

Transformation in AlCuZn : Changes in Transformation Entropy Due to Post-Quench

Aging in the or Martensitic Condition”, Scr. Metall., 23(2), 237-239 (1989)

(Experimental, 14)

[1989Tol] Tolley, A., Jara, R.D., Lovey, F.C., “18R to 2H Transformations in Cu-Zn-Al Alloys”, Acta

Metall., 37 (4), 1099-1108 (1989) (Crys. Structure, Experimental, 12)

[1990Gui] Guilemany, J.M., Gil, F.J., “The Relationship Between Chemical Composition and

Transformation Temperatures, Ms and As, in Polycrystals and Single Crystals of Cu-Zn-Al

Shape-Memory Alloys”, Thermochim. Acta, 167, 129-138 (1990) (Experimental, 6)

[1991Dim] Dimitropoulos, C., Borsa, F., Rubini, S., Gotthardt, R., “NMR Techniques Applied to

Martensitic Transformation”, J. Phys. Colloque C4, 1, 307-315 (1991) (Crys. Structure,


[1991Gui1] Guilemany, J.M., Gil, F.J., “The Gibbs Free Energies of Thermal and Stress-Induced

Martensite Formation in Cu-Zn-Al Single Crystal Shape Memory Alloys”, Thermochim.

Acta, 182, 193-199 (1991) (Experimental, Thermodyn., 14)

[1991Gui2] Guilemany, J.M., Gil, F.J., “The Martensitic Transformation Entropy Values of Thermal

and Mechanical Origin in Shape Memory Cu-Zn-Al Single Crystals”, Thermochim. Acta,

190, 185-189 (1991) (Experimental, Thermodyn., 7)

[1992Ahl] Ahlers, M., Pelegrina, L.J., “The Martensitic Phases and Their Stability in Cu-Zn and

Cu-Zn-Al Alloys-II. The Transformation Between the Close Packed Martensitic Phases”,

Acta Metall. Mater., 40(12), 3213-3220 (1992) (Crys. Structure, Experimental,

Thermodyn., 16)

[1992Ame] Amengual, A., “Partial Cycling Effects on the Martensitic Transformation of CuZnAl

SMA”, Scr. Metall. Mater., 26, 1795-1798 (1992) (Crys. Structure, Experimental, Phys.

Prop., 16)

[1992Bob] Bobic, I., Djuric, B., Jovanovich, M.T., Zec, S., “Improvement of Ductility of a Cast

Zn-25Al-3Cu Alloy”, Mater. Charact., 29, 277-283 (1992) (Equi. Diagram, Mechan.

Prop., 5)

[1992Cia] Ciach, R., Podosek, M., “Phase Transformations in Aluminum-Zinc alloys Solidifying at

Various Rates”, J. Therm. Anal., 38(9), 2077-2085 (1992) (Thermodyn., 13)

[1992Gui] Guilemany, J.M., Peregrin, F., “Comprehensive Calorimetric, Thermodynamic and

Metallographic Study of Copper-Aluminum-Manganese Shape Memory Alloys”, J. Mater.

Sci., 27(4), 863-868 (1992) (Crys. Structure, Equi. Diagram, Thermodyn., 12)

[1992Pel] Pelegrina, J.L., Ahlers, M., “The Martensitic Phases and Their Stability in Cu-Zn and

Cu-Zn-Al Alloys- III. The Transformation Between the High Temperature Phase and the 2H

Martensite”, Acta Metall. Mat.,40(12), 3221-3227 (1992) (Crys. Structure, Experimental,

Thermodyn., 10)

[1992Sau] Saule, F., Ahlers, M., Kropff, F., Rivero, E.B., “The Martensitic Phases and their Stability

in Copper-Zinc and Copper-Zinc-Aluminum Alloys - IV. The Influence of Lattice

Parameter Changes and Evaluation of Phase Stabilities”, Acta Metall. Mat., 40(12),

3229-3238 (1992) (Crys. Structure, 29)

[1992Tak] Takezawa, K., Sato, S., “Composition Dependence of Bainite Morphology in Cu-Zn-Al

Alloys”, Mater. Trans., JIM, 33(2), 102-109 (1992) (Crys. Structure, Equi. Diagram,

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[1993Ahl] Ahlers, M., “Martensite and Equilibrium Phases in Hume-Rothery Noble-Metal Alloys”,

J. Phys.: Condens. Matter, 5, 8129-8148 (1993) (Calculation, Review, Theory,

Thermodyn., 78)

192


MSIT®

Al–Cu–Zn

[1993Che] Chen, S.L., Chang, Y.A., “A Thermodynamic Analysis of the Al-Zn System and Phase

Diagram Calculation”, Calphad, 17(2), 113-124 (1993) (Equi. Diagram, Thermodyn.,

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J. Phase Equilib., 14(4), 432-438 (1993) (Equi. Diagram, Thermodyn., Calculations, #, 36)

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Plate in Cu-Base Alloys”, Metall. Mater. Trans. A, 25A, 2555-2563 (1994) (Calculation,

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Subramanian, P.R., Chakrabarti D.J., Laughlin, D.E., (Eds.), ASM International, Materials

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Cu-Zn-Al Aloys”, Metall. Mater. Trans. A, 25A, 2581-2599 (1994) (Crys. Structure,

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and Martensitic Transformation in Cu-Zn-Al and Cu-Al-Ni Industrial Alloys”, J. Phys. IV,

Colloque C2, 5, 159-163 (1995) (Experimental, Thermodyn., 13)

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V.A., “Influence of the Structure and Orientation of the Parent Phase on the Hysteresis of

Single-Crystal Shape Memory Alloys”, J. Phys. IV, Colloque C8, 5, 913-918 (1995) (Crys.

Structure, Phys. Prop., Thermodyn., 6)

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Prop., 17)

[1996Gar] Garcia, J., Pons, J., Cesari, E., “Effect of Precipitates on the Stabilization of Martensite in

Cu-Zn-Al Alloys”, Mater. Res. Bull., 31(6), 709-715 (1996) (Experimental, Phys. Prop.,

Mechan. Prop., 21)

193


MSIT®

Al–Cu–Zn

[1997Som] Somoza, A., Macchi, C., Romero, R., “Thermal Generation of Point Defects in Cu-Zn-Al

Alloys”, Mater. Sci. Forum, 255-257, 587-589 (1997) (Experimental, Thermodyn., 10)

[1997Zha] Zhang, M.R., Yang, D.Z., Tadaki, T., Hirotsu, Y, “Effects of Addition of Small Amounts of

Fourth Elements on Structure, Crystal Structure and Shape Recovery of Cu-Zn-Al Shape

Memory alloys”, Scr. Mater., 36(2), 247-252 (1997) (Crys. Structure, Experimental, 19)

[1998Buj] Bujoreanu, L.G., Craus, M.L., Stanciu, S., Sutiman D., “On the 2 to Phase

Transformation in a Cu-Zn-Al Based Shape Memory Alloy”, J. Alloys Compd., 278,

190-193 (1998) (Experimental, 12)

[1998Gal] Gall, K., Sehitoglu, H., Maier, H.J., Jacobus, K., “Stress-Induced Martensitic Phase

Transformation in Polycrystalline Cu-Zn-Al Shape Memory Alloys under Different Stress

States”, Metall. Mater. Trans. A, 29A (3), 765-773 (1998) (Mechan. Prop.,

Experimental, 58)

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J. Phase Equilib., 19 (1), 25-37 (1998) (Equi. Diagram, Thermodyn., Calculation, *, #, 72)

[1998Lop] Lopez-Hirata, V.M., Zhu, Y.H., Saucedo-Munoz, M.L., Hernandez, F., “Mechanical

Alloying of Zn-Rich Zn-Al-Cu Alloys”, Z. Metallkd., 89(3), 230-232 (1998) (Crys.

Structure, Mechan. Prop., 8)

[1998Man] Manosa L., Jurado M., Gonzalez-Comas A., Obrado E., Planes A., Zaretsky J., Stassis C.,

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Studied by Modulated Differential Scanning Calorimetry”, Metall. Mater. Trans. A,

29A(11), 2697-2705 (1998) (Experimental, Kinetics, Thermodyn., 36)

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at the Mesoscale Level and Interaction of Martensitic Transformation with Structural

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Structure, Theory, 163)

[1999Ago1] Agouram, S., Bensalah, M.O., Ghazali, A., “A Micromechanical Modelling of the

Hysteretic Behavior in Thermally Induced Martensitic Phase Transitions: Application to

Cu-Zn-Al Shape Memory Alloys”, Acta Mater., 47(1), 13-21 (1999) (Crys. Structure,

Experimental, Thermodyn. 27)

[1999Ago2] Agouram, S., Bensalah, M., Ghazali, A., “Thermomechanical Modelling of the One-Way

Memory Effect of a Cu-Zn-Al Shape Memory Alloys”, Compt. Rend. Acad. Sci. Paris, Ser.

II-B, 327, 573-579 (1999) (Experimental, Thermodyn., 13)

[1999Lon] Longauer, S., Makroczy, P., Janak, G., Longauerova, M., “Shape Memory in Cu-Zn-Al

Alloy with a Dual Phase Microstructure”, Met. Mater., 37(3), 120-126 (1999) translated

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Prop., 18)

[1999Rom] Romero, R., Somoza, A., “Point Defects Behavior in Cu-Based Shape Memory Alloys”,

Mater. Sci. Eng. A, A273-275, 572-576 (1999) (Crys. Structure, Experimental, 25)

[1999Zhu] Zhu, Y.H., Hernandez, R.M., Banos, L., “Phase Decomposition in Extruded Zn-Al Based

Alloy”, J. Mater. Sci., 34, 3653-3658 (1999) (Equi. Diagram, Experimental, 11)

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H.L., Seifert, H.-J., Oates, W.A., “Model for Composition Dependence”, Calphad, 24(1),

20-40 (2000) (Calculation, Equi. Diagram, Review, Thermodyn., 26)

[2000Dor] Dorantes-Rosales, H.J., Lopez-Hirata, V.M., Mendez-Velazquez, J.L., Saucedo-Munoz,

M.L., Hernandez-Silva, D., “Microstructure Characterization of Phase Transformations in

a Zn-22 wt%Al-2 wt%Cu alloy by XRD, SEM, TEM and FIM”, J. Alloys Compd., 313,


194


MSIT®

Al–Cu–Zn

[2000Kra] Kraft, T., “The Influence of Kinetic Effects on the Equilibrium Phase Diagram During

Solidification in the Aluminium-rich Corner of the Quaternary System Al-Cu-Mg-Zn”,

Z. Metallkd., 91(3), 221-226 (2000) (Calculation, Equi. Diagram, Kinetics, 19)

[2000Leg] Legendre, B., Feutelais, Y., San Juan, J.M., Hurtado, I., “Enthalpy of Formation of the

Ternary ’ Phase in the Al-Cu-Zn System”, J. Alloys Compd., 308, 216-220 (200)


[2000Pel] Pelegrina, J.L., Romero, R., “Calorimetry in Cu-Zn-Al Alloys Under Different Structural

and Microstructural Conditions”, Mater. Sci. Eng. A, A282, 16-22 (2000) (Crys. Structure,


[2000Sat] Satto, C., Jansen, J., Lexcellent, C., Schryvers, D., “Structure Refinement of L21 Cu-Zn-Al

Austenite, Using Dynamical Electron Diffraction Data”, Solid State Commun., 116,


[2000Yaw] Yawny, A., Lovey, F.C., Sade, M., “Pseudoelastic Fatigue of Cu-Zn-Al Single Crystals: the

Effect of Concominant Diffusional Processes”, Mater. Sci. Eng. A, A290, 108-121 (2000)

(Crys. Structure, Experimental, Thermodyn., 29)

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Formation and Martensitic Transformation in Cu-Zn-Al Alloys”, Phys. Met. Metallogr.,

89(3), 292-299 (2000) translated from Fiz. Met. Metalloved. 89(3), 85-92 (2000) (Phys.


[2001Bek] Beke, D.L., Daroczi, L., Lexcellent, C., Mertinger, V., “Effect of Hydrostatic Pressures on

Thermoelastic Martensitic Transformations”, J. Phys. IV (France), Pr8, 11, 119-124 (2001)

(Crys. Structure, Phys. Prop., 14)

[2001Che] Chen, S.-L., Daniel, S., Zhang, F., Chang, Y.A., Oates, W.A., Schmid-Fetzer, R., “On the

Calculation of Multicomponent Stable Phase Diagrams”, J. Phase Equilib., 22, 373-378

(2001) (Calculation, Equi. Diagram, #, 26)




[2001Zhu1] Zhu, Y.H., Lee, W.B., Yeung, C.F., Yue, T.M., “EBSD of Zn-Rich Phases in Zn-Al-Based

Alloys” Mater. Charact., 46(1), 19-23 (2001) (Crys. Structure, Experimental, 9)

[2001Zhu2] Zhu, Y.H., Yeung, C.F., Lee, W.B., “Phase Decomposition of Cast Alloy ZnAl11Cu3”,


[2002Che] Chen, S.-L., Daniel, S., Zhang, F., Chang, Y.A., Yan, X.-Y., Xie, F.-Y., Schmid-Fetzer, R.,

Oates, W.A., “The PANDAT Software Package and its Applications”, Calphad, 26(2),





[2002Mie] Miettinen, J., “Thermodynamic Description of the Cu-Al-Zn and Cu-Sn-Zn Systems in the

Copper-Rich Corner”, Calphad, 26(1), 119-139 (2002) (Calculation, Equi. Diagram,

Thermodyn., #, 20)




[2003Leb] Lebrun, N., “Cu-Zn (Copper-Zinc)”, MSIT Binary Evaluation Program, in MSIT



[2003Per] Perrot, P., “Al-Zn (Aluminium-Zinc)”, MSIT Binary Evaluation Program, in MSIT



195


MSIT®

Al–Cu–Zn


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Al)

660.452

cF4

Fm3m

Cu

a = 404.96 pure Al at 25°C, [Mas2]

dissolves up to 2.48 at.% Cu at 548.2°C

[2003Gro]

( Cu)

1084.87

cF4

Fm3m

Cu

a = 361.48 pure Cu at 25°C, [V-C]

dissolves up to 19.7 at.% Al at 559°C

[2003Gro]; disolves up to 35.84 at.% Zn

at 300°C [2003Leb]

( Zn)

419

hP2

P63/mmc

Mg

a = 266.46

c = 494.61

pure Zn at 22°C, [V-C]

dissolves up to 1.5 at.% Cu at 424°C

[2003Leb]

, CuAl2 591

tI12

I4/mcm

CuAl2

a = 605.0

c = 487.0

from 31.9 to 33.0 at.% Cu

at 33.3 at.% Cu, [1985Mur]

1, CuAl(h)

624-560

o*32 a = 408.7

b = 1200

c = 863.5

49.8 to 52.4 at.% Cu

[V-C2, Mas2, 1985Mur]


2, CuAl(r)

561

mC20

C 2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

[1985Mur],

from 49.8 to 52.3 at.% Cu

1, Cu47.8Al35.5(h)

590-530

oF88 - 4.7

Fmm2

Cu47.8Al35.5

a = 812

b = 1419.85

c = 999.28

55.2 to 59.8 at.% Cu, [Mas2, 1994Mur]


2, Cu11.5Al9(r)

< 570

oI24 - 3.5

Imm2

Cu11.5Al9

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu, [Mas2, 1985Mur]


1, Cu100-xAlx958-848

cubic ?

-

- 37.9 x 40.6 [1985Mur]

2, Cu1+xAl

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

0.22 x 0.57

[1985Mur]

1, Cu100-xAlx hR*

-

a = 869.0

= 89.78°

38.1 x 40.7 [1985Mur]

0, Cu100-xAlx1037-800

cI52

I43m

Cu5Zn8-

- 31 x 40.2 [1985Mur]

, Cu5(CuxZn2-2xAlx)7

, Cu9Al4 < 890

, Cu5Zn8

< 835

cP52

P43m

Cu9Al4

cI52

I43m

Cu5Zn8

a = 870.68

a = 886.9

Zn free 69.23 at.% Cu, [V-C2]

Al free [V-C2]

Cu9Al4 is ordered with Cu and Al on

2nd sites,

cP52-Cu9Al4 type

196


MSIT®

Al–Cu–Zn


2, Cu100-xAlx363°C

TiAl3-type

long period

superlattice

a = 366.6

c = 367.5

22 x 23.5

at 77.9 at.% Cu, [1985Mur]

', CuZn(r)

468

cP2

Pm3m

CsCl

a = 295.9 at 49.5 at % Zn [V-C2],

from 44.8 to 50.0 at.% Zn

, CuZn3

700-560

hP3

P6

CuZn3

a = 427.5

c = 259.0

[V-C2],

from 72.4 to 76.0 at.% Zn [1985Mur]

, CuZn4

598

hP2

P63/mmc

Mg

a = 274.18

c = 429.39

[V-C2],

from 78 to 88.0 at.% Zn

, (Cu,Zn,Al)

, CuZn(h)

903-454

, CuAl

1049-559

cI2

Im3m

W

a = 299.67

a = 285.64

a = 294.6

[V-C2],

from 36.1 to 55.8 at.% Zn

at 672°C in two-phase field, [1985Mur]

at 75.7 at.% Cu, 580°C [1985Mur] solid

solubility range: 70.6 to 82.0 at.%Cu

* , Cu5Zn2Al3< 740

* ’, Cu3Zn

cP2

CsCl

hR9

a = 290.4

a = 293.2

a = 867.6

= 27.41°

Cu40Zn7Al53 [1942Koe]

at Cu46Zn20Al34 [1942Koe]

rhombohedral superstructure of 5 CsCl

lattice [1942Koe], [1975Mur, 2000Dor]


Al Cu Zn

L + + 625 P2 L 29.7

26.3

33.5

27.9

26.9

45.4

46.7

44.1

43.4

28.3

19.8

28.0

L + 2 1 + 620 U6 L

2

62.6

22.0

25.5

24.0

35.2

53.0

51.4

51.0

2.2

25.0

23.1

25.0

L + 1 + 580 U8 L 65.9

29.4

47.0

30.0

31.6

48.1

32.5

46.0

2.5

22.5

20.5

24.0

1 + + 480 E2 19.1

15.2

26.2

17.2

43.2

44.4

48.0

40.2

37.7

40.4

25.8

42.6

L + (Al) + 422 U9 L

(Al)

44.5

66.8

54.4

52.1

11.3

32.0

1.4

39.0

44.2

1.2

44.2

8.9

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

197


MSIT®

Al–Cu–Zn

Table 3: Saturation Concentrations of Al and Cu in (Zn) at Different Temperatures

L+ (Al) + 396 U10 L

(Al)

28.2

50.4

42.0

11.2

9.4

39.2

1.5

22.0

62.4

10.4

56.5

66.8

L (Al) + + (Zn) 377 E3 L

(Al)

(Zn)

15.4

37.0

3.3

3.1

3.7

1.4

15.3

2.9

80.9

61.6

81.4

94.0

+ (Al)" (Al)' + 288 U11

(Al)"

(Al)'

59.2

50.3

80.5

2.8

35.7

1.8

1.4

16.6

5.1

47.9

18.1

80.6

(Al)" + (Al)' + (Zn) 278 U12 (Al)"

(Al)'

(Zn)

49.1

2.4

83.4

2.4

1.5

18.7

0.8

3.0

49.4

78.9

15.8

94.6

(Al)' + + (Zn) 268 U13 (Al)'

(Zn)

43.3

0.7

52.7

1.9

0.8

17.5

39.2

1.7

55.9

81.8

8.1

96.4

Temperature [°C] Al (at.%) Al (mass%) Cu (at.%) Cu (mass%)

375

350

300

275

250

3.0

2.7

2.2

1.9

1.5 (0.9)

1.25

1.1

0.9

0.8

0.6 (0.4)

2.8

2.5

2.1

1.7

1.2 (0.9)

2.8

2.5

2.1

1.7

1.2 (0.9)


Al Cu Zn

Cu,at.%

Zn, at.%

220

240

260

280

300

320

220

240

260

280

300

�´

�

Al

99.01.0

Al

Cu

90.010.0

Al

Zn

Fig. 1: Al-Cu-Zn.

Solvus of the (Al)

phase and three phase

equilibrium (Al)+ +

at different

temperatures [°C]

198


MSIT®

Al–Cu–Zn

Fig

. 2a:

Al-

Cu

-Zn

. R

eact

ion s

chem

e, p

art

1

Cu

-Zn

Al-

Cu

A-B

-C

l +

(αC

u)

β9

03

p3

l +

β

γ 0

10

37

p1

Lτ

+ ε 2

74

0e 4

Al-

Cu

-Zn

ε 1+

γ 0

L

+ γ1

U2

Al-

Zn

l +

γ1

δ6

65

p7

l+

βγ 1

83

5p6

l +

ε2

ε 1

62

4p9

l +

γ1

δ 1

68

6p7

γ 0β

+ γ1

78

0e 3

ε 1

ε 2 +

l

84

8e 2

ε 1 +

γ1

ε 2

85

0p5

γ 0 +

ε1

γ 1

87

3p4

l +

γ0

ε 1

95

8p2

l (

αCu)

+ β

10

32

e 1

ε 1L

+ ε 2

+ γ1

E1

L +

γ0

β +

γ 1U3

L +

ε2

+γ 1

δ

P1

L +

δ +

τε

62

5P2

ε 2 +

δγ 1

+ τ

680

U5L +

ε2

δ +

τU4

L +

ε2

η 1 +

τ6

20

U6

L+

β +

γ0

L +

ε 2 +

γ1

L+

γ 1+

γ 0L

+ ε1

+ γ 1

ε 2+

γ 1+

δL

+ ε 2

+ δ

L+

δ +

τ?

δ +

γ 1 +

τε 2+

γ 1+

τ

δ +

τ +

ε L+

ε +

τ

ε 2+

η 1+

τ

L+

η 1 +

τ

199


MSIT®

Al–Cu–Zn

Fig

. 2b

:

Al-

Cu

-Zn

. R

eact

ion s

chem

e, p

art

2

Cu

-Zn

Al-

Cu

A-B

-C

l +

η1

θ5

91

p10

Al-

Cu

-Zn

ε 2 +

τγ 1

+ η2

U7

Al-

Zn

l +

ε (

ηZn)

42

4p13

δε

+ γ 1

54

8e 8

l (

αAl)

+ θ

548.2

e 7

β (

αCu)

+ γ1

55

9e 6

ε 2ζ 1

+ δ

56

0e 5

ε 2 +

η1

ζ 1

59

0p11

L +

θ (

αAl)

+ τ

42

2U9

L +

η1

θ +

τ5

80

U8

δε

+ γ1 +

τ4

80

E2

(αA

l)´´

+ τ

(αA

l)´

+ ε

28

8U11

L (

αAl)

+ (

ηZn

) +

ε3

77

E3

L +

τ (

αAl)

+ ε

39

6U10

(αA

l)´´

+ε

(αA

l)´+

(ηZ

n)

27

8U12

(αA

l)´´

+ ε

(ηZ

n)

+ τ

26

8U13

(αA

l)´´

(αA

l)´+

(ηZ

n)

27

7e 10

l (

αAl)

+ (

ηZn)

38

1e 9

δ+γ 1

+τ

ε 2+γ1+τ

ε 2+η

1+τ

δ+τ+

ε

L+η

1+τ

ε +

γ 1+

τ

η 1+θ

+τL

+θ+τ

(αC

u)+

β+γ 1

L+

(αA

l)+

τ(α

Al)

+θ+τ

L+

(αA

l)+

ε

(αA

l)+

ε+τ

(αA

l)´´

+(α

Al)

´+τ

(αA

l)´+

ε+τ

(αA

l)´´

+(α

Al)

´+ε

(αA

l)´+

ε+(η

Zn)

(αA

l)´+

(ηZ

n)+

τ(η

Zn

)+ε+

τ

(αA

l)´´

+(η

Zn

)+ε

ca.

351.5

L+

ε+τ

τ+γ 1

+η1

?

l +

δε

57

4p12

200


MSIT®

Al–Cu–Zn

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αCu)

(αCu)+ββ

β+γ

γ

ε2 τL+τ L

δL+δ

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

e1

p1

p2

e2

p9

p10

e7

e9

p13p12p8p6p3

1050(αCu)

β

(αAl)

1000

γ0

950

900

850

ε1

U2P1

U3

γ

800

750

700

650600

550

550

600

650

500

U10

U9

P2

δ

U4

θ

ε

ε2

η1

U8

U6

τ

E1

400

450

E3

(ηZn)

e4

Fig. 4: Al-Cu-Zn.


700°C

Fig. 3: Al-Cu-Zn.

Liquidus surface

201


MSIT®

Al–Cu–Zn

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%(αAl)+L(αAl)

L+τ

γ

τ

ε2δ1

(αCu)

(αCu)+β

β+γδ

β

L

L+δ

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

L+δδ

L+εε

γ

τ+γ

L

(αAl)

(αAl)+L

L+τ

β(αCu)

(αCu)+ββ+γ

δ1

ε2

η1

τ

Fig. 6: Al-Cu-Zn.


600°C

Fig. 5: Al-Cu-Zn.


650°C

202


MSIT®

Al–Cu–Zn

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%(αAl)

(αAl)+L

L

ε+L

εδ+ε

δγ

β+γ

β

(αCu)

(αCu)+β

θ+Lθ

η2

L+τ

L+τ+ετ+ε

τ

τ'(ζ1,ζ2)

δ1

τ+γ

γ+ε

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αAl)

θ+(α

Al)

L+(αAl)

L+θ+(

αAl)

L+θ

θ+τ'+L

L+τ'

L+τ+ετ

ζ2+τ

τ'

η2

ζ2

δ1

τ+γ

L

L+ε

εγ+εγ

γ+β

β(αCu)

β+(αCu)

τ+ε

δ

(αCu)+γ

θ

Fig. 8: Al-Cu-Zn.


500°C

Fig. 7: Al-Cu-Zn.


550°C

203


MSIT®

Al–Cu–Zn

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αAl)+θ(αAl)

θ+τ´+(αAl)

L+ε+τ

L+τ

L+ε

(αAl)+τ'

L+(αAl)+τ'

τ+ε

ε

(ηZn)(αCu)

(αCu)+β

β

(αCu)+γ

δ1+γ+τ

τ+γ

τ

τ'

θ

η2

ζ2

δ1

γ

γ+εγ+β

L

L+(αAl)

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αCu)

α2

δ1

ζ2

η2

θ

(αAl)

(αAl)'+(αAl)´´

(ηZn)+(αAl)

(ηZn)ε

γ

γ+β

β

τ

τ'

τ'+θ+(αAl)

τ'+(αAl)

ε+τ'+(αAl)

ε+(α

Al)

(ηZn)+εε+γ

ε+τ+γ

ε+τγ+δ1+τ

η2+τor τ´

or τ'

θ+(αAl)

(αCu)+γ

Fig. 10: Al-Cu-Zn.


350°C

Fig. 9: Al-Cu-Zn.


400°C

204


MSIT®

Al–Cu–Zn

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αCu)

?

τ

θ

(αA

l)'+θ

(αA

l)'+θ

+τ

(αAl)'+τ

(αAl)'+(αAl)´´+τ

(αAl)"+τ

(αAl)"+τ+ε

(αA

l)"+ε+(ηZn)

(ηZn)εγ (αAl)"+(ηZn)

(αAl)"

β

(αAl)'+(αAl)´´

(αAl)´

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αCu)

τ'

(αAl)+θ

(αAl)+τ'+θ

(αA

l)+τ'

(αAl)+(ηZn)+τ'

(αAl)+(ηZn)

(αAl)

(ηZn)ε

τ'+(ηZn)

ε+(ηZn)+τ'γ

β

?

θ

Fig. 12: Al-Cu-Zn.


240°C

Fig. 11: Al-Cu-Zn.


300°C

205


MSIT®

Al–Cu–Zn

20

40

60

80

20 40 60 80

20

40

60

80

Cu Zn


Axes: at.%

(αCu) ? γ ε+γε (ηZn)

(αAl)+(ηZn)

(αAl)

θ

η2

ζ2 η2+τ'

τ'

τ

τ´+ε+(ηZn)

τ+γ+ε

(αAl)+τ´+(ηZn)

η2 +τ´+ε

τ´+θ

+(αA

l)

τ´+(

αAl)

Fig. 13: Al-Cu-Zn.


200°C

206


MSIT®

Al–Cu–Zr

Aluminium – Copper – Zirconium

Ludmila Tretyachenko

Literature Data


evaluation made by [1992Tre]. Since then the number of publications on Al-Co-Zr has almost doubled. The

isothermal sections at 800°C across the whole range of compositions and at 500°C for the Al rich part of

the diagram are mainly based on data given by [1970Mar]. The isothermal section at 400°C for Al rich part

was given by [1967Zar]. A tentative reaction scheme for the Cu rich part of ternary system close to the

Al-Cu system was proposed from data of [1964Pan] and [1969Hor]. Eight ternary compounds were reported

to exist at 800°C, one more compound was detected at 500°C by [1970Mar] but this compound was not

observed at 400°C by [1967Zar]. The crystal structures were established for only four of the ternary

compounds. So far most of the data have been considered in the reviews of [1979Dri, 1986Riv, 1990Kum].

[1990Mey1] further studied alloys in the vicinity of the Heusler type phase ZrCu2Al. Samples were melted

of pure elements (Al 99.99%, Cu 99.99% and Zr 99.9%) in argon, annealed at 800°C for 72 h in sealed

quartz ampoules under argon and quenched in ice water. The samples were crushed and powders were

annealed at 600°C for 48 h in quartz ampoules under argon quenched and studied by Debye - Scherrer

method. A new ternary compound Zr6Cu16Al7 was found and the crystal structure of this compound and

those of Zr15Cu71Al14 and Cu4ZrAl3 earlier reported by [1970Mar] were established. The compounds

ZrCu2Al and Zr6Cu16Al7 were not obtained as a single phase; but the alloys of the corresponding

compositions contained some amounts of other phases [1989Mey, 1990Mey1, 1990Mey2]. It is well

possible that those samples did not reach the equilibrium states because of far shorter heat treatments than

those applied by [1970Mar]. Interaction of ZrCu2Al with hydrogen has been studied [1989Mey, 1990Mey1,

1990Mey2].

Phase equilibria in the Al rich part of the Al-Cu-Zr system have been studied by [1997Soa, 1998Soa]. Six

alloys containing up to 14 at.% Zr and 25 at.% Cu were melted in an arc furnace by [1997Soa] and three Al

rich Al-Cu alloys with 0.4 and 1.1 at.% Zr were prepared in a resistance furnace by [1998Soa]. Both used

high purity elements and argon atmosphere. To determine by differential thermal analysis the temperatures

of the phase transformations the alloys were annealed at temperatures chosen after the results of DTA and

quenched in salty ice water. The alloys were analyzed by scanning electron microscopy (SEM) and energy

dispersive spectroscopy (EDS). Two earlier identified compounds were confirmed to exist. However

instead of the compound with the composition of 64Al-24Cu-12Zr (at.%) reported by [1970Mar], another

phase was found and its crystal structure established. The stability of the L12 (Cu3Au type) phase in

mechanically alloyed Al6-xCuxZr2 over the range 0 x 1 has been studied by [1991Des1, 1991Des2]. The

alloy powders were prepared ball-milling elemental powders of 99.99%, Al 99.999% Cu and 99.99% Zr

with significant amount of ZrH2 in the initial zirconium powder. The powders were studied using X-ray

diffraction (XRD) and differential scanning calorimetry (DSC).

[2002Moo] used elemental powders of Al 99.5%, Cu 99.5% and Zr 99.9% as starting materials to prepared

by planetary ball milling (PBM) powders of (Al+12.5 at.% Cu)3Zr with a nanocrystalline microstructure.

Subsequently the powder was sintered by spark plasma sintering (SPS) at 500, 600, 700 and 800°C with

subsequent holding times of 0, 180 and 300 seconds. XRD, SEM, TEM results were recorded, particle size

and density measured and optical microscopy was used to investigate and document the samples.

Magnetic susceptibility and lattice parameters of ZrCu1.2Al0.8 alloy have been measured by [1992Sle] in

the range between 5 K and room temperature. The alloy was arc melted from spectrally pure components

and annealed at 727°C for 7 days. The susceptibility was investigated by Faraday method at temperatures

between 80 and 600 K and a magnetic field of 6 kOe.

Amorphous alloys of the Al-Cu-Zr system have been studied by [1991Ino] using X-ray absorption

spectroscopy at room temperature and elevated temperatures, below and above the glass transition

temperature. [1997Sch] examined structural changes at the glass transition and in the undercooled liquid

207


MSIT®

Al–Cu–Zr

region of the metallic glass Zr65Cu27.5Al7.5, prepared by ultra rapid quenching in argon atmosphere.

[1997Kan] measured the specific heat of Zr65Cu7.5Al27.5 metallic glass - in the temperature range 77-800 K

by calorimeter at a heating rate of 5 K·min-1. The crystallization process was examined using differential

scanning calorimetry. [1998Tur] measured the enthalpies of formation of amorphous Al-Cu-Zr alloys in the

Zr0.65Cu0.35-Zr0.65Al0.35 section using the alloys prepared by melt spinning technique of iodine zirconium

(99.98 mass%), electrolytic copper (99.99 mass%) and high purity aluminium (99.995 mass%). The

enthalpies of formation of the amorphous alloys were determined by means of the solution calorimetry in a

high temperature isoperibolic Calvet type solution calorimeter.

Thermodynamic properties of liquid Al-Cu-Zr alloys were measured by high temperature calorimetry at

1177 to 1212 and at 1737 to 1807°C [1998Wit]. The samples were prepared from Cu (99.98%), Al

(>99.99%) and Zr (99.8%). The measurements were performed under pure argon at atmospheric pressure

for the alloys located in 10 vertical sections with various xCu/xZr, xCu/xAl and xAl/xZr ratios. [2001Aki]

developed a phenomenological model of ternary mixtures based on the Flory approximation and derived

expressions were solved numerically for liquid Al-Cu-Zr alloys.

A study of behavior of the superplastic Al-4.1Cu-0.5Zr (mass%) alloy during creep at a constant flow stress

was made by [1990Poy] using an investigation of structure at various stages of creep by means of optical

microscopy.

[1974Bus] studied the ageing of Al-Cu-Zr alloys with Al contents up to 7 mass% Al and 0.525 mass% Zr.

The alloys have been prepared by induction melting, annealed at 950°C for 40 h, hot forged, heated at 950°C

for 15 min in vacuum and quenched. The aging has been carried out at 800°C and 10-2 Torr.

[1984Kai] studied an influence of grain boundaries on superplastic behavior of the Al-2Cu-0.16Zr (at.%)

using an electron microscopy analysis.

Heterogeneous precipitation behavior of partially coherent intermediate phases on ZrAl3 dispersoids has

been studied by [1991Kan] in Al-4Cu-0.18Zr (mass%) alloys. The melted alloys have been homogenized

at 470°C for 86.4 ks, hot and cold rolled and subjected to the following heat treatment: solution treated at

470°C for 3.6 ks, quenched in bath held at 200°C and aged for times up to 60 ks. Subsequently they were

examined by TEM.

Binary Systems

The Al-Cu phase diagram assessed by [2003Gro] is accepted. The Al-Zr system is taken from [1993Oka].

The accepted Cu-Zr phase diagram is based on the assessment [2003Sem]. However, the eutectoid

decomposition of Zr3Cu8, which was established at 612°C by [1986Kne] and supposed to take place at a

temperature below 600°C according to [1998Bra], is taken into account.

Solid Phases

Three phases of nine reported by [1970Mar] were known earlier. These are the Heusler phase ZrCu2Al ( 4),

the Laves phase ZrCuxAl2-x ( 5) and Zr2CuAl5 ( 8). The crystal structure of one more phase, 7, was

established by [1970Mar]. The crystal structure of remaining five phases reported by [1970Mar] was not

determined. The existence of the Heusler phase ZrCu2Al also was confirmed by [1989Mey, 1990Mey1,

1990Mey2], but a single-phase region of this phase was not found. The existence of the 6 phase (ZrCu4Al3)

was confirmed too and its crystal structure was proposed to be bcc. Moreover, a new ternary phase

Zr6Cu16Al7 designated in the present assessment as 10 not identified before was found, and its crystal

structure was described. The Zr6Cu16Al7 was predominant in the 20.7Zr-55.2Cu-24.1Al alloy annealed at

800°C for 98 h and was present in ZrCu2Al alloy annealed at 600°C for 48 h as a minor constituent. It should

be noted that a hydride compound of similar structure was observed to form at an interaction of ZrCu2Al

with hydrogen [1989Mey, 1990Mey1, 1990Mey2].

In the Al rich part of the ternary system [1997Soa, 1998Soa] observed the 7 and 8 phases detected earlier

but the 9 phase, which was reported to exist at 500°C by [1970Mar], was never observed by [1997Soa,

1998Soa]. Instead of 9 phase shown by [1970Mar] at the composition of 64Al-24Cu-12Zr (at.%) another

phase was found. The composition of this phase was determined to be 67.2Al-15.7Cu-17.1Zr [1998Soa].

Its crystal structure was found to be bcc. In the present assessment the preference is given to this new phase,

208


MSIT®

Al–Cu–Zr

which is designated as 9', because its composition was established by [1997Soa, 1998Soa] more exactly.

It was not observed in the alloys annealed at 800°C but was present in the alloys annealed at 700°C and

below.

A compound Zr3Cu2Al with cubic Ti2Ni type structure reported by [1964Rie] was not taken into account

in the present assessment because it is most likely stabilized by impurity elements.

The homogeneity ranges were found for the Laves phase 5 with a linear variation of lattice parameters and

for the 7 phase [1970Mar]. [1991Des2] reported that alloys on the base of Zr2CuAl5 were single phase for

the compositions Zr2CuAl5-x at 0.7 x 1 in the powders produced by mechanical alloying and heated to

750°C. The content of 9 at.% Cu in the 8 phase detected by [1997Soa] is within the composition range

indicated by [1991Des2].

An appreciable solubility of the third component with a linear variation of the lattice parameters up to 10.5

at.% Cu has been established for Zr4Al3 [1970Mar]. The Cu solubility in ZrAl3 was determined using SEM/

EDS technique to be 0.5 at.% at 800°C [1997Soa, 1998Soa] but [1991Des2] observed single ZrAl3 based

phase up to 2.5 at.% Cu. According to the results of SEM/EDS the presence of zirconium was not found in

the phase (CuAl2) [1998Soa]. The maximum solubility about 0.1 mass% Zr was found in the phase

(Cu3Al) at temperatures below 950°C in the section at 10 mass% Al using microscopic examination

[1964Pan].

A metastable phase of the Cu3Au type (L12) was obtained in mechanically alloyed Zr2CuxAl6-x (0 x 1)

powders for all concentrations x [1991Des2].

Data on the crystal structure of the solid phases relevant to the considered ranges of temperatures and

compositions are listed in Table 1.


The invariant reactions in the Al rich part of the ternary system were established by [1997Soa, 1998Soa]

from the results of DTA and microstructure analysis using SEM/EDS. They are: the U-type reaction

L+ 8 7+ZrAl3 at 820 ± 10°C; the P-type peritectic reaction of 9' formation L+ZrAl3+ 7 9' at

740 ± 10°C; the U-type reaction L+ZrAl3 (Al)+ 9'. The temperature of last reaction was not

experimentally determined but it can be suggested to be lower than 600°C, because the three alloys with the

Cu:Al ratio ~5 and 3.1, 6.0, 9.3 at.% Zr, which are located in a region of supposed invariant equilibrium,

were found to consist of ZrAl3+L. From the data of [1997Soa, 1998Soa] two more invariant reactions can

be supposed: L+ 7 9'+ at a possible temperature of 560 ± 10°C and L+ 9' (Al)+ at a temperature very

close to the temperature of the eutectic reaction L (Al)+ in the binary Al-Cu system (548.2°C). A tentative

reaction scheme for Al rich part of the phase diagram is shown in Fig. 1.

The results of the microscopic investigation of alloys in the sections at 5 and 10 mass% Al with 0 to

5 mass% Zr [1964Pan] suggest the possibility of an invariant equilibrium of eutectic type E, L +(Cu)+ 1

(with the ternary eutectic E, localized close to the binary Al-Cu eutectic e1), or type D, L +(Cu), 1 at the

temperature T1 (900°C < T1 < 965°C) (alloys were homogenized at 900°C, initial melting was observed at

965°C). Data by [1969Hor] and [1964Pan] suggest the occurrence of a U type transition reaction,

+ 1 (Cu)+ 1 at 568°C. Zr was found to increase the temperature of the eutectoid transformation

(Cu)+ 1, when compared with the binary Al-Cu alloys [1969Hor]. A tentative reaction scheme for this

part of the ternary system is proposed in Fig. 2.

The presence of four phases ( 4+ 5+ 6+ 10) in the 26.5Al-49Cu-24.5Zr alloy annealed at 600°C and

three-phase alloys ( 4+ 10+ 5, 4+ 10+ 6 and 4+ 5+ 6) in an area around the above alloy allows to

postulate the existence of appropriate four-phase invariant equilibrium. However, neither temperature nor

the type of this equilibrium are known.

Solidus Surface

Figure 3 shows a tentative projection of the solidus surface in the Al rich part of the ternary phase diagram

composed mainly from data by [1997Soa] and [1998Soa]. The primary feature of the phase equilibria in this

region is the existence of the phase fields ZrAl3+ + 9' and (Al)+ + 9' and the phase fields of ZrAl3+(Al)+

and ZrAl3+ + 9 by [1970Mar] and ZrAl3+(Al)+ and ZrAl3+ + 8 by [1967Zar]. The present version was

209


MSIT®

Al–Cu–Zr

preferred because [1998Soa] has given results of a microscopic investigation and a phase composition of

alloys in the (Al)+ + 9', which give evidence of the existence of 9' in alloys of this concentration. On the

contrary, [1967Zar] and [1970Mar] did not give any firm data on the alloys studied. However, it should be

noticed that the alloys studied by [1998Soa] were not in equilibrium and contained also some amount of

ZrAl3, which was not fully consumed in the transformation reaction L+ZrAl3 9'+(Al).

Isothermal Sections

The phase equilibria in the Al rich part region at 860°C are shown in Fig. 4 according to the data by

[1997Soa]. The composition of the 8 phase, with 9 at.% Zr instead of 12.5 accepted in literature (Table 1),

must be regarded as tentative.

Figure 5 shows the isothermal section at 800°C taking into account the appropriate section by [1970Mar]

adjusted to the binary phase diagrams accepted in this assessment, the data presented by [1997Soa] and

[1998Soa] for the Al rich corner and the existence of the 10 (Zr6Cu16Al7) phase reported by [1990Mey1].

The phase equilibria in a vicinity of 10 and 4 phases do require further additional studies. [1990Mey1]

reported that in the 24.1Al-55.2Cu-20.7Zr alloy, which was annealed at 800°C for 98 h, more than 98 % of

10 coexist with a minor amount of ZrCu2Al.

Figure 6 shows the L+ 7+ 9' phase field in the isothermal section at 700°C according to the data by

[1997Soa]. The L+ZrAl3+ 9' region shown is tentative.

The partial isothermal section at 600°C is presented in Fig. 7 and takes into account the data reported by

[1997Soa, 1998Soa], [1990Mey1] as well as [1970Mar] and [1964Pan]. [1990Mey1] reported the existence

of three-phase alloys 4+ 10+ 6, 4+ 6+ 5 and 4+ 10+ 5 in a vicinity of the 26.5Al-49Cu-24.5Zr

composition, which was found to be four-phase when annealed at 600°C for 48 h. This gives clear evidences

that the studied alloys were not reduced to equilibrium state. Moreover, a simultaneous existence of the

phase fields 4+ 10+ 5, 4+ 10+ 6 and 4+ 6+ 5 at 600°C is possible only if these fields are parts of the

plane of the invariant equilibrium 4+ 5+ 6+ 10 or if the 5 in the 4+ 5+ 10 field contains more than 40

at.% Cu, that never has been observed.

The partial isothermal section at 500°C (Fig. 8) is constructed from the data by [1970Mar], [1997Soa],

[1998Soa] and [1990Mey1]. The data by [1997Soa] agree with the phase equilibria constructed by

[1970Mar], except for the phase equilibria in the ZrAl3-Al- - 9' region. Here the findings of [1970Mar] and

[1998Soa] are contradicting.

The isothermal section at 400°C presented by [1967Zar] agrees with [1970Mar] as to the existence of the

(Al)+ +ZrAl3 equilibrium but [1967Zar] did not find the 9 phase reported by [1970Mar] nor did he find

the 9' phase reported by [1997Soa, 1998Soa].

The partial isothermal sections of the Cu corner of the ternary Al-Cu-Zr diagram (up to 10 mass% Al and 5

mass% Zr) at 850°C and 500°C proposed by [1964Pan] show satisfactory agreement with the results of

[1970Mar].


The vertical sections at 5 and 10 mass% Al up to 5 mass% Zr were constructed by [1964Pan]. The isopleth

at 5 mass% Al intersects the two-phase region (Cu)+intermetallic compound (probably 1). After the

primary crystallization of the (Cu) phase the eutectic (Cu)+ 1 solidifies at 965°C. The isopleth at constant

10 mass% Al demonstrates an increasing +(Cu)+ 1 region with a temperature decrease and eutectoid

decomposition of the phase. [1964Pan] could not determine a change of eutectoid temperature by

additions of Zr. However the results of [1969Hor] indicate a slight temperature increase and are preferred.

Figure 9 shows the partial vertical section at 10 mass% Al up to 5 mass% Zr (3.1 at.% Zr) constructed from

results of [1964Pan] but corrected according to the phase rule and assuming the existence of the univariant

equilibrium L+ 1 , which is concluded from the microstructures of the alloys given in [1964Pan].

210


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Al–Cu–Zr

Thermodynamics

The partial and integral enthalpies of mixing of ternary Al-Cu-Zr alloys have been measured by [1998Wit].

The experimental data points of the enthalpy of mixing were treated by means of a least squares procedure

and the developed relationships were used to calculate the isolines of the integral enthalpy of mixing. The

minimal value was estimated to be -51.7 kJ·mol-1 close to the binary Al53Zr47 composition. The estimation

of the excess entropy of mixing of liquid ternary alloys on the basis of composition dependencies of the

measured enthalpies of mixing and the melting and boiling temperatures of pure components was applied

to the Al-Cu-Zr system. The liquid alloys near the binary composition Al53Zr47 were found to have large

negative values of the enthalpy of mixing and a large negative excess entropy. Therefore, the liquid alloys

in the vicinity of this composition were recognized to have the strongest chemical order.

[2001Aki] have derived analytical expressions for the free energy of mixing, enthalpy of mixing,

concentration fluctuations in the long wavelength limit and for the activity using the Flory approximation.

The derived expressions were used to obtain numerical results for the concentration dependence of these

thermodynamic values for the ternary liquid Cu0.33Zr0.67-Al alloys at 1772°C. The obtained results have

indicated that the chemical short range order exists for these liquid Al-Cu-Zr alloys, in quite good agreement

with available experimental data.

Enthalpies of formation of amorphous alloys (Zr0.65Cu0.35)1-x(Zr0.65Al0.35)x in the concentration range 0

x 0.8 from pure crystalline elements at 298 K measured by [1998Tur] can be represented by:

( fH298((Zr0.65Cu0.35)1-x(Zr0.65Al0.35)xam) = - 2964 - 31.915x (kJ·mol-1).

The absolute values of ( fH298((Zr0.65Cu0.35)1-x(Zr0.65Al0.35)xam) indicates strong chemical interaction

between Zr, Cu and Al atoms, which is rising with the increase of concentration of Al atom.


The influence of the state of grain boundaries on superplastic flow has been established experimentally by

[1984Kai] for the Al-2Cu-0.16Zr (at.%) alloys. Different factors, which can have an influence on

superplastic flow have been studied, including the presence of disperse precipitates in the grain boundaries.

It was shown that Al solid solution supersaturated with Zr has been formed through quick crystallization of

the alloy. Precipitation of dispersed ZrAl3 particles occurred during annealing at 380°C. The anneal at

300°C for 48 h after preliminary cold deformation of 3 % resulted in a formation of CuAl2 particles, which

disappeared at superplastic deformation.

Relationships of pore formation and failure of a superplastic Al-4.1Cu-0.5Zr (mass%) alloy have been

studied by [1990Poy] during creep at a constant flow stress. The most pronounced superplastic properties

were shown at 500°C. The optimum conditions of superplasticity development were obtained to be = 5.0

MPa, = 1.5·10-4s-1 in the studied interval of the stress = 3.0 to 6.0 MPa. In this case the maximum

elongation of the samples before the failure was 830 %.

Magnetic susceptibility measurements carried out for the Laves phase ZrCu1.2Al0.8 showed a Curie-Weiss

behavior of this alloy with the effective moment of 1.5 B.

A bulk intermetallic L12 compound was produced by means of the spark plasma sintering (SPS)

nanocrystalline powders of (Al+12.5 at.% Cu)3Zr and 65.6Al-9.4Cu-25Zr (at.%), which were prepared be

planetary ball milling. The highest density, the smallest grain size (20-300 nm) and the highest micro

hardness (989.5 Hv) was achieved with those samples prepared by SPS at 600°C [2002Moo].

Miscellaneous

The temperature of L12 D03 transformation of metastable phases in the mechanically alloyed Zr2CuxAl6-x

(0 < x < 1) was found to increase with increasing Cu content from 500 to 550°C in the studied

concentration interval, but the L12 structure of Zr2CuAl5 (x = 1) is stable at least up to 1300°C [1991Des1,

1992Des2]. The lattice parameter of metastable L12 phase decreases linearly with increasing Cu content

from 409.3 pm for ZrAl3(L12) (x = 0) to 405.8 pm at x = 1 is approximately constant after heating to 750°C

and are close to those of ZrAl3 annealed at 440°C, i.e. 407 pm [1991Des1] (a = 407.2 pm for

211


MSIT®

Al–Cu–Zr

Al-12.5Cu-25Zr (at.%) [1991Des2]. It was noted that hexane, was used as a surfactant by mechanical

alloying, gave rise to the formation of very fine dispersed carbides in the alloy [1991Des2].

Amorphous Al-Cu-Zr alloys were produced by melt spinning over wide composition range [1991Ino]. The

Al-Cu-Zr alloys were concluded to have a large glass-forming capacity. The high thermal stability of the

supercooled liquid was observed in the vicinity of the AlCuZr3 composition. Tg/Tm was measured to be

0.61.

The glass transition temperature Tg in the metallic glass Zr65Cu27.5Al7.5 was measured to be 350°C

[1997Sch]. Above Tg in the undercooled liquid region, a shift in the short range order was observed towards

the short range order of crystalline Zr2Cu. This change was found to be irreversible.

[1997Kan] reported a temperature variation of the specific heat of Zr65Cu27.5Al7.5 at temperatures around

Tg, Tg, Tx, (the temperatures of the initial stage of glass transition and crystallization, respectively) and Tm

were found to be 387, 447 and 475°C, respectively.

The lattice parameter variation with temperature determined for ZrCu1.2Al0.8 by [1992Sle] is shown in

Fig. 10.

Precipitation of metastable phases have been observed by [1974Bus] in Cu rich alloys with up to 7 mass%

Al and 0.525 mass% Zr quenched from 970°C and aged at 800°C. These phases were identified as ( Zr)

(a = 372 ± 1 pm) and (Zr) (a = 318 ± 1 pm), what is rather surprising for an alloy of a such composition.

The crystal structure of particles, which have been precipitated during aging at temperatures above 800°C,

has not be determined, yet. It is worth noting that [1974Bus] considered “ZrCu3” to be possibly a stable

phase with unknown crystal structure.

[1991Kan] observed partially coherent ' precipitates on ZrAl3 dispersoids in Al-4Cu-0.18Zr (mass%)

alloy. The precipitation behavior of the ' phase is different in the recrystallized and recovered condition.

References



[1962Poe] Poetschke, M., Schubert, K., “The Structure of some Systems Homologous and

Quasihomologous to T4-B3. II. The Binary Systems of Al with Ti, Hf, Zr and Mo”

(in German), Z. Metallkd., 53, 548-561 (1962) (Crys. Structure, Experimental, 45)

[1964Pan] Panseri, C., Leoni, M., “Studies on Complex Al Bronze. II. Ternary Equilibrium Diagram

Cu-Al-Zr” (in Italian), Allumino, 33, 63-70 (1964) (Equi. Diagram, Experimental, *, 5)

[1964Rie] Rieger, W., Nowotny, H., Benesovsky, F., “Structural Studies in the Systems with

Transition Elements (Cu, Ag) and (Al, Ga)” (in German), Monatsh. Chem., 95, 1573-1576


[1964Sch] Schubert, K., Raman, A., Rossteutscher, W., “Some Structural Data of Metallic Phases”

(in German), Naturwissenschaften, 51, 506-507 (1964) (Crys. Structure, Experimental, 0)

[1965Ram] Raman, A., Schubert, K., “On the Crystal Structure of Some Alloy Phases Related to TiAl3.

III. Investigations in Several T-Ni-Al and T-Cu-Al Systems” (in German), Z. Metallkd., 56,


[1966Mar] Markiv, V.Ya., Kripyakevich, P.I., “Compounds of the Type R(X’X’’)2 in Systems with R

= Ti, Zr, Hf, X’ = Fe, Co, Ni, Cu, and X’’ = Al, Ga and Their Crystal Structures”, Sov. Phys.

Crystallogr., 11, 733-738 (1967), translated from Kristallografiya, 11, 859-865 (1966)


[1967Hof] Hofer, G., Stadelmaier, H.H., “Co, Ni and Cu-Phases of the Ternary MnCu2Al Type”

(in German), Monatsh. Chem., 98, 408-411 (1967) (Crys. Structure, Experimental, 9)

[1967Zar] Zarechnyuk, O.S., Malinkovich, A.N., Lalayan, E.A., Markiv, V.Ya., “X-Ray Diffraction

Study of Al-Rich Alloys of the Ternary Al-Cu-Cr, Al-Cu-Zr and Al-Cr-Zr Systems and the

Quaternary Al-Cu-Cr-Zr System”, Russ. Metall., (6), 105-107 (1967), translated from Izv.

Akad. Nauk SSSR, Met., (6) 201-204 (1967) (Equi. Diagram, Experimental, *, 2)

[1969Hor] Hori, M., “On the Effects of Fe and Zr on the Eutectoid Transformation of Cu-Al Binary

Alloys” (in Japanese), J. Japan Inst. Metals, 33, 1067-1072 (1969) (Experimental, 23)

212


MSIT®

Al–Cu–Zr

[1969Tes] Teslyuk, M.Yu., Intermetallic Compounds with Structure of Laves Phases, Nauka,

Moscow, 1-138 (1969) (in Russian) (Crys. Structure, Experimental, Review, 312).

[1970Mar] Markiv, V.Ya., Burnashova, V.V., “Investigation of the Zr-Cr-Al and Zr-Cu-Al Systems”

(in Russian), Poroshk. Metall, (12), 53-58 (1970) (Crys. Structure, Equi. Diagram,

Experimental, *, 14)

[1974Bus] Bushnev, L.S., Payuk, V.A., Korokayev, A.D., “The Ageing of Copper-Zirconium and

Copper-Aluminium-Zirconium Alloys”, Phys. Met. Metallogr., 37, 111-116 (1975),

translated from Fiz. Met. Metalloved., 37, 573-579 (1974) (Experimental, 9)

[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, E.M., Rokhlin, L.L.,

Turkina, N.I., “Cu-Al-Zr” (in Russian), Binary and Multicomponent Copper-Base Systems.

Nauka Moskow, 85-86 (1979) (Equi. Diagram, Review, #, 2)

[1981Kin] King, H.W., “Crystal Structures of Elements at 25°C”, Bull. Alloy Phase Diagrams, 2,

401-402 (1981) (Crys. Structure, Review, 5)

[1984Kai] Kaibyshev, O.A., Valiev, R.Z., Tsenev, N.K., “Influence of the State of Grain Boundaries

on Superplastic Flow”, Sov. Phys.- Dokl. (Engl. Transl.), 29, 752-754 (1984), translated

from Dokl. Akad. Nauk SSSR, 278, 93-97 (1984) (Experimental, 12)



[1986Kne] Kneller, E., Khan, Y., Gorres, M., “The Alloy System Copper - Zirconium. Part I, Phase

Diagram and Structural Relations”, Z. Metallkd., 77, 43-48 (1986) (Crys. Structure, Equi.


[1986Riv] Rivlin, V.G., Miodownik, A.P., “A Provisional Assessment of the Literature Relevant to

AlCuZr Alloys”, Progr. Report 7, University of Surrey, 1-34 (1986) (Crys. Structure, Equi.


[1989Mey] Meyer zu Reckendorf, R., Schmidt, P.C., Weiss, A., “Reaction of Hydrogen with the

Heusler-Type Phases Cu2TiAl and Cu2ZrAl”, Z. Physik. Chemie, Neue Folge, 163, 103-108


[1990Kum] Kumar, K.S., “Ternary Intermetallics in Aluminium - Refractory Metal - X Systems (X=V,

Cr, Mn, Fe, Co, Ni, Cu, Zn)”, Int. Mater. Rev., 35, 293-327 (1990) (Equi. Diagram, Review,

#, 158)

[1990Mey1] Meyer zu Reckendorf, R., Schmidt, P.C., Weiss, A., “The Ternary Systems Cu-Ti-Al and

Cu-Zr-Al Around the Heusler Phase Composition Cu2XAl (X = Ti, Zr): Phase Diagrams

and Hydrogen Solubility”, J. Less-Common Met., 159, 277-289 (1990) (Crys. Structure,

Equi. Diagram, Experimental, *, 41)

[1990Mey2] Meyer zu Reckendorf, R., Schmidt, P.C., Weiss, A., “Hydrogen-Supported Formation of G

Phase Cu16Zr6Al7 in the Ternary System Copper - Zirconium - Aluminum”,


[1990Poy] Poyda, V.P., Kuznetsova, R.I., Tsenev, H.K., Sukhova, T.F., Pismennaya, A.N., “Evolution

of Porosity and Failure of the Al-4.1 mass% Cu-0.5 mass% Zr in Conditions of Superplastic

Flow” (in Russian), Metallofizika, 12, 44-79 (1990) (Experimental, 21)

[1991Des1] Desch, P.B., Schwarz, R.B., Nash, P., “Formation of Metastable L12 Phases in Al3Zr and

Al-12.5 % X-25 % Zr (X = Li, Cr, Fe, Ni, Cu)”, J. Less-Common Met., 168, 69-80 (1991)


[1991Des2] Desch, P.B., Schwarz, R.B., Nash, P., “Phase Stability in the Al6-xCuxZr2 System for

0<x<1”, Mater. Res. Soc. Symp. Proc., 186, 439-444 (1991) (Crys. Structure, Experimental,

*, 21)

[1991Ino] Inoue, A., Zhang, T., Masumoto T., “New Amorphous Alloys with Significant Supercooled

Liquid Region and Large Reduced Glass Transition Temperature”, Mater. Sci. Eng. A,

A134, 1125-1128 (1991) (Experimental, 8)

[1991Kan] Kanno, M., Ou, B.-L., “Heterogeneous Precipitation of Intermediate Phases on Al3Zr

Particles in Al-Cu-Zr and Al-Li-Cu-Zr Alloys”, Mat. Trans., JIM, 32, 445-450 (1991),

translated from J. Jpn. Inst. Light Met., 40, 672-677 (1990) (Experimental, 13)

213


MSIT®

Al–Cu–Zr

[1992Sle] Slebarski, A., Hafez, M., Zarek, W., “Spin Fluctuations in ZrM1.2Al0.8 with Transition

Metal M of the 3d Type”, Solid State Commun., 82, 59-61 (1992) (Crys. Structure,

Experimental, 12)

[1992Tre] Tretyachenko, L.A., “Aluminium - Copper - Zirconium”, MSIT Ternary Evaluation



Diagram, Assessment, #, 15)

[1993Oka] Okamoto, H., “Al-Zr (Aluminium - Zirconium)”, J. Phase Equilib., 14, 259-260 (Equi.

Diagram, Review, *, 2)

[1994Ari] Arias, D., Abriata, J.P., “Cu-Zr (Copper - Zirconium)”, in “Phase Diagrams of Binary

Copper Alloys”, Subramanian, P.R., Chakrabarty, D.J., Laughlin. D.E. (Eds.), ASM

Materials Park, OH, 497-502 (1994) (Crys. Structure, Equi. Diagram, Review,

Themodyn., 50)

[1994Zen] Zeng, K.-J., Haemaelaeinen, M., “A New Thermodynamic Description of the Cu-Zr

System”, J. Phase Equilib., 15, 577-586 (Equi. Diagram, Review, Thermodyn., 55)

[1997Kan] Kanomata, T., Sato, Y., Sugawara, Y., Aburatani, S., Kimura, H., Kaneko, T., Inoue, A.,

Masumoto, T., “Heat Capacity of Pd-Si, Ni-Si-B and Zr-Based Metallic Glasses”, Sci. Rep.

Res. Inst., Tohoku Univ., Ser. A, A43(2), 89-95 (1997) (Experimental, Thermodyn., 13)

[1997Sch] Schumacher, H., Oelgeschlaeger, D., Traverse, A., Samwer, K., “Structural Changes of the

Metallic Glass in the Undercooled Liquid Region”, J. Appl. Phys., 82, 155-162 (1997)

(Experimental, 34)

[1997Soa] Soares, D., Castro, F., “Study of Phase Equilibria in the Al-Cu-Zr System at the Al-Rich

Part”, J. Chim. Phys., 94, 958-963 (1997) (Crys. Structure, Equi. Diagram, Experimental,

*, 5)

[1998Bra] Braha, M.H., Malheiros, L.F., Castro, F., Soares, D., “Experimental Liquidus Points and

Invariant Reactions in the Cu-Zr System”, Z. Metallkd., 89, 341-345 (1998) (Equi. Diagram,


[1998Don] Dong, C., Zhang, Q.H., Wang, D.H., Wang, Y.M., “Al-Cu Approximants in the Al3Cu4

Alloy”, Eur. Phys. J. B, B6, 25-32 (1998) (Crys. Structure, Experimental, 16)

[1998Soa] Soares. D.F., de Castro, F.P., “Study of the Effect of Zirconium Addition to the Al-Rich

Alloys of the Al-Cu and Al-Cu-Mg Systems”, Ber. Bunsen-Ges. Phys. Chem., 102,

1181-1184 (1998) (Crys. Structure, Equi. Diagram, Experimental, *, 6)

[1998Tur] Turchanin, A.A., Tomilin, I.A., “Experimental Investigations of the Enthalpies of

Formation of Zr-Based Metallic Amorphous Binary and Ternary Alloys”, Ber. Bunsen-Ges.

Phys. Chem., 102, 1252-1258 (1998) (Experimental, Thermodyn., 29)

[1998Wit] Witusiewicz, V., Stolz, U.K., Arpshofen, I., Sommer, F., “Thermodynamic of Liquid

Al-Cu-Zr Alloys”, Z. Metallkd., 89, 704-713 (1998) (Experimental, Thermodyn., 16)

[2000Don] Dong, C., Zhang, Q.-H., Wang, D.-H., Wang, Y.-M., “Al-Cu Approximants and Associated

B2 Chemical-Twinning Modes”, Micron, 31, 507-514 (2000) (Crys. Structure,

Experimental, 21)

[2001Aki] Akinlade, O., Sommer, F., “Concentration Fluctuations and Thermodynamic Properties of

Ternary Liquid Alloys”, J. Alloys Compd., 316, 226-235 (2001) (Theory, Thermodyn., 27)




[2002Moo] Moon, K.I., Kim, S.Ch., Lee, K.S., “A Study on the Microstructure of D023 Al3Zr and L12

(Al+12.5at.%Cu)3Zr Intermetallic Compounds Synthesized by PBM and SPS”,

Intermetallics, 10, 185-194 (2002) (Crys. Structure, Experimental, 20)




214


MSIT®

Al–Cu–Zr

[2003Sem] Semenova, E., Sidorko., V., “Cu-Zr (Copper-Zirconium)”, MSIT Binary Evaluation


Services GmbH, Stuttgart; to be published, (2003) (Equi. Diagram, Assessment, Crys.

Structure, 31)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/ References

(Al)

< 660.42

cF4

Fm3m

Cu

a = 404.96 at 25°C [1981Kin]

Cu solubility 0 to 2.48 at.% [Mas2]

Zr solubility 0 to 0.08 at.% [1993Oka]

(Cu)

< 1084.87

cF4

Fm3m

Cu

a = 361.49 at 25°C [1981Kin]

Al solubility 0 to 19.7 at.% [2003Gro]

Zr solubility 0 to 0.12 at.% [1994Ari,

2003Sem]

( Zr)(h)

1855-863

cI2

Im3m

W

a = 360.90 [Mas2]

Cu solubility 0 to 5.7 at.% [1994Ari,

2003Sem]

Al solubility 0 to 25.9 at.% [1993Oka]

( Zr)(r)

< 863

hP2

P63/mmc

Mg

a = 329.17

c = 514.76

at 25°C [1981Kin]

Cu solubility 0 to 0.2 at.% [1994Ari,

2003Sem]

Al solubility 0 to 8.3 at.% [1993Oka]

, CuAl2< 591

tI12

14/mcm

CuAl2

a = 606.7

c = 487.7

31.9 to 33 at.% Cu [2003Gro]

[V-C2, 2003Gro]

1, CuAl(h)

624-560

o*32

a = 408.7

b = 1200c = 863.5

49.8 o 52.4 at.% Cu [2003Gro]

[V-C, 2003Gro]

2, CuAl(r)

< 563

mC20

C2/m

CuAl(r)

a = 1206.6

b = 410.5

c = 691.3

= 55.04°

49.8 to 52.4 at.% Cu

[V-C2, 1985Mur]Pearson symbol: [1931Pre]

1(h1)

958-848

cubic ? 59.4 to 62.1 at.% Cu [2003Gro]

2(h2)

850-560

hP6

P63/mmc

Ni2In

a = 414.6

c = 506.3

55.0 to 61.1 at.% Cu [2003Gro]

[V-C2, 2003Gro]

215


MSIT®

Al–Cu–Zr

1(h), Cu47.8Al35.5(h)

590-530

hP42

oF*

oF88-4.7

Fmm2

Cu47.8Al35.5

a = 810

c = 1000 (or 1237)

a = 816

b = 1414

c = 999

a = 812.67 ± 0.03

b = 1419.85 ± 0.05

c = 999.28 ± 0.03

55.2 to 56.9 at.% Cu [Mas2]

Cu56.8Al43.2 in the Al43Cu57 sample

annealed at 500°C for 10 h [1998Don,

2000Don]

for Cu47.8Al35.5 (57.5Cu-42.5Al)

annealed at 550°C for 240 h

(single-phase sample) [2002Gul]

2(r) Cu11.5Al9(r)

< 570

m*21

oI*

oI24-3.5

Imm2

Cu11.5Al9.0

a = 707

b = 408

c = 1002

= 90.63°

a = 408

b = 707

c = 999

a = 409.72

b = 703.13

c = 997.93

55.2 to 56.3 at.% Cu [Mas2]

[V-C]

Cu58.7Al41.3 in the Al43Cu57 sample

annealed at 500°C for 10 h [1998Don,

2000Don]

for Cu11.5Al9.0 (56.8Cu-43.2Al)

annealed at 550°C for 240 h (single

phase sample) [2002Gul]

Cu1-xAlx< 686

hR*

R3m

a = 1226

c = 1511

[V-C2, 2003Gro] for Cu61.1Al38.9

59.3 to 61.1 at.% Cu [Mas2, 2003Gro]

0Cu~2Al

1037-800

cI52

I43m

Cu5Zn8

59.8 to 69 at.% Cu [2003Gro]

1

890

cP52

P43m

Cu9Al4

a = 870.23

62.5 to 69 at.% Cu [2003Gro]

[V-C2]

CuAl(h)

1049-559

cI12

Im3m

W

a = 295.64

70.9 to 82.0 at.% Cu [2003Gro]

at 672°C in +(Cu) alloy [V-C2,

2003Gro]

ZrAl3< 1580

tI16

I4mmm

ZrAl3

a = 401.4

c = 1732

[1993Oka, V-C2]

Cu solubility < 0.5 at.% in homogeneity

range at 750°C [1997Soa, 1998Soa];

Zr2CuxM6-x at 0 x 0.9 [1991Des2]

ZrAl2< 1660

hP12

P63/mmc

MgZn2

a = 528.24

c = 874.82

[1993Oka, V-C2]

Zr2Al3< 1590

oF40

Fdd2

Zr2Al3

a = 960.1

b = 1390.6

c = 557.4

[1993Oka, V-C2]

ZrAl

< 1275

oC8

Cmcm

CrB

a = 335.9

b = 1088.7

c = 427.4

[1993Oka, 1962Poe]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


216


MSIT®

Al–Cu–Zr

Zr4Al3-xCux

Zr4Al3 1030

hP7

P6

Zr4Al3

a = 543 to 537a

c = 539a

a = 543.4

c = 539.0

0 x 0.735 [1970Mar]

[1993Oka, V-C2]

Zr3Al2< 1480

tP20

P42/mnm

Zr3Al2

a = 763

c = 699.8

[1993Oka, V-C2]

Zr2Al

< 1215

hP6

P63/mmc

Ni2In

a = 489.39

c = 592.83

[1993Oka, Mas2, V-C2]

Zr3Al

< 1019

cP4

Pm3m

Cu3Au

a = 437.2 [1993Oka, V-C2]

Zr2Cu

< 950

tP150 a = 1592.4

c = 1132.8

[2003Sem, 1986Kne, 1998Bra]

ZrCu

960-725

cP2

Pm3m

CsCl

a = 325.87 [1998Bra, 2003Sem]

Zr7Cu10

< 935

oC68

C2ca

Zr7Ni10

a = 1267.29

b = 931.63

c = 934.66

[2003Sem, 1998Bra]

Zr3Cu8(h)

1028- 600

oP44

Pnma

Hf3Cu8

a = 786.93

b = 815.47

c = 998.48

[2003Sem, V-C2]

[1986Kne, 1998Bra]

Zr14Cu51

< 1112

hP68

P6/m

Gd14Ag51

a = 1124.44

b = 828.15

[2003Sem, V-C2]

ZrCu5

< 1032

cF24

F43m

AuBe5

a = 687 [1986Kne, 1994Zen, 1998Bra,

2003Sem]

* 1 unknown 14Al-71Cu-15Zr [1970Mar]



* 4, ZrCu2Al oF16

MnCu2Al

a = 621.5 ± 0.3

a = 619

a = 622

a = 621.63 ± 0.03

[1970Mar]

[1964Sch, 1965Ram]

[1967Hof]

[1989Mey, 1990Mey1, 1990Mey2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


217


MSIT®

Al–Cu–Zr

a as scaled from diagram

* 5, ZrCuxAl2-x cF24

Fd3m

MgCu2

a = 730.8 to 744.0

a = 740

a = 739.7

a = 738.1

a = 739.1 ± 0.3

a = 738.83

0.95 x 0.36 at 800°C

[1966Mar, 1969Tes, 1970Mar]

for ZrCuAl [1964Sch]

in as cast alloy Zr25Cu25Al50

[1965Ram]

in the ZrCu2Al alloy annealed at 600°C

[1990Mey1, 1990Mey2]

the phase present in ZrCu2Al at 600°C

(2 %) [1989Mey]

for ZrCu1.2Al0.8 (Zr35.3Cu40Al26.7)

annealed at 1000 K for 7 d [1992Sle]

* 6, ZrCu4Al3cI* a = 1730.0

37Al-51Cu-12Zr [1970Mar]

37Al-51Cu-12Zr [1970Mar]

* 7 tI26

I4/mmm

ThMn12

a = 512 to 490

c = 850 to 856

(50-41)Al-(42.3-51.3)Cu-7.7Zr

(ZrCu5.50-6.70Al6.50-5.90) at 800°C

[1970Mar]

* 8, Zr2CuAl5 cP4

Pm3m

Cu3Au

a = 402

a = 404

62.5Al-12.5Cu-25Zr [1970Mar]

[1964Sch, 1965Ram]

(62.5-66.25)Al-(12.5-8.75)Cu-25Zr

at 750°C [1991Des2]

* 9

< 740

tI*. a = 579

c = 396

for 67.2Al-15.7Cu-17.1Zr [1998Soa]

* 10, Zr6Cu16Al7 cF116

Mg6Cu16Si7

a = 1194.1 ± 0.03

a = 1192.5

a = 1193.3

the phase present in ZrCu2Al annealed

at 600°C (3 %) [1989Mey]

in the ZrCu2Al alloy annealed at 600°C

for 48 h [1990Mey1, 1990Mey2]

in the 20.7Zr-55.2Cu-24.1Al alloy

( 10+ 4) annealed at 800°C for 98 h

[1990Mey1]

Zr2CuxAl6-x cP4

Pm3m

Cu3Au

a = 409.5 to

405.5

0 x 1; metastable phase in a

mechanically alloyed powders

[1991Des2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


218


MSIT®

Al–Cu–Zr

Fig. 1: Al-Cu-Zr. Tentative partial reaction scheme in the Al-rich corner

Al-Zr Al-Cu-Zr

L + τ8

ZrAl3 + τ

7820±10 U

1

ZrAl3 + τ

8 + τ

7

Al-Cu

L + ZrAl3

(Al)

660.8 p

L + ZrAl3

+ τ7

τ9'740±10 P

L + ZrAl3

(Al) + τ9'T

1<600 U

2

L + τ7

θ + τ9'560±10? U

3

L + τ9' (Al) + θ560>T

2>T

eU4

L (Al) + θ548.2 e

ZrAl3 + τ

8 + L τ

7+ τ

8 + L

L + ZrAl3 + τ

7

ZrAl3 + τ

9'+ L

τ7

+ τ9' + L

τ9'+ θ + L

(Al) + θ + L

ZrAl3

+ τ7 + τ

9'

ZrAl3

+ τ9' + (Al) τ

7+ θ + L

τ7 + τ

9' +θ

τ9' + (Al) + θ

Fig. 2: Al-Cu-Zr. Tentative partial reaction scheme near the Al-Cu side for the Cu-rich part

l β + (Cu)

1032 e1

L β + (Cu) + τ1

900<T1<965 E

β (Cu) + γ1

559 e2

β + τ1

(Cu) + γ1

568 U

L + τ1 + β L + (Cu) + τ

1

β + (Cu) + τ1 β + τ

1 + γ

1

(Cu) + γ1

+ τ1

Al-Cu Al-Cu-Zr Al-Zr

219


MSIT®

Al–Cu–Zr

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Zr 60.00Cu 0.00Al 40.00

Zr 0.00Cu 60.00Al 40.00


Axes: at.%

Zr2Al3

Zr5Al4

τ8

ZrAl2

ZrAl3

(Al)

ε2

η1

θ

τ7

τ5

τ9´

560820

740

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Zr 60.00Cu 0.00Al 40.00

Zr 0.00Cu 60.00Al 40.00

Data / Grid: at.%

Axes: at.%

ZrAl2

ZrAl3

Zr2Al3

Zr4Al3

τ5 τ

7

τ8 L

Al

Fig. 3: Al-Cu-Zr.

Ternatative solidus

projection for the

Al-rich part

Fig. 4: Al-Cu-Zr.

Partial isothermal

section at 860°C for

the Al-rich part

220


MSIT®

Al–Cu–Zr

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Zr 60.00Cu 0.00Al 40.00

Zr 0.00Cu 60.00Al 40.00

Data / Grid: at.%

Axes: at.%

Zr2Al3

ZrAl

τ8

ZrAl2

ZrAl3

L

Zr4Al3ε

2

τ7

τ5

τ9´

Al

20

40

60

80

20 40 60 80

20

40

60

80

Zr Cu


Axes: at.%

(Cu)

γ1

ε2

L

ZrAl3

ZrAl2

Zr2Al3

ZrAl

Zr4Al3

Zr3Al2

Zr2Al

Zr3Al

(αZr)

Zr2CuZrCu

Zr7Cu10

Zr3Cu8 Zr14Cu51

ZrCu5

τ1

τ2

τ3 τ4

τ5

τ6

τ7

τ8

β

γ0τ10

Fig. 6: Al-Cu-Zr.

Partial isothermal

section at 700°C for

the Al-rich part

Fig. 5: Al-Cu-Zr.


800°C

221


MSIT®

Al–Cu–Zr

20

40

60

80

20 40 60 80

20

40

60

80

Zr Cu


Axes: at.%(Al)

ZrAl3

ZrAl2Zr2Al3

(Cu)

τ1

τ4

γ1

δ

ε2

η1τ

5

τ6

τ7

τ9´

τ8

Zr14Cu51 ZrCu5

τ10

L

β

20

40

60

80

20 40 60 80

20

40

60

80

Zr Cu


Axes: at.%(Al)

ZrAl3

ZrAl2Zr2Al3

(Cu)

τ1

τ4

γ1

δ

ζ2

η2

θ

τ5

τ6

τ7

τ9´

τ8

Zr7Cu10Zr14Cu51 ZrCu5

τ10

Fig. 8: Al-Cu-Zr.

Partial isothermal

section at 500°C

Fig. 7: Al-Cu-Zr.

Partial isothermal

section at 600°C

222


MSIT®

Al–Cu–Zr

400

500

600

700

800

900

1000

1100

Zr 3.10Cu 75.90Al 21.00

Zr 0.00Cu 79.30Al 20.70Cu, at.%

Tem

pera

ture

, °C

(Cu)+γ1(Cu)+τ1+γ1

β+(Cu)+γ1568

β+(Cu)β+(Cu)+τ1

β+τ1

β

β+LLL+τ1

L+β+τ1

7976 77 78

Fig. 9: Al-Cu-Zr.

Polythermal section

for 10 mass% Al

Temperature, K

Latticeparameter,pm

0735

50 100 150 200 250 300

736

737

738

739Fig. 10: Al-Cu-Zr.

The lattice parameter

a of ZrCu1.2Al0.8 vs

temperature

[1992Sle]

223


MSIT®

Al–Dy–Fe

Aluminum – Dysprosium – Iron

Riccardo Ferro, Paola Riani, Laura Arrighi

Literature Data


evaluation made by [1991Gri] considering a fast amount of new published data. However the Al-Dy-Fe

system has been investigated only up to 33.3 at.% Dy and most experimental work deals with magnetic

properties measurements and crystal structure determination, either by X-ray or neutron diffraction.

At 500°C a partial isothermal section has been determined by [1973Viv] in the above mentioned region, by

means of X-ray diffraction and microscopy, and by [2001Yan] at the Dy2(Fe,Al)17 composition at the same

temperature. In the [1973Viv] section no indication was given about the phase based on Dy6Fe23 and on the

solubility range of DyFe3. The phase 3 moreover was presented as a point phase (DyFe1.2Al0.8). The

section RFe2-RAl2 was studied at 800°C by [1975Dwi] and by [1998Psz]. [1977Oes] studied the solid

solution phases based on DyFe3, Dy6Fe23 and Dy2Fe17. The alloys were prepared either by induction

melting only or by melting and annealing (Dy6Fe23 200 h at 1000°C).

Binary Systems

The binary phase equilibria in the Al-Fe system are accepted in this evaluation as described by [2003Pis],

who based his evaluation on the assessment of [1993Kat] and incorporated in the Fe-rich region the ordering

equilibria between the ( Fe), FeAl and Fe3Al solid solutions which have been recently investigated by

[2001Ike].

The Dy-Fe and Al-Dy systems are accepted as reported by [1993Oka] and [2002Gry], respectively.

Solid Phases

Crystal structure data are reported in Table 1.

The binary Laves phases DyAl2 and DyFe2 are isostructural both to the MgCu2 type; DyAl2 dissolves about

26 at.% Fe at 800°C ([1975Dwi]) or 20 at.% Fe [1998Psz] (after melting and cooling down); DyFe2

dissolves at 800°C about 22.7 at.% Al [1975Dwi]. At intermediate compositions, however, a different

Laves phase ( 3, MgZn2 type) is formed [1962Wer, 1971Oes, 1972Oes, 1973Oes, 1973Viv, 1973Zar,

1974Oes, 1975Dwi, 1976Gro, 1998Psz].

According to [2001Yan], Dy2Fe17 (Th2Ni17 type) too presents large Al solubility and at increasing Al

contents it transforms into the related structures TbCu7 and Th2Zn17 type, respectively. The hexagonal

Th2Ni17 and TbCu7 type structures dominate at, or below, the theoretical molar ratio Dy/(Fe+Al) = 2:17

(10.5±9.5 at.% Dy) while the rhombohedral Th2Zn17 type structure dominates at higher Dy content

( 11.5 at.%). In the same composition range X-ray diffraction investigations have been performed also by

[1977Oes] and [1999Hao] (see Table1). According to [1996Mao] the TbCu7 type structure is also present

as a DyFe7 metastable phase in the Dy-Fe binary system.

At even higher Al content another ternary phase, with a larger Dy/(Fe,Al) ratio, is formed ( 4, ThMn12 type)

studied by [1973Viv, 1974Viv, 1976Bus, 1988Sch, 1988Won, 2000Pai] at the composition DyFe4Al8, and

by [1980Fel, 1981Fel, 1988Che] at DyFe6Al6. The ThMn12 type structure of R(Fe1-xAlx)12 compounds and

the preferential site occupancies of Fe and Al in 8f and 8i position respectively have been studied by

[2001Sch] for several rare earth metals (R). It was observed that higher Fe concentrations obtained by

substitution of Al by Fe (RFe4Al8 → RFe5Al7 → RFe6Al6 → RFe7Al5) lead to a gradual decrease of the

lattice parameters. In the case of Ho and Er the structures of RFe7Al5 were clearly observed, in the case of

Dy (and Tb) their formation is questionable (probably due to limits related to the atomic dimension of R).

Finally, with the same Dy/(Fe,Al) ratio, another ternary phase ( 5, at the composition DyFe2Al10) was

studied by [1973Viv, 1998Thi, 2000Ree].

224


MSIT®

Al–Dy–Fe

The phase based on the binary DyFe3 dissolves Al, in the PuNi3 type form, up to about 5 at.% (alloys

prepared by induction melting only) [1977Oes]. A higher solubility (see Table 1) was observed in the CeNi3modification (up to -33 at.% Al); however this solution can be considered as a ternary phase stable at higher

temperature.

The binary Dy6Fe23 phase dissolves up to 20 at.% Al at 1000°C [1977Oes].

Isothermal Sections

A “quasi” isothermal section of the system is proposed in Fig. 1. Notice however that it has been built

assembling various parts investigated at different temperatures. The region from 0 to 18 at.% Dy may be

considered determined at 500°C [1973Viv, 2001Yan]. In the region between 20 and 30 at.% Dy only data

probably relevant to higher temperature are available in literature [1977Oes] and have been included.

Finally in the region around 33 at.% Dy the data obtained at 800°C by [1975Dwi] have been included.


Mössbauer measurements on the 3 Dy(Fe1-xAlx)2 phase have been carried out by [1998Psz] and, at the

DyFeAl composition, by [1975Dwi, 1976Gro].

Magnetic properties of 3 Dy(Fe1-xAlx)2 and DyFe2Al10 were investigated by [1991Su, 1996Kor, 1996Mus,

1999Zho] and by [1998Thi, 2000Ree], respectively.

Magnetic properties of Dy2(Fe1-xAlx)17 alloys have been studied by [1984Plu], calculated by [1999Hao],

reviewed by [1994Liu, 2002Ram] and, at the Dy2Fe9Al8 composition, studied by [1996Rid].

Magnetic properties of 4 Dy(Fe1-xAlx)12 have been investigated by low temperature Cp measurements,

neutron diffraction, etc. by [1978Bus, 1988Sch, 1997Pai, 1998Hag, 2000Hag, 2000Pai] at the DyFe4Al8composition, by [1981Fel, 1988Che] at DyFe6Al6 and by [2001Sch] at DyFe7Al5.

Moreover [1998Ima] investigated the crossover from Heisemberg to Ising spin-glass-like magnetic

properties in random anisotropy magnets of amorphous Dy16Fe84-x Alx (0 x 62) and [2002Kon] studied

the magnetic properties and microstructure of melt-spun ribbons of Dy60Fe30Al10 alloys.

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225


MSIT®

Al–Dy–Fe

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226


MSIT®

Al–Dy–Fe

Terbium, Dysprosium, Holmium, and Erbium”, J. Less-Common Met., 143, L7-L10 (1988)


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Exchange Interaction in Intermetallic Compounds”, J. Magn. Magn. Mater., 132, 159-179

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ThMn12 Structure”, Physica B, B234-B236, 614-616 (1997) (Magn. Prop., Experimental, 6)

227


MSIT®

Al–Dy–Fe

[1998Ali] Aliravci, C.A., Pekgueleryuez, M.O., “Calculation of Phase Diagrams for the Metastable

Al-Fe Phases Forming in Direct-Chill (DC)-Cast Aluminium Alloy Ingots”, Calphad, 22,


[1998Hag] Hagmusa, I.H., Brueck, E., de Boer, F.R., Buschow, K.H.J., “Magnetic Properties of

RFe4Al8 Compounds Studied by Specific Heat Measurements“, J. Alloys Compd., 278,

80-82 (1998) (Magn. Prop., Experimental, 9)

[1998Ima] Imai, K., Masago, E., Saito, T., Shinagawa, K., Tsushima, T., “Crossover from Heisemberg

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Magn. Prop., Moessbauer, Experimental, 33)

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Sm, Gd = Lu and T=Fe, Ru, Os) with YbFe2Al10 Type Structure and Magnetic Properties

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the 3d Sublattice of Dy2Fe17-xAlx Compounds”, J. Phys.: Condens. Matter, 11, 6113-6119

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Single Crystal Dy(Fe0.8Al0.2)2”, Acta Phys. Sin.(Chin. J. Phys.), 48(12), S204-S210 (1999)

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Some RFe4Al8 Compounds (R = Ce, Pr, Nd, Dy, Ho, Tm)”, J. Alloys Compd., 298, 77-81

(2000) (Crys. Structure, Thermodyn., Experimental, 16)

[2000Pai] Paixao, J.A., Silva, M.R., Sorensen, S.A., Lebech, B., Lander, G.H., Brown, P.J., Langridge,

S., Talik, E., Goncalves, A.P., “Neutron-Scattering Study of the Magnetic Structure of

DyFe4Al8 and HoFe4Al8”, Phys. Rev. B, 61B(9), 6176-6188 (2000) (Crys. Structure, Magn.


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Order in TbFe2Al10 and DyFe2Al10”, Physica B, 276B-278B, 594-595 (2000) (Crys.

Structure, Magn. Prop., Experimental, 4)

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Equilibria in the 0 to 66.7 at.% Al Composition Range”, Z. Metallkd., 91(1), 17-23 (2000)


[2001Ike] Ikeda, O., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria and Stability of Ordered

BCC Phases in the Fe-Rich Portion of hte Fe-Al System”, Intermetallics, 9, 755-761 (2001)


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Earth-Iron-Aluminium Intermetallics RFe7Al5 (R = Tb, Dy, Ho, Er)”, Mater. Sci. Forum,

378-381, 414-419 (2001) (Crys. Structure, Magn. Prop., Experimental, 12)

[2001Yan] Yanson, T., Manyako, M., Bodak, O., Cerny, R., Yvon, K., “Effect of Aluminium

Substitution and Rare-Earth Content on the Structure of R2(Fe1-xAlx)17 (R = Tb, Dy, Ho,

Er) Phases”, J. Alloys Compd., 320(1), 108-113 (2001) (Crys. Structure, Equi. Diagram,

Experimental, 9)

228


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Al–Dy–Fe

[2002Kon] Kong, H.Z., Ding J., Dong, Z.L., Wang, L., White, T., Li, Y., “Observation of Clusters in

Re60Fe30Al10 Alloys and the Associated Magnetic Properties“, J. Phys. D: Appl. Phys., 35,

423-429 (2002) (Crys. Structure, Magn. Prop., Experimental, 26)

[2002Ram] Rama Rao, K. V. S., Ehrenberg, H., Markandeyulu, G., Varadaraju, U. V., Venkatesan, M.,

Suresh, K. G., Murthy, V. S., Schidt, P. C., Fuess, H., “On the Structural and Magnetic

Properties of R2Fe(17-x)(A, T)x (R = Rare Earth, A = Al, Si, Ga, T=Transition Metal)

Compounds”, Phys. Status Solidi A, 189A(2), 373-388 (2002) (Crys. Structure, Magn.

Prop., Review, 51)

[2002Gry] Grytsiv, A., “Al-Dy (Aluminium-Dysprosium)”, MSIT Binary Evaluation Program, in


GmbH, Stuttgart; Document ID: 20.20073.1.20 (2002) (Equi. Diagram, Assessment, Crys.

Structure, 8)

[2003Pis] Pisch, A., “Al-Fe (Aluminum-Iron)” MSIT Binary Evaluation Program, in MSIT


Stuttgart, to be published, (2003) (Equi. Diagram, Assessment, Crys. Structure, 58)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0

at 25°C, 13 GPa [Mas2]

( Fe)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2, 1993Kat]

dissolves up to 1.2 at.% Al

( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60.to 290.12

pure Fe at 25°C [Mas2]


0-18.8 at.%Al, HT [1958Tay]

0-19.0 at.% Al, HT [1961Lih]

0-18.7 at.% Al, 25°C [1999Dub]

( Dy)

1412-1381

cI2

Im3m

W

a = 398.0 [Mas2]

dissolves up to 3 at.% Al at 1300°C

[1988Gsc]

( Dy)

< 1381

hP2

P63/mmc

Mg

a = 359.15

c = 565.01

[Mas2]

dissolves up to 1 at.% Al at 1300°C

[1988Gsc]

229


MSIT®

Al–Dy–Fe

Fe4Al13

< 1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16-76.70 at.% Al [1986Gri]

at 76.0 at.% Al [1994Gri]

Fe2Al5< 1169

oC24

Cmcm

Fe2Al5

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [1994Bur]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [1993Kat]

1232-1102

cI16?

-

a = 598.0 at 61 at.% Al [1993Kat]

FeAl

< 1310

cP8

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5 - 47.5 at.% Al [1961Lih]

36.2 - 50.0 at.% Al [1958Tay]

39.7 - 50.9 at.% Al [1997Kog] 500°C

quenched in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

24 - 37 at.% Al [2001Ike]

23.1 - 35.0 at.% Al [1958Tay]

24.7 - 31.7 at.% Al [1961Lih]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [1993Kat]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [1993Kat]

[1998Ali]

FeAl4+x t** a = 884

c = 2160

(0 < x < 0.4) metastable [1998Ali]

DyAl31090-1005

hR60

R3m

HoAl3

a = 607.0

c = 3590

[1988Gsc]

(preparable also at 800°C

under 15 kbar)

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

230


MSIT®

Al–Dy–Fe

DyAl3< 1005

hP16

P63/mmc

TiNi3

a = 609.1

c = 953.3

[1988Gsc]

DyAl3 (I)

Dy(FexAl1-x)3 (h)

cP4

Pm3m

AuCu3

a = 423.6

a = 425.3

HP [V-C]

x = 0.067 (1000°C) Fe stabilised phase

[1977Oes]

DyAl2< 1500

Dy(FexAl1-x)2

cF24

Fd3m

MgCu2

a = 784

a = 783.5 to 766

x = 0 [1988Gsc], [2000Sac]

0 x 0.39 [1975Dwi]

0 x 0.3 [1998Psz]

DyAl

< 1110

oP16

Pbcm

ErAl

a = 582

b = 1137 to 1134

c = 560 to 559

[1988Gsc, 2000Sac]

Dy3Al2< 1025

tP20

P42/mnm

Zr3Al2

a = 817 to 820

c = 754 to 755

[1988Gsc, 2000Sac]

Dy2Al

< 990

oP12

Pnma

Co2Si

a = 654 to 653

b = 508

c = 940 to 938

[1988Gsc, 2000Sac]

Dy2Fe17

< 1375

Dy2(Fe1-xAlx)17

hP38

P63/mmc

Th2Ni17

a = 844.4

c = 831.0

a = 845.5 to 853.8

c = 830.9 to 836.0

a = 846.5 to 855.5

c = 829.6 to 836.1

a = 849 to 857

c = 833 to 838

[1966Bus]

0 x 0.168 [1977Oes]

0 x 0.18 ( at 1050°C) [1999Hao]

[2001Yan]:

0 x 0.2 (at 10.5 at.% Dy, data taken

from graph)

0 x 0.25 (at 9.5 at.% Dy, data taken

from graph)

DyFe7 hP8

P6/mmm

TbCu7

a = 487

c = 418

metastable phase prepared by annealing

mechanically alloyed powders

[1996Mao] (lattice parameters from

graph)

Dy6Fe23

< 1290

Dy6(Fe1-xAlx)23

cF116

Fm3m

Th6Mn23

a = 1206

a = 1206.2

a = 1205.64

a = 1214.94

[1966Kri]

[1970Goo]

0 x 0.25 at 1000°C [1977Oes]

x = 0 [1977Oes]

x = 0.25 [1977Oes]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

231


MSIT®

Al–Dy–Fe

DyFe3

< 1305

Dy(Fe1-xAlx)3

hR36

R3m

PuNi3

hP24

P63/mmc

CeNi3(related to the

PuNi3-type:

aPuNi3aCeNi3,

cPuNi33/

2cCeNi3)

a = 511.6

c = 2455

a = 511.8 to 513.3

c = 2454 to 2454

a = 517.7 to 522.7

c=1658.4 to 1679.0

[1970Goo]

0 x 0.067 [1977Oes]

0.13 x 0.43 [1977Oes]

Possibly this structure can be considered

as a high temperature ternary phase (not

reported in Fig. 1). Further research

required.

DyFe2

< 1270

Dy(Fe1-xAlx)2

cF24

Fd3m

MgCu2

a = 732.5

a = 732.4 to 747.4

a 731 to 748

[1970Bus]

0 x 0.34 at 800°C [1975Dwi]

0 x 0.3 [1998Psz] (data taken from

graph)

DyFe2 (l)

< 23

t** [1981And]

tetragonal distorsion of the cubic form

* 1, Dy2(Fe1-xAlx)17 hP8-x

P6/mmm

TbCu7

or hP22

P622

Tb2Fe14Al3(related to TbCu7

type: aTbCu7aTb2Fe14Al3/31/2)

a = 495 to 497

c = 419 to 421

a = 857.2

c = 419.3

0.22 x 0.28 (at 10.5 at.% Dy, data

taken from graph)

x 0.28 (at 9.5 at.% Dy) [2001Yan]

at x = 0.22 [1977Oes]

* 2, Dy2(Fe1-xAlx)17 hR57

R3m

Th2Zn17

a = 866.3 to 876.9

c = 1261.1 to 1270.2

a = 859.7 to 877.9

c = 1255.2 to 1271.4

a = 863 to 877

c = 1260 to 1266

0.28 x 0.50 [1977Oes]

0.23 x 0.52 [1999Hao]

[2001Yan]

0.30 x 0.50 (at ~9.5±10.5 at.% Dy,

data from graph)

0.17 x 0.50 (at ~11.5 at.% Dy)

* 3, Dy(Fe1-xAlx)2 hP12

P63/mmc

MgZn2

a = 534.8

c = 869.5

a = 532 to 538

c = 869 to 874

0.375 x 0.56 at 800°C [1975Dwi]

x = 0.48 [1973Oes]

0.4 x 0.52 [1998Psz] (data from

graph)

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

232


MSIT®

Al–Dy–Fe

* 4 , Dy(Fe1-xAlx)12 tI26

I4/mmm

ThMn12 a = 871.5

c = 503.7

a = 865.0

c = 500.1

a = 864.2

c = 502.6

0.54 x 0.71 at 500°C [1973Viv]

at x = 0.67 [1976Bus]

at x = 0.5 at 800°C [1980Fel]

at x = 0.5 [1988Che]

* 5, DyFe2Al10 oC52

Cmcm

YbFe2Al10

(related to the

ThMn12 type:

ao at, bo 2ct,

co at)

a = 895.4

b = 1014.1

c = 900.0

a = 893.3

b = 1010.6

c = 896.9

[1998Thi] (annealed at 800°C and

cooled at 6°C h-1)

neutron diffraction at 1.5 K [2000Ree]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

20

40

60

80

20 40 60 80

20

40

60

80

Dy Fe


Axes: at.%

τ5

τ3

Dy(Fe1-xAlx)2

Dy(Fe1-xAlx)3

Dy6(Fe1-xAlx)23

Fe3Al

τ4

DyAl3Fe4Al13

FeAl2

Fe2Al5

τ2

τ1

FeAl

(αFe)

Dy(FexAl1-x)2

Dy2(Fe1-xAlx)17

(Al)Fig. 1: Al-Dy-Fe.

Subsolidus phase

equilibria concluded

from studies made at

different

temperatures.

See section

“Isothermal Sections“

233


MSIT®

Al–Dy–Ni

Aluminium – Dysprosium – Nickel

Riccardo Ferro, Gilda Zanicchi, Rinaldo Marazza

Literature Data

Several investigations have been carried out mainly concerning the intermediate phases, their crystal

structures and magnetic properties [1962Wer, 1968Dwi, 1970Leo, 1972Ryk, 1973Oes, 1973Ryk, 1973Zar,

1977Ryk, 1978Ryk, 1980Ryk, 1981Zar, 1982Roml, 1982Rom2, 1987Tsv1, 1987Tsv2, 1993Gla, 1995Sor,

1997Ehl, 1997Kol, 2002Bur, 2002Dan, 2002Lam]. Different alloys were prepared by arc melting or by

levitation melting carried out under He or Ar. The alloys were generally annealed at temperatures between

600 and 900°C. An investigation of the section DyNi2-DyAl2 was carried out by [1970Leo]. Ranges of

stability of the different phases (DyNi2 and DyAl2-based solid solutions and the intermediate DyNiAl

phase) and structural and magnetic properties were studied. A systematic investigation of the 800°C

isothermal section in the 0 to 33.3 at.% Dy composition range was also carried out by [1980Ryk]. This study

was performed by preparing 45 alloys from 99.98 mass% Al, 99.9 % Ni and 99.6 % Dy. Alloys were

prepared by arc melting under purified argon, annealing at 800°C for 700 h and then quenching in ice water.

A high pressure form of DyNiAl (MgZn2 type) prepared by annealing the initial powdered components at

1450 to 1500°C at a pressure of 7.7 GPa has also been reported [1987Tsvl]. The same information is given

in [1987Tsv2]. [1993Gla] determined the structure of the new DyNi3Al9 compound which crystallizes in

the rhombohedral hR78- ErNi3Al9 type.

Binary Systems

The Al-Dy from [2003Gry], Al-Ni from [2003Sal] and Dy-Ni from [2000Oka] systems have been accepted.

Solid Phases

Special attention was dedicated to the 0 to ~ 30 at.% Dy composition range. Several solid phase pertaining

to this composition field have been described. [1993Gla] determined the structure of the new DyNi3Al9compound which crystallizes in the trigonal ErNi3Al9 type structure, with partly disordered arrangement of

Al-atom triangles and rare earth metal atoms. The crystal properties of the unary, binary and ternary phases

are reported in Table 1. [1973Oes] and [1980Ryk] describe 9, DyNiAl, as a point phase. According to

[1970Leo], however, a certain range of homogeneity between 44 and 52 mole% DyAl2 could be assigned

to this phase along the DyAl2-DyNi2 section.

Notice that on the basis of the lattice parameter values, an analogy between the crystal structures of 1 and

5 may be envisaged a( 1) ≅ a( 5), b( 1) ≅ b( 5), c( 1) ≅ 4 c( 5).

[1995Sor] studied structural properties of the DyNi5-xAlx-hydrogen system. It was found that the hexagonal

crystal structure of the prototype compound DyNi5 (CaCu5 type) exists up to DyNi3Al2, beyond this

composition and up to DyNi2Al3 another related hexagonal structure (YCo3Ga2 type) was observed.

The two forms, conventionally indicated as Dy2Ni7 and Dy2Ni7 have a similar stability, even if in

[1970Bus] an indication is given that probably in rare earth - nickel compounds R2Ni7 the hexagonal form

is stable at high temperature and the rhombohedral at low temperature (at variance however with

[1969Vir]). The transformation between the two forms is sluggish and possibly of the martensitic type. No

indication about a transformation temperature may be reported in Table 1 and in Fig. 1, only a generic

indication to Dy2Ni7 is given.

Isothermal Sections

The partial isothermal section at 800°C, given in Fig. 1, is based on the data of [1980Ryk] who used long

homogenizing annealing periods, followed by quenching in ice water. The solubility limits seem to be

established not very precisely in [1980Ryk], therefore some tie-lines are shown in Fig. 1 by dashed lines.

The liquid phase equilibria in the Al corner have not been studied. [1980Ryk] did not report in his section

234


MSIT®

Al–Dy–Ni

the new phase DyNi3Al9 identified more recently by [1993Gla], it has been included in Fig. 1 with an

indication of a possible trend of the tie-lines (dashed lines).

Miscellaneous

Magnetic properties of the Al-Dy-Ni (and more generally of Al-R-Ni) alloys have been studied and

discussed in several papers. [1970Leo] studied AlxNi2-xR alloys: magnetic properties of Al-Ni-Dy, for

x = 0.16 and 1.80, have been measured. Magnetic parameters of DyNiAl have been reported by [1973Oes].

Magnetic properties of DyNiAl2 and of Dy2Ni2Al have been studied by [1982Roml] and [1982Rom2].

Hydrogen adsorption in RNi4Al alloys has been studied [1978Tak].

[1995Sor] studied hydrogen absorption in the DyNi5-xAlx system. All alloys were exposed to hydrogen gas

at pressure up to 15 MPa and temperatures between 77 and 700 K. Under these conditions ternary alloys

having the CaCu5 structure react with hydrogen, the other ternary alloys do not exhibit any significant

hydrogen absorption. The pressure-composition isotherms were measured.

[1997Kol] studied hydrogen absorption - desorption, crystal structure and magnetism in intermetallic

compound of the series RNiAl (R = Y, Gd, Tb, Dy, Er, Lu), by means of neutron diffraction and

susceptibility measurements. These compounds, crystallizing in the ZrNiAl-type of crystal structure, form

hydrides containing up to 1.4 H/f.u. and the hydrogenation leads to a drastic reduction of magnetic ordering

temperatures. The crystallographic characteristics of RNiAl compounds and of their hydrides or deuterides

were reported.

[1997Ehl] investigated magnetic order in rare-earth based intermetallic compounds of the series RNiAl

(R = Pr, Nd, Tb, Dy, Ho), by means of neutron diffraction and susceptibility measurements.

[2002Lam] measured magnetic moments as a function of temperature in a magnetic field of 0.04T for

DyNi5-xAlx alloys (x = 0; 1; 1.5; 2; 2.5; 3). Magnetic parameters, magnetic behavior and cell dimensions

were reported.

[2002Bur] reported magnetic and X-ray photoelectron spectroscopy (XPS) measurements for DyNi5-xAlx.

[2002Dan] investigated the temperature changes of the lattice parameters in DyNiAl, using low temperature

X-ray powder diffraction: these changes were related to magnetic ordering of the compound. The values of

the refined structure parameter (for 300 and 50K) were reported and compared with those obtained from

powder neutron diffraction.

References

[1962Wer] Wernick, J.H., Haszko, S.E., Dorsi, D., “Pseudobinary Systems Involving Rare-Earth Laves

Phases”, J. Phys. Chem. Solids, 23, 567-572 (1962) (Crys. Structure, Experimental, 22)

[1968Dwi] Dwight, A.E., Mueller, M.H., Conner, R.A., Downey, J.W., Knott, H., “Ternary



[1969Vir] Virkar, A.V., Raman, A.J., “Crystal Structures of AB3 and A2B7 Rare-Earth - Nickel

Phases”, Less-Common Met., 18, 59-66 (1969) (Crys. Structure, Experimental)

[1970Bus] Buschow, K.H.J., van der Goot, A.S., “The Crystal Structure of Rare-Earth - Nickel

Compounds of the type R2Ni7”, J. Less-Common Met., 22, 419-428 (1970) (Crys. Structure,

Experimental, 10)

[1970Leo] Leon, B., Wallace, W.E., “Magnetic and Structural Characteristics of Ternary Intermetallic

Systems Containing Lanthanides”, J. Less-Common Met., 22, 1-10 (1970) (Crys. Structure,


[1972Ryk] Rykhal, R.M., Zarechnyuk, O.S., Pyshchick, G.V., “New Ideas on the MgCuAl2-Structure

Type” (in Russian), Visn. L’viv. Derz. Univ., Ser. Khim., 14, 13-15 (1972) (Crys. Structure,

Experimental, 3)

[1973Oes] Oesterreicher, H., “Structural and Magnetic Studies on Rare-Earth Compounds RNiAl and

RCuAl”, J. Less-Common Met., 30, 225-236 (1973) (Crys. Structure, Magn. Prop.,

Experimental, 21)

235


MSIT®

Al–Dy–Ni

[1973Ryk] Rykhal’, R.M., Zarechnyuk, O.S., Pyshchik. G.V., “New Representatives of the MgCuAl2and YNiAl4 Types of Structure” (in Russian), Dop. Akad. Nauk Ukr. RSR, Fiz-Mat. Tekh.,

(6), 568-570 (1973) (Crys. Structure, Experimental, 2)

[1973Zar] Zarechnyuk, O.S., Rykhal, R.M., Vivchar, O.I., “Laves Phases in Ternary Systems

Rare-Earth Metal-Transition Metal of the IV Period-Aluminium”, Sb. Nauch. Rabot Inst.

Metallofiz., Akad. Nauk Ukr. SSR, (42), 92-94 (1973) (Crys. Structure, Experimental,

Review, 22)

[1977Ryk] Rykhal, R.M., “The Crystal Structure of Y3Ni6Al2 and Relative Compounds”, Vestn. L’vov.

Univ. Ser. Khim., 19, 34-36 (1977) (Crys. Structure, Experimental)

[1978Ryk] Rykhal, R.M., “New Representatives of Structural Types Ce3Co8Si and Mo2NiB2 in Rare

Earth-Ni-Al-Systems” (in Russian), Tret’ya Vses. Konf. Kristall. Intermetallicheskikh

Soyedineniy, 17 (1978) (Crys. Structure, Experimental, 0)

[1978Tak] Takeschita, T., Malik, S.K., Wallace, W.E., “Hydrogen Absorption in RNi4Al (R = Rare

Earth) Ternary Compounds”, J. Solid State Chem., 23, 271-274 (1978) (Crys. Structure,

Experimental, 8)

[1980Ryk] Rykhal, R.M., Zarechnyuk, O.S., Mandzin, V.M., “X-Ray Structural Studies of Terbium,

Dysprosium-Nickel-Aluminum Ternary Systems in the Range of 0-33.3 at.% Rare Earth

Metal” (in Ukrainian), Dopov. Akad. Nauk. Ukr. RSR, Ser. A: Fiz.- Mat.Tekh.Nauki, (12)

77-79 (1980) (Equi. Diagram, Crys. Structure, Experimental, 10)

[1981Zar] Zarechnyuk, O.S., Rykhal’, R.M., “The Crystal Structure of the Compound YNi2Al3 and

Related Phases” (in Russian), Vestn. L’vov. Univ. Ser. Khim., 23, 45-47 (1981) (Crys.


[1982Rom1] Romaka, V.A., Zarechnyuk, O.S., Rykhal, R.M., Yarmolyuk,Ya.P., Skolozdra, R.V.,

“Magnetic Susceptibility and Crystal Structure of RNiAl2 Compounds” Phys. Met. Metall.,

54(2), 191-193 (1982), translated from Fiz. Met. Metalloved., 54(2), 410-412 (1982) (Crys.


[1982Rom2] Romaka, V.A., Grin, Yu.N., Yarmolyuk, Ya.P,. Zarechnyuk, O.S., Skolozdra, R.V.,

“Magnetic and Crystallographic Parameters of R2Ni2Ga and R2Ni2Al Compounds” Phys.

Met. Metall. 54(4) 58-64, (1982), translated from Fiz. Met. Metalloved., 54(4), 691-696



Compounds RTAl (R = Rare Earth Metal, T = Cu, Ni)”, Inorg. Mater. (Engl. Trans.), 23(7),


[1987Tsv2] Tsvyashchenko, A.V., Fomicheva, L. N., “Crystallization of the Laves Phases Rare Earth

Nickel Aluminum (RNiAl) (C14 Type) at High Pressure”, J. Less-Common Met., 135(1),

L9-L12 (1987) (Crys. Structure, Experimental, 10)

[1992Mur] Murakami, Y., Otsuka, K., Hanada, S., Watanabe, S., “Crystallography of Stress-Induced

B2 7R Martensitic Transformation in a Ni-37.0 at.% Al Alloy”, Mater. Trans., JIM, 33(3),


[1993Gla] Gladyshevskii, R.E., Cenzual, K., Flack, H.D., Parthé, E., “Structure of RNi3Al9 (R=Y, Gd,

Dy, Er) with either Ordered or Partly Disordered Arrangement of Al-Atom Triangles and

Rare Earth Metal Atoms”, Acta Cryst., B49, 468-474 (1993) (Crys. Structure,

Experimental, 9)

[1994Mur] Murthy, A.S., Goo, E., “Triclinic Ni2Al Phase in 63.1 at.% Al”, Met. Mater. Trans., A,

25A(1), 57-61 (1994) (Crys. Structure, Experimental, 10)

[1995Sor] Sorgic, B., Drasner, A., Blazina, Z., “On the Structural and Thermodynamic Properties of

the DyNi5-xAlx -Hydrogen System”, J. Phys. Condens. Matter., 7, 7209-7215 (1995) (Crys.

Structure, Thermodyn., Experimental, 20)

[1997Ehl] Ehlers,G., Maletta, H., “Frustrated Magnetic Moments in RNiAl Intermetallic Compounds”

Physica B, 234-236, 667-669 (1997) (Crys. Structure, Magn. Prop., Experimental, 4)

[1997Kol] Kolomites, A.V., Havela, L., Yarys, V.A., Andreev, A.V., “Hydrogen

Absorption-Desorption, Crystal Structure and Magnetism in RENiAl Intermetallic

236


MSIT®

Al–Dy–Ni

Compounds and their Hydrides”, J. Alloys Compd., 253-254, 343-346 (1997) (Crys.


[2000Oka] Okamoto, H., “Desk Handbook Phase Diagrams for Binary Alloys, ASM International,

Materials Park, O.H. 44073-0002, (2000) (Equi. Diagram, Review)

[2002Bur] Burzo, E., Chiuzbaian, S.G., Neumann, M., Valeanu, M., Chioncel, L., Creanga, I.,

“Magnetic and Electronic Properties of DyNi5-xAlx Compounds”, J. Appl. Phys. 92(12),

7362-7368 (2002) (Electr. Prop., Experimental, 31)

[2002Dan] Danis, S., Javorsky, P., Rafaja, D., “Magneto-Crystalline Anisotropy in TbPdIn, DyNiAl

and GdNiAl Studied by Using X-ray Powder Diffraction at Low Temperatures”, J. Alloys

Compd., 345, 10-15 (2002) (Experimental, 8)

[2003Gry] Grytsiv, A., “Al-Dy (Aluminium-Dysprosium)”, MSIT Binary Evaluation Program, in


GmbH, Stuttgart; Document ID 20.20073.1.20 (2003) (Crys. Structure, Equi. Diagram,

Assessment, 8)

[2002Lam] Lambrick, D.B., Blazina, Z., Hoon, S.R., “On Magnetic Properties of DyNi5-xAlx (x = 0, 1,

1.5, 2, 2.5, 3) Intermetallics”, J. Mat. Sci. Lett., 21, 807-809 (2002) (Crys. Structure, Magn.







Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

dissolves 0.01 at.% Ni at 639.9°C

[Mas2]

(Ni)

< 1455

cF4

Fm3m

Cu

a = 352.40 at 25°C [Mas2]

dissolves 20.2 at.% Al at 1362°C [Mas2]

~14 at.% at 800°C [2000Oka]

( Dy) hR3

R3m

Sm

a = 343.6

c = 2483

at 25°C, 7.5 GPa

[Mas2]

given as CdCl2-type [Mas2]

given as Sm-type [V-C2]

( Dy)

1412-1381

cI2

Im3m

W

a = 398.0 [Mas2]

( Dy)

< 1381-(-187)

hP2

P63/mmc

Mg

a = 359.15

c = 565.01

[Mas2]

( ’Dy)

<-187

oC4

Cmcm

’Dy

a = 359.5

b = 618.4

c = 567.8

[Mas2]

237


MSIT®

Al–Dy–Ni

DyAl3< 1005

hP16

P63/mcm

TiNi3

a = 609.1

c = 953.3

[V-C2]

DyAl31090-1005

hR60

Rm

HoAl3

a = 608.0

c = 3594.0

[V-C2]

Dy(Al1-xNix)2

DyAl2 < 1500

cF24

Fd3m

MgCu2

a = 784 to 773

a = 783.6

a = 784.0

0 x 0.19 [1970Leo]

0 x 0.22 [1980Ryk]

[2003Gry]

[2003Gry]

DyAl

< 1100

oP16

Pbcm

ErAl

a = 582.2

b = 1137

c = 560.4

a = 582.3

b = 1134

c = 559.3

[2003Gry]

[2003Gry]

Dy3Al2< 1025

tP20

P42/mnm

Zr3Al2

a = 816.7

c = 754.1

a = 820.2

c = 755.4

[2003Gry]

[2003Gry]

Dy2Al

< 990

oP12

Pnma

Co2Si

a = 654.3

b = 507.5

c = 939.7

a = 653.0

b = 507.7

c = 937.6

[2003Gry]

[2003Gry]

Dy3Ni

< 762

oP16

Pnma

Fe3C

a = 685

b = 960

c = 626

[V-C2]

Dy3Ni2< 928

mC20

C2/m

Dy3Ni2

a =1332.1

b = 366.2

c = 951.2

= 105.72°

[V-C2]

DyNi

< 1248

oP8

Pnma

FeB

a = 703

b = 417

c = 544

[V-C2]

DyNi2< 1258

cF24

Fd3m

MgCu2

a = 716 [V-C2]

DyNi3< 1283

hR36

R3m

NbBe3

a = 495.9

c = 2437.9

[V-C2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

238


MSIT®

Al–Dy–Ni

Dy2Ni7< 1307

hP36

P63/mmc

Ce2Ni7

a = 493

c = 2405

[V-C2]

Dy2Ni7< ?

hR54

R3m

Er2Co7

a = 492.8

c = 3618

[V-C2]

DyNi4< 1336

[2000Oka]

Dy4Ni17

< 1352

[2000Oka]

Dy(Ni1-xAlx)5

DyNi5 < 1387

hP6

P6/mmm

CaCu5

a = 489.6

c = 396.5

a = 503.5

c = 403.5

a = 487.56

c = 396.73

0 x 0.4 [1980Ryk]

at 0 at.% Al [1980Ryk]

~30 at.% Al [1980Ryk]

[V-C2]

Dy2(Ni1-xAlx)17

Dy2Ni17

< 1321

hP38

P63/mmc

Th2Ni17 a = 829.9

c = 803.7

0 x 0.04 read from a diagram

[1980Ryk]

[V-C2]

NiAl3< 856

oP16

Pnma

Fe3C

a = 661.3 0.01

b = 736.7 0.01

c = 481.1 0.01

[2003Sal]

Ni2Al3< 1138

hP5

P3m1

Ni2Al3

a = 402.8

c = 489.1

36.8 to 40.5 at.% Ni [Mas2]

[2003Sal]

Ni3Al4< 702

cI112

Ia3d

Ni3Ga4

a = 1140.8 0.01 [V-C2]

NiAl

< 1651

cP2

Pm3m

CsCl

a = 286.0

a = 287

a = 288.72 0.02

a = 287.98 0.02

at 42 to 69.2 at.% Ni [Mas2]

~45 to 60 at.% Ni [2000Oka]

[2003Sal]:

at 63 at.% Ni

at 50 at.% Ni

at 54 at.% Ni

Ni5Al3< 723

oC16

Cmmm

Pt5Ga

a = 753

b = 661

c = 376

63 to 68 at.% Ni [Mas2]

at 63 at.% Ni [2003Sal]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

239


MSIT®

Al–Dy–Ni

Ni3Al

< 1372

cP4

Pm3m

AuCu3 a = 356.77

a = 358.9

a = 356.32

a = 357.92

73 to 76 at.% Ni [Mas2]

[2003Sal]:

at 63 at.% Ni

disordered

ordered

Ni2Al9 mP22

P21/a

Co2Al9

a = 868.5 0.06

b = 623.2 0.06

c = 618.5 0.04

= 96.50 0.05°

Metastable

[2003Sal]

NixAl1-x tP4

P4/mmm

AuCu

m**

a = 383.0

c = 320.5

a = 379.5

c = 325.6

a = 379.5

c = 325.6

a = 375.1

c = 330.7

a = 379.9 to 380.4

c = 322.6 to 323.3

a = 371.7 to 376.8

c = 335.3 to 339.9

a = 378.00

c = 328.00

a = 418

b = 271

c = 1448

= 93.4°

Martensite, metastable; 0.60 < x < 0.68

[2003Sal]:

at 62.5 at.% Ni,

at 63.5 at.% Ni,

at 66.0 at.% Ni,

at 64 at.% Ni,

at 65 at.% Ni,

[1992Mur]

Ni2Al hP3

P3m1

CdI2

aP126

P1

a = 407

b = 499

a = 1252

b = 802

c = 1526

= 90°

= 109.7°

= 90°

Metastable

[2003Sal]

[1994Mur]

D1 Decagonal

Metastable, [2003Sal]

D4 Decagonal

Metastable, [2003Sal]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

240


MSIT®

Al–Dy–Ni

* 1, DyNi3Al16 oC*

Cmcm

a = 402.1

b = 1586

c = 2701

[1980Ryk]

* 2, DyNi3Al9 hR78

R32

ErNi3Al9

a = 727.23 ± 0.09

c = 2734.4 ± 0.06

[1993Gla]

with partly disordered arrangement of Al

and Dy atoms

* 3, DyNi2Al3 hP18

P6/mmm

YNi2Al3

or hP18

Ho2Ni5Ga5

a = 892

c = 393.6

a = 903

c = 407

[1973Ryk, 1980Ryk]

[1981Zar]

according to

[2002Bur]

* 4, Dy2Ni3Al7 hP* a =1782

c = 398.8

[1973Ryk, 1980Ryk, 1981Zar]

* 5, DyNiAl4 oC24

Cmcm

YNiAl4

a = 405.6

b = 1513

c = 663

[1973Ryk, 1980Ryk, 1981Zar]

* 6, Dy3Ni8Al hP24

P63/mmc

Ce3Co8Si

a = 503.7

c =1610

[1973Ryk, 1980Ryk, 1982Rom2]

* 7, DyNiAl2 oC16

Cmcm

CuMgAl2(ord. Re3B)

a = 407.7

b = 1008

c = 693

a = 408

b =1015

c = 688

[1973Ryk, 1980Ryk]

[1982Rom1]

* 8, Dy3Ni6Al2 cI44

Im3m

Ce3Ni6Si2(ord. Ca3Ag8)

a = 891 [1980Ryk]

* 9, Dy(Ni1-xAlx)2

DyNiAl (I)

hP9

P62m

ord. Fe2P

or ZrNiAl

a = 699.39

c = 384.70

a = 699.4

c = 382.1

0.44 x 0.52 [1970Leo]

[1973Oes]

[1980Ryk]

* 10, Dy2Ni2Al oI10

Immm

Mo2NiB2

a = 538.8

b = 833.3

c = 417.3

a = 833.8

b = 538.8

c = 417.3

[1980Ryk, 1982Rom2]

[V-C2]

* 11, DyNiAl (II) hP12

P63/mmc

MgZn2

a = 538.3

c = 854.9

[1987Tsv1] and [1987Tsv2]

high pressure phase

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

241


MSIT®

Al–Dy–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Dy Ni


Axes: at.%

Ni3Al

NiAl

Ni2Al3

NiAl3

DyAl3

DyAl2

Dy2Ni17

DyNi5Dy2Ni7

DyNi3DyNi2

τ1

τ5

τ3

τ4

τ7

τ9

τ10 τ8

τ6

L

τ2

(Ni)

Fig. 1: Al-Dy-Ni.

Partial isothermal

section up to 33 at.%

Dy at 800°C

242


MSIT®

Al–Er–Fe

Aluminium – Erbium – Iron

Bernd Grieb, updated by Alexander Pisch

Literature Data

Two ternary phases were observed besides solid solutions based on binary compounds. The ternary phase

ErFeAl [1971Oes1, 1971Oes2, 1973Zar] and the section along ErAl2-ErFe2 [1971Oes2, 1973Zar, 1974Oes,

1975Dwi, 1977Gua] are well investigated regarding structural and magnetic properties. The structural and

magnetic properties of ErFe4+xAl8-x have been studied at x=0 [1973Zar, 1974Viv, 1976Bus, 1988Sch,

1995Cac, 1998Hag], x=2 [1981Fel, 1988Che, 1998Sch] and x=3 [2000Sch, 2001Sch] using X-ray and

neutron diffraction. Magnetic properties were studied as a function of temperature and composition by the

Faraday method and by SQUID/Vibrating Sample magnetometer. Stoichiometric samples have been

prepared by arc melting of the elements in argon atmosphere and subsequent anneal at 850°C for 10-30d

(ErFe7Al5) [2000Sch] or 800°C for 7d (ErFe6Al6) [1998Sch]. [1998Hag] measured the specific heat from

1.5K to 200K on ErFe7Al5 samples prepared in an arc furnace in reduced Ar atmosphere starting from the

elements (purity > 99.9 mass%) followed by a vacuum anneal at 800°C for several weeks. The

Er2(Fe1-xAlx)17 solid solution has been studied using X-ray and neutron diffraction [1992Jac, 1996Cha,

1998Che, 1998Wan, 2001Yan]. Samples were prepared by arc melting from the pure elements (99.9 mass%

purity) and annealed at 1127°C for 120h followed by a water quench [1998Che],1100°C for 24h [1996Cha],

900°C for 10h [1998Wan] or 500°C for 720h [2001Yan]. In order to determine the exact phase limits,

[2001Yan] varied the Er content from 5 to 15 at.% and an isothermal section at 500°C in the Fe-rich corner

has been constructed based on the XRD results. The magnetic intersublattice constant JErFe for

Er2(Fe1-xAlx)17 has been determined as function of the composition by the high field powder method

(HFFO) by [1994Liu]. [1998Thi] studied the structure and magnetic properties of ErFe2Al10 by X-ray

diffraction and SQUID magnetometry. The sample has been prepared slightly Al-rich by melting the

elements (Fe: 99.5 mass%, Er, Al 99.9 mass%) in Al2O3 crucibles which were sealed in quartz tubes and

annealed for 400h at 800°C. The remaining Al has been removed by hydrochloric acid. [1972Zar] presented

an isothermal section up to 33.3 at.% Er which was investigated by means of X-ray and microscopic

analysis.

Binary Systems

The binary Al-Fe system is taken from [2003Pis], Er-Fe and Al-Er are accepted from [Mas]. Er-Fe from

[1972Zar] is not in agreement with [Mas] because the ErFe3 compound has been neglected.

Solid Phases

The ternary Laves phase ErFeAl ( 3) has the MgZn2 structure and is different from the solid solutions of

the two binary compounds ErAl2 and ErFe2 which crystallize in the MgCu2 prototype. The homogeneity

ranges of theses two binary intermetallics have been determined by [1971Oes2, 1974Oes] and are in good

agreement with the results of [1975Dwi]. The second known ternary phase ErFe4+xAl8-x ( 4) has the

ThMn12 structure [1976Bus]. Aluminium can be substituted by Fe at least up to x=2 [1981Fel, 1988Che,

1998Sch]. Lattice parameters for ErFe4Al8 [1974Viv, 1976Bus, 1988Sch, 1995Cac] are in good agreement.

The Er2(Fe17-xAlx) solid solution crystallizes in different crystallographic structures: hexagonal Th2Ni17 for

0 < x < 4 (0 to 21 at.% Al) and rhombohedral Th2Zn17 for 4 < x < 9 (21 to 47.4 at.% Al) assuming a

stoichiometric Er content (10.5 at.%) and after annealing at 1100/1127°C [1996Cha, 1998Che]. Annealing

at 500°C stabilizes a new TbCu7 type structure around 27 at.% Al [2001Yan], the hexagonal variant being

stable from 0 to 25 at.% Al and the rhombohedral from 30 to 37 at.% Al. [2001Yan] investigated also lower

and higher Er contents leading to the hexagonal type from 0 to 27 at.% Al, TbCu7 type from 30 to 32 at.%

Al and rhombohedral from 35 to 40 at.% Al for an Er content of 9.5 at.% and only rhombohedral from 22

243


MSIT®

Al–Er–Fe

to 35 at.% Al for an Er-content of 11.5 at.%. The lattice parameters from [1992Jac, 1996Cha, 1998Che,

2001Yan] are in good agreement. The ternary phase ErFe2Al10 ( 5) has a YbFe2Al10 prototype structure

[1998Thi]. Details of crystal structure of solid phases are given in Table 1.

Isothermal Sections

An isothermal section up to 33.3 at.% Er based on the work of [1972Zar, 2001Yan] is reproduced in Fig. 1.

The homogeneity ranges of the MgCu2 and MgZn2 types given by [1972Zar] have been corrected to be in

agreement with [1975Dwi] and [1974Oes].


The magnetic coupling constants for Er2Fe10Al7 / Er2Fe9Al8 at 4.2K are nRT=2.27 / 2.54 (Tf.u./ B) and JRT/

k = -8.16/-9.16 K [1992Jac]. Er2Fe15Al2 has a Curie temperature of 383K [1998Wan]. ErFe6Al6 presents a

paramagnetic to ferrimagnetic phase transition at 340K [1998Sch]. ErFe2Al10 ( 5) has probably a

metamagnetic type behavior with a Néel temperature below 15K and an effective magnetic moment of

9.5(1) B [1998Thi].

References



Experimental, 49)

[1961Lih] Lihl, F., Ebel, H., “X-Ray Examination of the Constitution of Iron-Rich Alloys of the

Iron-Aluminium System” (in German), Arch. Eisenhuettenwesen, 32, 483-487, (1961)


[1971Oes1] Oesterreicher, H., “Structural Studies of Rare Earth Compounds RFeAl”, J. Less-Common


[1971Oes2] Oesterreicher, H., “Structural and Magnetic Studies on ErFe2-ErAl2”, J. Appl. Phys., 42,


[1972Zar] Zarechnyuk, O.S., Vivchar, O.I., Ryabov, V.R., “An X-ray Study of the Er-Fe-Al System

for Er Contents up to 33.3 at.%” (in Russian), Vestn. L'vov Univ., Ser. Khim., 14, 16-19

(1972) (Experimental, Crys. Structure, Equi. Diagram, #, 9)

[1973Zar] Zarechnyuk, O.S., Rikhal' R.M., Vivchar, O.I., “Laves Phases in Ternary Systems of the

Type Rare Earth Metal - Transition Metal - Al” (in Russian), Akad. Nauk Ukr. SSR,

Metallofizika., 46, 92-94 (1973) (Experimental, Crys. Structure, 22)

[1974Oes] Oesterreicher, H., “Constitution of Al Base Rare Earth Alloys RT2-RAl2 (R = Pr, Gd, Er; T

= Mn, Fe, Co, Ni, Cu)”, Inorg. Chem., 13, 2807-2811 (1974) (Experimental, Crys.

Structure, 30)

[1974Viv] Vivchar, O.I., Zarechnyuk, O.S., “Compounds of the ThMn12- Type Structure in R-Fe-Al

Systems” (in Russian), Tezisy. Dokl. Vses. Konf. Kristallokhim. Intermet. Soedin., Rykhal,

R.M., (Ed.), L'vov. Gos. Univ.: Lvov, 2nd, 41, (1974) (Experimental, Crys. Structure, 0)

[1975Dwi] Dwight, A.E., Kimball, C.W., Preston, R.S., Taneja S.P., Weber, L., “Crystallographic and


40, 285-291 (1975) (Experimental, Crys. Structure, 8)

[1976Bus] Buschow, K.H.J., van Vucht J.H.N., van Den Hoogenhof, W.W., “Note on the Crystal


J. Less-Common Met., 50, 145-150 (1976) (Experimental, Crys. Structure, 2)

[1977Gua] Gualtieri, D.M., Wallace, W.E., “Hydrogen Capacity and Crystallography of ErFe2-Based

and ErCo2-Based Ternary Systems”, J. Less-Common Met., 55, 53-59 (1977)


244


MSIT®

Al–Er–Fe


RFe6Al6 (R = Rare Earth)”, J. Phys. Chem. Solids, 42, 369-377 (1981) (Experimental, Crys.

Structure, 6)


Investigations of Rare Earth- Aluminium-Iron (REAl6Fe6) Compounds for RE = Yttrium,



[1988Gsc] Gschneidner Jr, K.A., Calderwood, F.W., “The Al-Er (Aluminum-Erbium) System”, Bull.

Alloy Phase Diagrams, 9, 676-678 (1988) (Equi. Diagram, Review, 29)


Rare Earth-Iron-Aluminum Compounds”, Mater. Sci. Forum, 27-28, 243-248 (1988)


[1989Kuz] Kuz'ma, Yu.B., Pan'kiv, T.V., “X-Ray Structural Study of the Er-Cu-Al System”, Russ.

Metall., (3), 208-210 (1989), translated from Izv. Akad. Nauk SSSR Met., (3), 218-219


[1992Jac] Jacobs, T.H., Buschow, K.H.J., Zhou, G.F., de Boer, F.R., “Intersublattice Interactions in

R2Fe17-xAlx Compounds (R = Tb, Dy, Er and Tm)”, Physica B, (Amsterdam), 179(3),

177-183 (1992) (Abstract, Crys. Structure, Magn. Prop., 15)

[1994Liu] Liu, J.P., de Boer, F.R., de Chatel, P.F., Coehoorn, R.,Buschow, K.H.J., “On the 4f-3d



[1995Cac] Caciuffo, R., Amoretti, G., Buschow, K.H.J., Moze, O., Murani, A.P., Paci, B., “Neutron

Spectroscopy Studies of the Crystal-field Interaction in RET4 Al8 Compounds (RE=Tb, Ho

or Er; T=Mn, Fe or Cu)”, J. Phys.: Condensed Matter, 7, 7981-7989 (1995) (Crys. Structure,

Experimental, 23)

[1996Cha] Chang W.C., Lu S.L., Chen S.K., Yao Y.D., “Structural and Magnetic Studies of

Er2Fe17-xMxCy (M=Ga and Al)”, J. Appl. Phys., 79(8), 5533-5535 (1996) (Crys. Structure,

Experimental, 9)



Experimental, 23)

[1998Che] Cheng, Z., Shen, B., Yan, Q., Guo, H., Chen, D., Gou, C., Sun, K., de Boer, F.R., Buschow,

K.,H.J., “Structure, Exchange Interactions, and Magnetic Phase Transition of Er2Fe17-xAlxIntermetallic Compounds”, Phys. Rev. B, 57(22), 14299-14309 (1998) (Crys. Structure,

Experimental, 35)

[1998Hag] Hagmusa I.H., Brueck E., de Boer F.R., Buschow K.H.J., “Magnetic Properties of RFe4Al8Compounds Studied by Specific Heat Measurements”, J. Alloys Compd., 278, 80-82 (1998)

(Experimental, Magn. Prop., 9)

[1998Sch] Schaefer, W., Kockelmann, W., Jansen, E., Fredo, S., Gal, J., “Structural Characteristics of

Rare Earth (R = Tb, Ho, Er) Ternary Magnetic Intermetallics RFexAl12-x with Iron

Concentrations x = 6”, Mater. Sci. Forum, 278-281, 542-547 (1998) (Crys. Structure,

Experimental, 14)

[1998Thi] Thiede, V.M.T., Ebel, T., Jeitschko, W., “Ternary Aluminides LnT2Al10

(Ln = Y,La-Nd,Sm,Cd-Lu and T = Fe,Ru,Os) with YbFe2Al10 Type Structure and Magnetic

Properties of the Iron-Containing Series”, J. Mater. Chem., 8(1), 125-130 (1998) (Crys.


[1998Wan] Wang, J., de Boer, F.R., Zhang, C., Brueck, E., Tang, N., Yang, F., “Structural and Magnetic

Properties of Er2Fe15M2 Compounds with M = Mn, Fe, Ni, Al, Ga and SI”, J. Magn. Magn.

Mater., 185, 345-352 (1998) (Crys. Structure, Experimental, Magn. Prop., 20)




245


MSIT®

Al–Er–Fe

[2000Sch] Schaefer, W., Barbier, B., Halevy, I., “ThMn12-Type Magnetic ErFe7Al5 and

Non-Magnetic YFe7Al5 Studied by X-ray and Neutron Diffraction”, J. Alloys Compd.,

303-304, 270-275 (2000) (Crys. Structure, Experimental, Magn. Prop., 7)




[2001Ike] Ikeda, O.,Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria and Stability of Ordered


(Equi. Diagram, Experimental, Mechan. Prop., 18)


Substitution and Rare-Earth Content on the Structure of R2(Fe1-xAlx)17 (R = Tb,Dy, Ho, Er)

Phases”, J. Alloys Compd., 320(1), 108-113 (2001) (Crys. Structure, Equi. Diagram,

Experimental, 9)

[2003Pis] Pisch, A., “Al-Fe (Aluminum-Iron)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart; to be published, (2003) (Equi. Diagram, Assessment, 58)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


( Fe)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

< 1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2] dissolves up to

1.2 at.% Al

( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12

at 25°C [Mas2]


0-18.8 at.% Al, HT [1958Tay]

0-19.0 at.% Al, HT [1961Lih]

0-18.7 at.% Al, 25°C [1999Dub]

(Er)

< 1529

hP2

P63/mmc

Mg

a = 355.92

c = 558.50

at 25°C [Mas2]

ErAl3< 1070

cP4

Pm3m

AuCu3

a = 421.4 [1988Gsc]

246


MSIT®

Al–Er–Fe

ErAl2< 1455

ErCuxAl2-x

cF24

Fd3m

Cu2Mg a = 779.3

a = 773.7

0 x 0.38 (~19 at.% ErCu2) at 600°C

[1989Kuz]

at x = 0 [1988Gsc, 1989Kuz]

at x = 0.38 [1989Kuz]

ErAl

< 1140

oP16

Pbcm

ErAl

a = 580.1

b = 1127

c = 557.0

[1988Gsc]

Er3Al2< 1060

tP20

P42/mnm

Gd3Al2

a = 812.3

c = 748.4

[1988Gsc]

Er2Al

< 1040

oP12

Pnma

Co2Si

a = 651.6

b = 501.5

c = 927.9

[1988Gsc]

Fe3Al14

< 1160

mC102

C2/m

Fe3Al14

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16-76.70 at.% Al [2003Pis]

sometimes called FeAl3 in the literature

at 76.0 at.% Al [2003Pis]

Fe2Al5< 1169

oC24

Cmcm

-

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [2003Pis]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [2003Pis]

1102 - 1232

cI16?

-

a = 598.0 at 61 at.% Al [2003Pis]

FeAl

< 1310

cP2

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5 - 47.5 at.% Al [1961Lih]

36.2 - 50.0 at.% Al [1958Tay]

39.7 - 50.9 at.% Al [1997Kog] 500°C

quenched in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

~24 - ~37 at.% Al [2001Ike]

23.1 - 35.0 at.% Al [1958Tay]

24.7 - 31.7 at.% Al [1961Lih]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [2003Pis]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

247


MSIT®

Al–Er–Fe

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [2003Pis]

[2003Pis]

FeAl4+x t** a = 884

c = 2160

(0 < x < 0.4) metastable

[2003Pis]

Er(FexAl1-x)2

ErAlr

cF24

Fd3m

MgCu2 a = 779.2

0 x 0.333 [1971Oes2]

(0 to 22.2 at.% Fe)

[V-C]

Er(Fe1-xAlx)2

ErFer

cF24

Fd3m

MgCu2 a = 728.3

0 x 0.363 [1971Oes2]

(0 to 24.2 at.% Al)

[V-C]

Er6(Fe1-xAlx)23 cF116

Fm3m

Th6Mn23

a = 1203 ± 2

a = 1213 ± 2

0 x 0.37 [1972Zar]

at x = 0, Er6Fe23

at Er6Fe14.5Al8.5

Er2(Fe1-xAlx)17

Er2Fe17

hP38

P63/mmc

Th2Ni17 a = 844 ± 2

c = 827 ± 2

a = 847.7

c = 830.3

a = 851.1

c = 831.9

a = 853.5

c = 833.9

0 x 0.3 at 9.5 at.% Er [2001Yan]

0 x 0.28 at 10.5 at.% Er [2001Yan]

at x = 0,

at Er2Fe16Al1 [1998Che]



* 1

Er2(Fe1-xAlx)17

hP*

P6/mmm

TbCu7

0.335 x 0.358 at 9.5 at.% Er;

x = 0.3 at 10.5 at.% Er [2001Yan]

* 2

Er2(Fe1-xAlx)17

hR57

R3m

Th2Zn17

a = 859.0

c = 1253.2

a = 861.8

c = 1257.6

a = 866.7

c = 1260.3

a = 871.0

c = 1262.2

a = 875.5

c = 1265.5

a = 878.2

c = 1273.1

0.39 x 0.45 at 9.5 at.% Er [2001Yan]

0.335 x 0.414 at 10.5 at.% Er;

0.246 x 0.391 at 11.5 at.% Er;







Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

248


MSIT®

Al–Er–Fe

* 3,

Er(Fe1-xAlx)2

ErFeAl

hP12

P63/mmc

MgZn2

a = 538.4

c = 870.7

0.382 x 0.645 [1971Oes2]

(41.2 to 23.7 at.% Fe,

25.5 to 43.0 at.% Al)

at x = 0.5 [1971Oes2, 1975Dwi]

* 4,

ErFe4+xAl8-x tI26

I4/mmm

ThMn12

a = 870.4

c = 503.8

a = 861.1

c = 501.1

a = 859.4(1)

c = 598.1(1)

0 x 1.6 [1972Zar]

at x = 0, ErFe4Al8 [1976Bus]

at x = 2, ErFe6Al6 [1988Che]

at x = 3, ErFe7Al5 [2001Sch] and 20°C

* 5, ErFe2Al10 oC36

YbFe2Al10

a = 895.8 ± 0.2

b = 1013.6 ± 0.3

c = 898.8 ± 0.3

[1972Zar]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

20

40

60

80

20 40 60 80

20

40

60

80

Er Fe


Axes: at.%

τ4

Fe4Al13Fe2Al5

FeAl2

FeAl

ErFe3Er2(Fe1-xAlx)17

Er(FexAl1-x)2

Er(Fe1-xAlx)2

τ5

ErAl3

τ1

τ2τ3

Fe3Al

(αFe)

(Al)

Er6(Fe1-xAlx)23

Fig. 1: Al-Er-Fe.


500°C

249


MSIT®

Al–Er–Ni

Aluminium – Erbium – Nickel

Riccardo Ferro, Gilda Zanicchi, Rinaldo Marazza

Literature Data

Investigations have been carried out on the intermediate phases, their crystal structures [1968Dwi,

1973Ryk, 1974Oes, 1981Zar, 1982Rom2, 1987Tsv2, 1998Jav], magnetic properties [1970Leo, 1972Oes,

1973Oes, 1982Rom1, 1996Jav, 2002Jav], and hydrogen absorption characteristics [1978Tak, 1996Sor].

Most of the samples were annealed at temperatures between 600 and 900°C.

An investigation of the section ErNi2-ErAl2 was carried out by [1970Leo] who investigated structural and

magnetic properties of the ErNiAl intermediate phase together with the mutual solubility of ErNi2 - and

ErAl2. A systematic investigation of phase equilibria at 800°C and in the range of 0 to 33 at.% Er was made

by [1982Zar]. In this study, 49 alloys were prepared from 99.98Al, 99.9Ni and 99.6 mass% Er by arc

melting under purified argon. The alloys were annealed at 800°C for 700 h and then quenched in ice-water.

A high pressure modification of ErNiAl (MgZn2 type) has been prepared from the powder components at

1450 to 1500°C at a pressure of 7.7 GPa [1987Tsv1]. The same information is also given in [1987Tsv2].

Gladyshevskii et al. [1993Gla] determined the structure of the ErNi3Al9 compound which crystallizes in the

rhombohedral hR78 - ErNi3Al9 type. The present evaluation updates and completes the evaluation made

earlier by [1991Fer] in the MSIT Evaluation Program.

Binary Systems

The present evaluation of ternary data is consistent with the description of the edge binary Al-Er by

[2003Ria], the Er-Ni by [2000Oka] and the Al-Ni diagram as published by [2003Sal] except for the fact that

the phases Er5Ni22, Er4Ni17 and ErNi4 listed by [2000Oka] are omitted as they could not been detected by

[1982Zar].

Solid Phases

Special attention was dedicated to the 0 to 33 at.% Er composition range. Several solid phases pertaining to

this composition field have been described. Their structural properties are summarized in Table 1. For the

ErNi2 - based phase, a solubility of 8.5 mole% ErAl2 was proposed by [1970Leo] in the investigation of the

system ErNi2-ErAl2, however, the negligible solubility suggested by [1982Zar] is presented in Fig. 1.

Magnetic properties of the two terminal solid solutions are given for various compositions by [1970Leo].

According to [1973Oes] and [1982Zar] ErNiAl ( 9) is a point phase. However, [1970Leo] found a range of

homogeneity between 50 and 60 mole% ErAl2.

Isothermal Sections

The partial isothermal section at 800°C, given in Fig. 1, is mainly based on the data of [1982Zar] who used

long homogenizing annealing periods, followed by quenching in cold water. However, [1982Zar] did not

report in his work the ErNi3Al9 phase identified later by [1993Gla]. We introduced this phase in Fig. 1 as

2 with possible tie-lines. The equilibria with the melt in the Al corner have not been investigated.

[1996Sor] investigated the substitution of aluminium for nickel. Nickel may be replaced by aluminium up

to the composition ErNi3Al2 without changing the crystal prototype, i.e. the CaCu5 type structure. However

beyond this composition and up to ErNi2Al3 exists a ternary single phase with a structure of the YCo3Ga2

type (possibly a high temperature phase: the alloys were annealed at about 1000°C).

Miscellaneous

Magnetic properties of the Al-Er-Ni alloys, and more generally of Al-Ni-Rare Earth alloys, have been

discussed in several papers. [1970Leo] studied RNi2-xAlx alloys; Er2Ni2Al and ErNiAl2 have been studied

250


MSIT®

Al–Er–Ni

by [1982Rom1, 1982Rom2]. Hydrogen adsorption in RNi4Al alloys has been studied by [1978Tak].

[1996Jav] studied polycrystalline samples of ErNiAl by powder neutron diffraction and by susceptibility

measurements. [1996Sor] investigated the substitution of aluminium for nickel and its effect on the

structural and hydrogen absorption properties of ErNi5-xAlx system. It was found that all ternary alloys

having the CaCu5 structure absorb between 1.95 and 2.95 hydrogen atoms per formula unit at room

temperature. These authors reported also crystallographic and thermodynamic data for ErNi5-xAlx-

hydrogen system .

[1997Kol] studied hydrogen absorption-desorption, crystal structure and magnetism in intermetallic

compounds of the series RNiAl (R = Y, Gd, Tb, Dy, Er, Lu). These compounds, crystallizing in the ZrNiAl

type of crystal structure, form hydrides containing up to 1.4 H by formula unit and the hydrogenation leads

to a drastic reduction of the magnetic ordering temperatures.

[1998Jav] presented an inelastic neutron scattering study of the crystal field in the ErNiAl intermetallic

compound. The results were compared with the specific heat data and the lower portion of the crystal-field

energy level scheme was determined.

[2002Jav] presented a study of the crystal field and electronic structure in an ErNiAl intermetallic alloy

based on inelastic neutron spectroscopy, magnetic susceptibility, specific heat data and first-principles

density-functional calculations.

References

[1968Dwi] Dwight, A.E., Mueller, M.H., Conner, R.A., J.R., Downey, Knott, H., “Ternary Compounds

with the Fe2P-Type Structure”, Trans. Met. Soc. AIME, 242, 2075-2080 (1968) (Crys.


[1970Leo] Leon, B., Wallace, W.E., “Magnetic and Structural Characteristics of Intermetallic Systems

Containing Lanthanides”, J. Less-Common Met., 22, 1-10 (1970) (Crys. Structure,

Experimental, 13)

[1972Oes] Oesterreicher, H., “Metamagnetism in ErNiAl and TmNiAl”, Phys. Status Solidi A, 12,

K109-K110 (1972) (Experimental, 2)


RCuAl”, J. Less-Common Met., 30, 225-236 (1973) (Crys. Structure, Experimental, Magn.

Prop., 21)

[1973Ryk] Rykhal, R.M., Zarechnyuk, O.S., Pyshchik, G.V., “New Representatives of MgCuAl2 and

YNiAl2 Structural Types” (in Ukrainian), Dop. Akad. Nauk Ukr. RSR. Ser. A, Fiz.-Mat.

Tekh. Nauki, 35(6), 568-570 (1973) (Crys. Structure, Experimental, 2)

[1974Oes] Oesterreicher, H., “Constitution of Aluminum Base Rare Earth Alloys RT2-RAl2 (R = Pr,

Gd, Er; T = Mn, Fe, Co, Ni, Cu)”, Inorg. Chem., 13, 2807-2811 (1974) (Crys. Structure,


[1978Tak] Takeshita, T., Malik, S.K., Wallace, W.E., “Hydrogen Absorption in RNi4Al (R = Rare

Earth) Ternary Compounds”, J. Solid State Chem., 23, 271-274 (1978) (Crys. Structure,

Experimental, 8)

[1981Zar] Zarechnyuk, O.S., Rykhal, R.M., “The Crystal Structure of the YNi2Al3 Compound and its

Related Phases” (in Russian), Vestn. L'vov. Univ., Ser. Khim., 23, 45-47 (1981) (Crys.


[1982Rom1] Romaka, V.A., Zarechnyuk, O.S., Rykhal, R.M., Yarmolyuk, Ya.P., Skolozdra, R.V.,

“Magnetic Susceptibility and Crystal Structure of RNiAl2 Compounds”, Phys. Met.

Metallogr., 54(2), 191-193 (1982), translated from Fiz. Met. Metalloved., 54, 410-412


[1982Rom2] Romaka, V.A., Grin, Yu.A., Yarmolyuk, Ya.P., Zarechnyuk, O.S., Skolozdra, R.V.,

“Magnetic and Crystallographic Parameters of R2Ni2Ga and R2Ni2Al Compounds”, Phys.

Met. Metallogr., 54(4), 58-64 (1982), translated from Fiz. Met. Metalloved., 54, 691-696


251


MSIT®

Al–Er–Ni

[1982Zar] Zarechnyuk, O.S., Rykhal, R.M., Romaka, V.A., Kovalska, O.K., Shazabura, G.I.,

“Isothermal Sections of the Holmium, Erbium-Nickel-Aluminium Ternary Systems at

800°C in the 0 to 0.333 Atomic Fraction Range of the Rare-Earth Metal” (in Ukrainian),

Dop. Akad. Nauk Ukr. RSR, Ser. A, Fiz.-Mat. Tekh. Nauki, (1), 81-83 (1982) (Crys.

Structure, Equi. Diagram, Experimental, #, *, 11)

[1986Hua] Huang, S.C., Briant, C.L., Chang, K.-M., Taub, A.I., Hall, E.L., “Carbon Effects in Rapidly

Solidified Ni3Al”, J. Mater. Res., 1(1), 60-67 (1986) (Experimental, Mechan. Prop., 27)

[1987Tsv1] Tsvyashchenko, A.V., Fomicheva, L.N., “Crystallization of the Laves Phases RNiAl (C14

Type) at High Pressure”, J. Less-Common Met., 135, L9-L12 (1987) (Crys. Structure,

Experimental, 10)


Compounds RTAl (R = Rare Earth Metal, T = Cu, Ni)”, Inorg. Mater., 23, 1024-1027

(1987), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 23, 1148-1152 (1987) (Crys.


[1988Li] Li, F., Ardell, A.J., “The Incoherent / ' Solvus in Ni-Al Alloys”, J. Phase Equilib., 19(4),

334-339 (1998) (Equi. Diagram, Theory, Calculation, 25)



[1991Fer] Ferro R., Zanicchi, G., Marazza, R., ”Al-Er-Ni (Aluminium - Erbium - Nickel),” MSIT

Ternary Evaluation Program, in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials

Science International Services GmbH, Stuttgart; Document ID: 10.13103.1.20, (1991)

(Crys. Structure, Equi. Diagram, Assessment, 15)

[1991Kim] Kim, Y.D., Wayman, C.M., “Transformation and Deformation Behavior of Thermoelastic

Martensite Ni-Al Alloys Produced by Powder Metallurgy Method” (in Korean), J. Korean

Inst. Met. Mater., 29(9), 960-966 (1991) (Mechan. Prop., Experimental, 15)


B2→7R Martensitic Transformation in a Ni-37.0 at.% Al Alloy”, Mater. Trans., JIM, 33(3),


[1993Gla] Gladyshevskii, R.E., Cenzual, K., Flack, H.D., Parthé, E., “Structure of RNi3Al9 (R = Y,

Gd, Dy, Er) with Either Ordered or Partly Disordered Arrangement of Al-Atom Triangles

and Rare-Earth-Metal Atoms”, Acta Crystallogr., Sect. B: Struct. Cystallogr. Cyst. Chem.,

B49, 468-474 (1993) (Crys. Structure, Experimental, 9)

[1993Kha] Khadkikar, P.S., Locci, I.E., Vedula, K., Michal, G.M., “Transformation to Ni5Al3 in a

63.0 at.% Ni-Al Alloy”, Metall. Trans. A, 24A, 83-94 (1993) (Equi. Diagram, Crys.


[1994Mur] Murthy, A.S., Goo, E., “Triclinic Ni2Al Phase in 63.1 at.% NiAl”, Metal. Mater. Trans. A,

25A(1), 57-61 (1994) (Crys. Structure, Experimental, 10)

[1996Jav] Javorsky, P., Burlet, P., Ressouche, E., Sechovsky, V., Michor, H., Lapertot, G., “Magnetic

Structure Study of ErCuAl and ErNiAl”, Physica B, 225 230-236, (1996) (Crys. Structure,



Ni1+xAl1-x”, Acta Crystallogr., Sect. A: Found. Crystallogr., A52, C319 (1996) (Crys.


[1996Sor] Sorgic, B., Drasner, A., Blazina, Z., “The Effect of Aluminium on the Structural and

Hydrogen Sorption Properties of ErNi5”, J. Alloys Compd., 232, 79-83 (1996) (Crys.

Structure, Experimental, Equi. Diagram, 22)

[1996Vik] Viklund, P., Häußermann, U., Lidin, S., “NiAl3: a Structure Type of its Own?”, Acta

Crystallogr., Sect. A: Found. Crystallogr., A52, C-321 (1996) (Crys. Structure,




252


MSIT®

Al–Er–Ni

[1997Kol] Kolomites, A.V., Havela, L., Yarys, V.A., Andreev, A.V., “Hydrogen Absorption-

Desorption, Crystal Structure and Magnetism in RENiAl Intermetallic Compounds and

their Hydrides”, J. Alloys Compd., 253-254, 343-346 (1997) (Crys. Structure, Experimental,

Magn. Prop., 13)

[1997Poh] Pohla, C., Ryder, P.L., “Crystalline and Quasicrystalline Phases in Rapidly Solidified Al-Ni

Alloys”, Acta Mater., 45, 2155-2166 (1997) (Experimental, Crys. Structure, 48)

[1997Pot] Potapov, P.L., Song, S.Y., Udovenko, V.A., Prokoshkin, S.D., “X-Ray Study of Phase

Transformations in Martensitic Ni-Al Alloys”, Metall. Mater. Trans. A, 28A, 1133-1142


[1997Vil] Villars, P., Prince, A., Okamoto, H., Handbook of Ternary Alloy Phase Diagrams, ASM

International, Materials Park, OH, 3, 3480 (1997) (Equi. Diagram)

[1998Jav] Javorsky, P., Nakotte, H., Robinson, R.A., Kelley, T.M., “Crystal Field in ErNiAl Studied

by Inelastic Neutron Scattering”, J. Magn. Magn. Mater., 186, 373-376 (1998) (Crys.




57(2), 862-869 (1998) (Thermodyn., Theory, Calculation, 43)

[1998Sim] Simonyan, A.V., Ponomarev, V.I., Khomenko, N.Yu., Vishnyakova, G.A., Gorshkov, V.A.,

Yukhvid, V.I., “Combustion Synthesis of Nickel Aluminides”, Inorg. Mater., 34(6), 558-

561 (1998), translated from Neorgan. Mater., 34(6), 684-687 (1998) (Crys. Structure,

Experimental, 12)

[2000Oka] Okamoto, H., Desk Handbook Phase Diagrams for Binary Alloys, ASM International,

Materials Park, OH 44073-0002, (2000) (Equi. Diagram)

[2002Jav] Javorsky, P., Divis, M., Sugawara, H., Sato, H., Mutka, H., “Crystal Field and Magneto-

Crystalline Anisitropy in ErNiAl”, Phys. Rev. B, 65(1), 014404-1 - 014404-8, (2002)

(Experimental, Theory, Magn. Prop., 25)

[2003Ria] Riani, P., Arrighi, L., Marazza, R., Mazzone, D., Zanicchi, G., Ferro, R., “Ternary Rare

Earth Aluminium Systems with Copper: a Review and the Contribution to Their

Assessment”, submitted to J. Phase Equilib., (2003) (Review, Assessment, 267)

[2003Sal] Saltykov, P., Cornish, L., Cacciamani, G., “Al-Ni (Aluminium-Nickel)”, MSIT Evaluation


Services GmbH, Stuttgart, to be published, (2003) (Assessment, Equi. Diagram, Crys.

Structure, 164)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

dissolves 0.01 at.% Ni at 639.9°C

[Mas2]

(Ni)

< 1455

cF4

Fm3m

Cu

a = 352.40 at 25°C [Mas2]

dissolves 20.2 at.% Al at 1385°C [Mas2]

(Er)

< 1529

hP2

P63/mmc

Mg

a = 355.92

c = 558.50

at 25°C [Mas2]

253


MSIT®

Al–Er–Ni

NiAl3< 856

oP16

Pnma

NiAl3

oP16

Pnma

Fe3C

a = 661.3 ± 0.1

b = 736.7 ± 0.1

c = 481.1 ± 0.1

a = 659.8

b = 735.1

c = 480.2

[1996Vik]

[1997Bou, V-C]

Ni2Al3< 1138

hP5

P3m1

Ni2Al3

a = 402.8

c = 489.1

36.8 to 40.5 at.% Ni [Mas2]

[1997Bou, V-C]

Ni3Al4< 702

cI112

Ia3d

Ni3Ga4

a = 1140.8 ± 0.1 [1989Ell, V-C]

NiAl

< 1651

cP2

Pm3m

CsCl

a = 287

a = 288.72 ± 0.02

a = 287.98 ± 0.02

42 to 69.2 at.% Ni [Mas2]

at 63 at.% Ni [1993Kha]

at 50 at.% Ni [1996Pau]

at 54 at.% Ni [1996Pau]

Ni5Al3< 723

oC16

Cmmm

Pt5Ga3

a = 753

b = 661

c = 376

63 to 68 at.% Ni [1993Kha, Mas2]

at 63 at.% Ni [1993Kha]

Ni3Al

< 1372

cP4

Pm3m

AuCu3

a = 356.77

a = 358.9

a = 356.32

a = 357.92

73 to 76 at.% Ni [Mas2]

[1986Hua]

at 63 at.% Ni [1993Kha]

disordered [1998Rav]

ordered [1998Rav]

Ni2Al9 mP22

P21/c

Ni2Al9

a = 868.5 ± 0.6

b = 623.2 ± 0.4

c = 618.5 ± 0.4

= 96.50 ± 0.01°

Metastable

[1988Li, 1997Poh]

NixAl1-x

0.60 < x < 0.68

tP4

P4/mmm

AuCu

m**

a = 383.0

c = 320.5

a = 379.5

c = 325.6

a = 379.5

c = 325.6

a = 375.1

c = 330.7

a = 379.9 to 380.4

c = 322.6 to 323.3

a = 371.7 to 376.8

c = 335.3 to 339.9

a = 378.00

c = 328.00

a = 418

b = 271

c = 1448

= 93.4°

Martensite, metastable

[1993Kha]

at 62.5 at.% Ni [1991Kim]

at 63.5 at.% Ni [1991Kim]

at 66.0 at.% Ni [1991Kim]

at 64 at.% Ni [1997Pot]

at 65 at.% Ni [1997Pot]

[1998Sim]

[1992Mur]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

254


MSIT®

Al–Er–Ni

Ni2Al hP3

P3m1

CdI2

a*126

P1

a = 407

b = 499

a = 1252

b = 802

c = 1526

= 90°

= 109.7°

= 90°

Metastable

[1993Kha]

[1994Mur]

D1(Ni,Al) Decagonal Metastable [1988Li]

D4(Ni,Al) Decagonal Metastable [1988Li]

ErAl3< 1070

cP4

Pm3m

AuCu3

hR60

R3m

HoAl3

a = 421.4

a = 602.5

c = 3567.5

[V-C2]

[V-C2]

ErNixAl2-x

ErAl2< 1455

cF24

Fd3m

MgCu2

a = 770.2

a = 780.1

a = 779.3

0 < x < 0.44 (~15at.% Ni) [1982Zar]

~15 at.% Ni [1982Zar]

0 at.% Ni [1982Zar]

0 at.% Ni [V-C2]

ErAl

< 1140

oP16

Pbcm

ErAl

a = 580.1

b = 1127

c = 557.0

[V-C2]

Er3Al2< 1060

tP20

P42/mnm

Gd3Al2

a = 812.3

c = 748.4

[V-C2]

Er2Al

< 1040

oP12

Pnma

Co2Si

a = 651.6

b = 501.5

c = 927.9

[V-C2]

Er2Ni17

< 1315

hP38

P63/mmc

Ni17Th2

a = 828

c = 801

[V-C2]

Er5Ni22 hP108 a = 486.2

c = 717.7

[V-C2], not reported in [1982Zar]

ErNi5-xAlx

ErNi5< 1380

hP6

P63/mmm

CaCu5

a = 497.5

c = 402.6

a = 485.4

c = 396.6

a = 485.4

c = 396.4

0 < x <~ 2 (~30 at.% Al) [1982Zar]

~30 at.% Al [1982Zar]

0 at.% Al [1982Zar]

0 at.% Al [V-C2]

Er4Ni17 hP16 a = 486.9

c = 840.7

[V-C2], not reported in [1982Zar]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

255


MSIT®

Al–Er–Ni

ErNi4hP90

mC30

C2/m

Ni4Pu

a = 487.4

c = 601.3

a = 485.5

b = 844.4

c =1023.1

= 99.54°

not reported in [1982Zar]

[V-C2]

[V-C2]

Er2Ni7< 1275

hR54

R3m

Er2Co7

a = 490.9

c = 3606.7

[V-C2]

ErNi3< 1320

hR36

R3m

Ni3Pu

a = 494.8

c = 2427

[V-C2]

ErNi2< 1255

cF24

Fd3m

MgCu2

a = 712.46 [V-C2]

solubility: see text

Er3Ni2 hR45

R3

Er3Ni2

a = 847.2

c = 1568.0

[V-C], not reported in [1982Zar]

ErNi

< 1100

oC8

CrB

or

oP8

Pmna

BFe

a = 369.2

b = 1008.8

c = 418.4

a = 699

b = 412

c = 541

[V-C2]

[V-C2]

Er5Ni3< 800

o*24 a = 845

b = 597.5

c = 1065

[V-C2]

Er3Ni

< 845

oP16

Pnma

Fe3C

a = 680.4

b = 943

c = 624.5

[V-C2]

* 1, ErNi3Al16 oC*

Cmcm

a = 396.0

b = 1563

c = 2681

[1982Zar], possibly oC24 - YNiAl4 -

type with c’ = 670 (=c/4) [V-C2]

* 2 ErNi3Al9 hR78

R32

ErNi3Al9

a = 727.16 ± 0.05

c = 2734.6 ± 0.3

[1993Gla]

* 3, ErNi2+xAl3-x hP*

P6/mmm

a = 901

c = 404.9

small solubility ~ 33 to 40 at.% Ni

[1973Ryk, 1981Zar, 1982Zar]

probably hP18 - YNi2Al3 or hP18 -

Ho2Ni5Ga5 -type

* 4, Er2Ni3Al7 hP* a = 1777

c = 397.1

[1973Ryk, 1981Zar, 1982Zar]

* 5, ErNiAl4 oC24

Cmcm

YNiAl4

a = 404.4

b = 1508

c = 663.1

[1973Ryk, 1981Zar, 1982Zar]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

256


MSIT®

Al–Er–Ni

* 6, Er3Ni8Al hP24

P63/mmc

CeNi3

a = 500.2

c = 1599

[1982Zar]

* 7, ErNiAl2 oC16

Cmcm

ordered Re3B

a = 406.4

b = 1006

c = 689.8

[1973Ryk, 1982Zar]

* 8, Er3Ni6Al2 cI44

Im3m

Ce3Ni6Si2

a = 888 [1982Zar]

* 9, ErNiAl hP9

P62m

ZrNiAl

a = 697.4

c = 380.1

a = 697.44

c = 379.78

a = 697.8

c = 379.9

[1982Zar]

solubility: see text

[1968Dwi]

[1973Oes]

* 10, Er2Ni2Al oI10

Immm

Mo2NiB2

a = 534.7

b = 837.4

c = 415.7

a = 837.4

b = 534.7

c = 415.7

[1982Rom2, 1982Zar]

[1997Vil]

* 11, ErNiAl(I) hP12

P63/mmc

MgZn2

a = 531.2

c = 854.8

[1987Tsv1] high pressure phase

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

20

40

60

80

20 40 60 80

20

40

60

80

Er Ni


Axes: at.%

NiAl3

Ni2Al3

ErAl2

ErAl3

τ3

τ4

τ5

τ7

τ1

NiAl

Ni3Al

τ6

τ8

τ10

τ9

Er2Ni17ErNi5Er2Ni7ErNi3ErNi2

τ2

(Ni)

Fig. 1: Al-Er-Ni.

Partial isothermal

section up to 33 at.%

Er at 800°C

257


MSIT®

Al–Fe–Gd

Aluminium – Iron – Gadolinium

Gabriele Cacciamani and Laura Arrighi

Literature Data

The Al-Fe-Gd phase diagram has been investigated only for x(Gd) < 0.33 and most experimental works

concerned crystal structure determinations and magnetic property measurements.

The 500°C isothermal section has been investigated by [1973Viv] in the above mentioned region by means

of X-ray diffraction and microscopy. [2002Hac] studied stable phase equilibria and amorphisation

properties in the Al-rich corner (for x(Al) > 0.75) combining experiments (XRD, TEM-EDS, DTA) and

thermodynamic modelling. Previous evaluations had been compiled by [1992Rei, 1992Rag, 2003Rag].

Binary Systems

The accepted Al-Fe phase diagram [2003Pis] is mainly based on the assessment by [1993Kat], except for

the Fe-rich region where the ordering equilibria between the (Fe), FeAl and Fe3Al solid solutions have been

recently investigated by [2001Ike].

The Al-Gd and Fe-Gd phase diagrams are accepted from the recent assessments by [2002Bod] and

[2000Zin], respectively.

Solid Phases


The binary Laves phases GdAl2 and GdFe2 (isostructural, MgCu2 type) dissolve an appreciable amount of

the third element [1967Oes, 1973Viv, 1974Oes, 1975Dwi, 1976Gro]. At intermediate compositions,

however, a different Laves phase ( 1, MgZn2 type) is formed [1969Tes, 1971Oes, 1973Viv, 1973Zar,

1974Oes, 1975Dwi, 1983Bus].

The phases at the Gd2(Fe,Al)17 composition also present appreciable Al solubility. The composition and

temperature ranges of stability of the two structure types Th2Zn17 and Th2Ni17, however, are not well

defined. According to the accepted Fe-Gd binary system the Th2Ni17 type phase should be stable at higher

temperature (at 1335-1225°C). Ternary solubility of these phases has been investigated by [1973Viv,

1976McN].

At higher Al content a ternary phase with a Gd/M (M = Fe, Al) ratio equal to 1/12, is formed ( 2, ThMn12

type) studied by [1973Viv, 1974Viv, 1976Bus, 1987Liu] at the composition GdFe4Al8, and by [1980Fel,

1981Fel, 1987Liu, 1988Che] at GdFe6Al6. The same phase was obtained by melt spinning at higher Fe

concentrations, up to GdFe10Al2 [1988Wan].

Finally, with the same Gd/M ratio, another ternary phase ( 3, at the composition GdFe2Al10) was studied

by [1973Viv, 1998Thi].


Al-rich invariant equilibria determined by [2002Hac] are reported in Table 2. On the basis of these results

[2003Rag] elaborated the reaction scheme shown in Fig. 1.

Liquidus Surface

The Al-rich liquidus surface shown in Fig. 2 has been determined by [2002Hac] by combining experiments

and thermodynamic modeling. In the same figure the region of good glass formability determined by the

same author is also shown. In order to keep the internal consistency of the figure, isothermal curves have

not been modified and do not exactly meet the accepted Al-Gd binary liquidus, the reliability of which is

rather uncertain.

258


MSIT®

Al–Fe–Gd

Isothermal Sections

The 500°C isothermal section for x(Gd) < 0.33 was first determined by [1973Viv]. The Al-rich corner has

been recently investigated by [2002Hac], who substantially confirmed the results by [1973Viv]. The section

is reported in Fig. 3, where results by [1974Oes, 1983Bus] have also been considered. With respect to

[1973Viv] the solubility of 2 (between the GdFe4Al8 and GdFe6Al6 compositions) has been included and

only one Gd2(Fe,Al)17 phase has been drawn, considering the second one stable at higher temperature. From

a thermodynamic point of view the convergence of five tie triangles at the extremum of the 2 solid solution

may be unlikely: nevertheless in Fig. 3 the equilibria reported in the experimental investigations have been

kept.


Vertical sections at 5 at.% Fe and 5 at.% Gd have been experimentally investigated and thermodynamically

modelled by [2002Hac] in the Al-rich region (x(Al) > 0.75). They are reported in Figs. 4 and 5.

Miscellaneous

Ternary phase 1 has been investigated by Mössbauer spectroscopy [1975Dwi, 1980Ara] and by XRD, XPS

and ESR [2001Jar]. Magnetic, electric and thermal properties have been studied by [1984Sim].

Magnetic properties of 2 have been studied by [1978Bus, 2001Duo1, 2001Duo2] at the GdFe4Al8composition, by [2002Duo] at GdFe5Al7, by [1981Fel, 1988Che, 2001Duo1] at GdFe6Al6 and by [1987Liu,

1988Wan] in the complete solubility range. [1988Wan] extended the measurements to metastable

compositions richer in Fe, up to GdFe10Al2.

Magnetic properties of the phases at the Gd2(Fe,Al)17 composition have been studied by [1976McN] and

reviewed by [1994Liu]. [1998Thi] investigated the low temperature magnetization of 3.

Good glass forming ability in the Al-rich corner (reported in Fig. 2) has been determined by [2002Hac] and

magnetic properties of amorphous alloys at the Gd60Fe30Al10 composition have been studied by

[2002Kon].

References


Iron-Aluminium Alloys”, J. Phys. Chem. Solids, 6, 16-37 (1958) (Crys. Structure, Magn.


[1961Lih] Lihl, F., Ebel, H., “X-ray Examination of the Constitution of Iron-rich Alloys of the

Iron-Aluminium System” (in German), Arch. Eisenhuettenwes., 32, 483-487 (1961) (Crys.


[1967Oes] Oesterreicher, H., Wallace, W.E., “Studies of Pseudo-Binary Laves-Phase Systems

Containing Lanthanides”, J. Less-Common Met., 13, 91-102 (1967) (Crys. Structure,

Experimental, 22)

[1969Tes] Teslyuk, M.Y., Intermetallic Compounds with Structure of Laves Phases (in Russian),

Moscow, Nauka, 1-138 (1969) (Crys. Structure, Equi. Diagram, Review, Theory)



[1973Viv] Vivchar, O.J., Zarechnyuk, O.S., Ryabov, V.R., “Study of the Gd-Fe-Al System in the Low

Gd Region” (in Russian), Dopov. Akad. Nauk Ukrain. RSR, Ser. A, Fiz-Mat. Tekh. Nauki,

11, 1040-1042 (1973) (Crys. Structure, Equi. Diagram, Experimental, #, 14)

[1973Zar] Zarechnyuk, O. S., Rykhal, R. M., Vivchar, O. I., “Laves Phases in Ternary Systems

Rare-Earth Metal-Transition Metal of the IV Period-Aluminium”, Sb. Nauchn. Rab. Inst.

Metallofiz., Akad. Nauk Ukr. SSR, 42, 92-94 (1973) (Crys. Structure, Experimental,

Review)

259


MSIT®

Al–Fe–Gd

[1974Oes] Oesterreicher, H., “Constitution of Al Base Rare Earth Alloys RT2-RAl2 (R = Pr, Gd, Er; T

= Mn, Fe, Co, Ni, Cu)”, Inorg. Chem., 13, 2807-2811 (1974) (Crys. Structure,

Experimental, 30)

[1974Viv] Vivchar, O.I., Zarechnyuk, O.S., “Compounds of the ThMn12-type Structure in R-Fe-Al

Systems” (in Russian), Tezisy Dokl. - Vses. Konf. Kristallokhim. Intermet. Soedin, Rykhal,

R.M. (Ed.), Vol. 2, L'vov. Gos. Univ., Lvov, 41 (1974) (Crys. Structure, Experimental, 0)


Mössbauer Study of (Sc,Y,Ln)(Fe,Al)2 Intermetallic Compounds”, J. Less-Common Met.,

40, 285-291 (1975) (Crys. Structure, Experimental, Moessbauer, 8)




[1976Gro] Groessinger, R., Steiner, W., Krec, K., “Magnetic Investigations of Pseudobinary

RE(Fe,Al)2 Systems (RE = Y, Gd, Dy, Ho)” (in German), J. Magn. Magn. Mater., 2,

196-202 (1976) (Magn. Prop., Experimental, 20)

[1976McN] McNeely, D., Oesterreicher, H., “Structural and Low-Temperature Magnetic Studies on

Compounds Sm2Fe17 with Al Substitution for Fe”, J. Less-Common Met., 44, 183-193


[1978Bus] Buschow, K.H.J., van der Vucht, J.H.N, Kran, A. M., “Magnetic Ordering in Ternary Rare

Earth Iron Aluminium Compounds (RFe4Al8)”, J. Phys., F: Met. Phys., 8, 921-932 (1978)


[1980Ara] Aranjo, S. I., Guimaraes, A. P., “Mössbauer Studies of the Pseudobinary Intermetallic

Compounds Gd(AlxFe1-x)2”, J. Phys. F: Met. Phys., 10, 1313-1321 (1980) (Magn. Prop.,

Moessbauer, 18)


RT6Al6 Type”, J. Less-Common Met., 72, 241-249 (1980) (Experimental, Crys.

Structure, 10)


RFe6Al6 (R = Rare Earth)”, Phys. Chem. Solids, 42, 369-377 (1981) (Crys. Structure, Magn.


[1983Bus] Buschow, K.H.J., van Engen, P.G., Jongebreur, R., “Magneto-Optical Properties of

Metallic Ferromagnetic Materials”, J. Magn. Magn. Mater., 38, 1-22 (1983) (Magn. Prop.,

Optical Prop., 23)

[1984Sim] Sima, V., Grossinger, R., Sechovsky, V., Smetana, Z., Sassik, H., “The Effect of Local

Disorder on the Magnetic, Electric and Thermal Properties of RE (Fe1-xAlx)2 (RE = Gd,

Dy)”, J. Phys. F: Met. Phys., 14(4), 981-1004 (1984) (Magn. Prop., Electr. Prop.,

Experimental, 36)

[1987Liu] Liu, W. L., “The Temperature-Composition Magnetic Phase Diagram and Its Relation to the

Site Occupancy of Fe Atom in GdFeAl (GdFe4+xAl8-x, 0 x 2)”, J. Sci. Hiroshima Univ.,

51(3), 221-246 (1987) (Crys. Structure, Magn. Prop., 34)


Investigations of REAl6Fe6 Compounds for RE = Y, Gd, Tb, Dy, Ho, and Er”, J.

Less-Common Met., 143, L7-L10 (1988) (Crys. Structure, Magn. Prop., Experimental, 12)

[1988Gsc] Gschneidner Jr, K.A., Calderwood, F.W., “The Al-Gd (Aluminum-Gadolinium) System”,

Bull. Alloy Phase Diagrams, 9(6), 680-683 (1988) (Assessment, #, 41)

[1988Wan] Wang, X.-Z., Chevalier, B., Berlureau, T., “Fe-Rich Pseudobinary Alloys with the ThMn12

Structure Obtained by Melt Spinning: Gd(FenAl12-n), n = 6, 8, 10”, J. Less-Common Met.,

138(2), 235-240 (1988) (Crys. Structure, 17)

[1992Rei] Reinsch, B., “Aluminum – Iron - Gadolinium”, MSIT Ternary Evaluation Program, in MSIT


Stuttgart; Document ID: 10.16514.1.20, (1992) (Equi. Diagram, Assessment, Crys.

Structure, 15)

260


MSIT®

Al–Fe–Gd

[1992Rag] Raghavan, V., “The Al-Fe-Gd (Aluminum-Iron-Gadolinium) System”, in “Phase Diagrams

of Ternary Iron Alloys”, Part 6A, Ind. Inst. Metals, Calcutta, 108-112 (1992) (Equi.

Diagram, Crys. Structure, Review, #, 12)

[1993Kat] Kattner, U.R. Burton, B.P., “Al-Fe (Aluminum-Iron)”, in “Phase Diagrams of Binary Iron

Alloys”, Okamoto, H. (Ed.), ASM International, Materials Park, Ohio, 12-28 (1993)

(Assessment, 99)

[1994Liu] Liu, J.P., de Boer, F.R., de Chatel, P.F., Coehoorn, R., Buschow, K.H.J., “On the 4f-3d



[1996Mao] Mao, O., Yang, J., Altounian, Z., Ström-Olsen, J.O., “Metastable RFe7 Compounds (R =

Rare Earths and their Nitrides with TbCu7 Structure)”, J. Appl. Phys., 79(8), 4605-4607


[1997Kog] Kogachi, M., Haraguchi, T., “Quenched-in Vacancies in B2-Structured Intermetallic

Compound FeAl”, Mater. Sci. Eng. A, 230A, 124-131 (1997) (Crys. Structure,

Experimental, 23)




[1998Thi] Thiede, V.M.T., Ebel, T., Jeitschko, W., “Ternary Aluminides LnT2Al10 (Ln = Y, La-Nd,

Sm, Cd-Lu and T = Fe, Ru, Os) with YbFe2Al10 Type Structure and Magnetic Properties of

the Iron-Containing Series”, J. Mater. Chem., 8(1), 125-130 (1998) (Crys. Structure,





[2000Sac] Saccone, A., Cardinale, A.M., Delfino, S., Ferro, R., “Gd-Al and Dy-Al Systems: Phase

Equilibria in the 0 to 66.7 at.% Al Composition Range”, Z. Metallkd, 91(1), 17-23 (2000)

(Experimental, Equi. Diagram, Crys. Structure, #, 12)

[2000Zin] Zinkevich, M., Mattern, N., Seifert H.J., “Reassessment of the Fe-Gd (Iron-Gadolinium)

System”, J. Phase Equilib., 21(4), 385-394 (2000) (Assessment, Calculation, 28)

[2001Duo1] Duong, N.P., Klaasse, J.C.P., Brueck, E., de Boer, F.R., Buschow, K.H.J., “Magnetic

Properties of GdT4Al8 and GdT6Al6 Compounds (T = Cr, Mn, Cu)”, J. Alloys Compd., 315,


[2001Duo2] Duong, N.P., Brück, E., de Boer, F:R., Buschow, K.H.J., “Magnetic Properties of GdFe4Al8and Related Compounds”, Physica B, 294B-295B, 212-216 (2002) (Experimental, Magn.

Prop., 5)


BCC Phases in the Fe-Rich Portion of the Fe-Al System”, Intermetallics, 9, 755-761 (2001)


[2001Jar] Jarosz, J., Talik, E., “Electronic Structure and ESR in GdTAl Ternary Compounds; T = 3d,

4d Transition Metals”, J. Alloys Compd., 317-318, 385-389 (2001) (Crys. Structure,


[2002Bod] Bodak, O., “Al-Gd (Aluminum-Gadolinium)”, MSIT Binary Evaluation Program, in MSIT

Workplace, Effenberg, G. (Ed.), Materials Science International Services GmbH, Stuttgart;

Document ID: 20.12303.1.20 (2002) (Equi. Diagram, Assessment, Crys. Structure, 15)

[2002Duo] Duong, N.P., Brück, E., de Boer, F.R., Buschow, K.H.J., “Magnetic Properties of GdFe5Al7and TbFe4.45Al7.55”, J. Alloys Compd., 338, 213-217 (2002) (Crys. Structure, Experimental,

Magn. Prop., 5)

[2002Hac] Hackenberg, R.E., Gao, M.C., Kaufman, L., Shiflet, G.J., “Thermodynamics and Phase

Equilibria of the Al-Fe-Gd Metallic Glass-Forming System”, Acta Mater., 50, 2245-2258

(2002) (Calculation, Equi. Diagram, Experimental, Thermodyn., 39)

261


MSIT®

Al–Fe–Gd

[2002Kon] Kong, H.Z., Ding, J., Dong, Z.L., Wang, L., White, T., Li, Y., “Observation of Clusters in

Re60Fe30Al10 Alloys and the Associated Magnetic Properties”, J. Phys. D: Appl. Phys.,

35(5), 423-429 (2002) (Experimental, Magn. Prop., 26)




[2003Rag] Raghavan, V., “Al-Fe-Gd (Aluminum-Iron-Gadolinium)”, J. Phase Equilib., 24(2),

170-173 (2003) (Review, #, 7)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


( Fe)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2, 1993Kat]


( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12



0 - 18.8 at.%Al, HT [1958Tay]

0 - 19.0 at.% Al, HT [1961Lih]

0 - 18.7 at.% Al, 25°C [1999Dub]

( Gd) hR3

P3m

Sm

a = 361

c = 2603

at 25°C, 3.0 GPa [Mas2]

( Gd)

1313-1235

cI2

Im3m

W

a = 406 [Mas2]

( Gd)

< 1235

hP2

P63/mmc

Mg

a = 363.36

c = 578.10

at 25°C [Mas2]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [1993Kat]

262


MSIT®

Al–Fe–Gd

1102 - 1232

cI16?

-

a = 598.0 at 61 at.% Al [1993Kat]

FeAl

< 1310

cP8

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5 - 47.5 at.% Al [1961Lih]

36.2 - 50.0 at.% Al [1958Tay]

39.7 - 50.9 at.% Al [1997Kog]

quenched in water from 500°C

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

~24 - ~37 at.% Al [2001Ike]

23.1 - 35.0 at.% Al [1958Tay]

24.7 - 31.7 at.% Al [1961Lih]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [1993Kat]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [1993Kat]

[1998Ali]

FeAl4+x t** a = 884

c = 2160


[1998Ali]

Fe4Al13

1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

[2003Pis], 74.16 to 76.7 at. % Al

solid solubility ranges

from 74.5 to 75.5 at.% Al

[2003Pis], at 76.0 at.% Al.

Also denoted FeAl3 or Fe2Al7

Gd2Al

< 940

oP12

Pnma

Co2Si

a = 674.2

b = 525.4

c = 975.6

a = 661.2

b = 515.0

c = 957.8

a = 660.6

b = 514.6

c = 953.1

as cast, [2000Sac]


[1988Gsc]

Gd3Al2< 970

tP20

P42/mnm

Zr3Al2

a = 832.0

c = 762.8

a = 833.9

c = 762.0


[1988Gsc]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


263


MSIT®

Al–Fe–Gd

GdAl

< 1070

oP16

Pbcm

DyAl

a = 589.3

b = 1159

c = 569.5

a = 588.8

b = 1152.7

c = 565.6


[1988Gsc]

Gd(FexAl1-x)2

GdAl2< 1520

cF24

Fd3m

MgCu2

a = 790.6

0 x 0.37 [1967Oes, 1974Oes]

at x = 0, cooled 10 K min-1, [2000Sac]

GdAl3< 1125

hP8

P63/mmc

Ni3Sn

a = 633.1

c = 460.0

[1988Gsc]

Gd(Fe1-xAlx)2

GdFe2

< 1080

cF24

Fd3m

MgCu2

a = 740.0

a = 749.3

a = 752.1

0 x 0.26 [1974Oes]

at x = 0 [2000Zin, V-C2]

at x = 0.2 [1976Gro]

at x = 0.25 [1967Oes]

GdFe3

< 1160

hR36

R3m

PuNi3

a = 514.8

c = 2462

[2000Zin, V-C2]

Gd6Fe23

< 1280

cF116

Fm3m

Th6Mn23

a = 1212 [2000Zin, V-C2]

Gd2(Fe1-xAlx)17

Gd2Fe17

1335-1215

hP38

P63/mmc

Th2Ni17

a = 849.6

c = 834.5

a = 860

c = 840

0 x 0.147 [1973Viv]

at x = 0.0, HT [2000Zin, V-C2]

at x = 0.147, [1973Viv] probably HT

Gd2(Fe1-xAlx)17

Gd2Fe17

< 1215

hR57

R3m

Th2Zn17 a = 851.7

c = 1242.9

a = 875.8 to 882.0

c = 1269.8 to 1279.4

0 x 0.56 [1973Viv]

at x = 0 [2000Zin, V-C2]

at 0.45 x 0.56 [1976McN]

GdFe7 a = 492

c = 415

metastable. [1996Mao]

(lattice parameters from graph)

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


264


MSIT®

Al–Fe–Gd

Table 2: Invariant Equilibria in the Al-rich Corner [2002Hac]

* 1, Gd(Fe1-xAlx)2 hP12

P63/mmc

MgZn2

a = 541.4

c = 881.2

a = 544.5

c = 880.9

a = 538.8

c = 870.9

0.28 x 0.52 [1974Oes]

at x = 0.5 [1971Oes]

GdFeAl

at x = 0.5 [1983Bus]

GdFeAl

at x = 0.4 [1983Bus]

* 2, Gd(FexAl1-x)12 tI26

I4/mmm

ThMn12

a = 875.6

c = 503.6

a = 877.8 to 869.4

c = 505.5 to 502.1

a = 868.7

c = 501.5

a = 857

c = 495

a = 849

c = 489

0.33 x 0.50 [1988Che]

at x = 0.33 [1974Viv, 1976Bus]

GdFe4Al8at x = 0.33 - 0.5 [1987Liu]

at x = 0.5 [1980Fel, 1981Fel]

GdFe6Al6metastable, at GdFe8Al4 [1988Wan]

metastable, at GdFe10Al2 [1988Wan]

* 3, GdFe2Al10 oP52

Cmcm

YbFe2Al10

a = 897.0

b = 1016.2

c = 902.3

[1998Thi]


Al Fe Gd

L + Fe2Al5 Gd2(Fe,Al)17 + Fe4Al13 1137 U1 L

Gd2(Fe,Al)17

75.23

50.00

22.56

39.47

2.21

10.53

L + Fe4Al13 Gd2(Fe,Al)17 + 2 1100 U2 L

Gd2(Fe,Al)17

78.20

50.00

14.53

39.47

7.27

10.53

L + Gd2(Fe,Al)17 GdAl2 + 2 1097 U3 L

Gd2(Fe,Al)17

GdAl2

78.18

50.00

-

13.74

39.47

-

8.08

10.53

33.33

L + 2 Fe4Al13 + GdAl2 1092 U4 L

GdAl2

78.58

-

13.28

-

8.14

33.33

L + GdAl2 Fe4Al13 + GdAl3 1041 U5 L

GdAl2GdAl3

82.21

-

74.00

8.20

-

1.00

9.59

33.33

25.00

L + Fe4Al13 + GdAl3 3 1040 P1 L

GdAl3

82.27

74.00

8.15

1.00

9.58

25.00

L + Fe4Al13 (Al) + 3 647 U10 L 98.6 0.80 0.60

L (Al) + GdAl3 + 3 638 E1 L

GdAl3

95.96

75.00

0.20

0

3.84

25.00

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


265


MSIT®

Al–Fe–Gd

Fig. 1: Al-Fe-Gd. Partial Al-Fe-Gd reaction scheme [2003Rag]. Designation "2:17" is used to

denote αGd2(Fe,Al)

17 phase.

Al-Fe Al-Fe-Gd Al-Gd

l+GdAl2

GdAl3

1125 p2

l (Al)+Fe4Al

13

655 e1

L + Fe4Al

13+ GdAl

3τ3

1040 P1

L + Fe4Al

13τ3

+ (Al)647 U10

GdAl2+Fe

4Al

13τ3+τ

21000>U

c>500 U

8

Fe4Al

13+GdAl

3τ3+GdAl

21020 U

6

Fe4Al

13+2:17 τ

2+Fe

2Al

51000 U

7

GdAl2+τ

3GdAl

3+τ

2Uc>U

d>500 U

9

L+GdAl2

Fe4Al13

+GdAl3

1041 U5

L + τ2

GdAl2 + Fe

4Al

131092 U

4

L + 2:17 τ2 + GdAl

21097 U

3

L + Fe4Al

132:17 + τ

21100 U

2

L+Fe2Al

5Fe

4Al

13+2:171137 U

1

L (Al) + GdAl3 + τ

3638 E

1

l+Fe2Al

5Fe4Al

13

1160 p1

L+Fe2Al

5+2:17

L+2:17+GdAl2

L+Fe4Al

13+2:17 Fe

2Al

5+Fe

4Al

13+2:17

L+2:17+τ2

Fe4Al

13+2:17+τ

2

2:17+τ2+GdAl

2L+τ2+GdAl

2

L+GdAl2+Fe

4Al

13τ2+GdAl

2+Fe

4Al

13

L+Fe4Al

13+GdAl

3

Fe4Al13

+GdAl3+τ

3L+GdAl3+τ

3L+Fe

4Al

13+τ

3

GdAl3+τ

3+GdAl

2Fe

4Al

13+τ

3+GdAl

2

Fe4Al

13+τ

2+Fe

2Al5

2:17+τ2+Fe

2Al5

Fe4Al

13+τ

3+τ

2GdAl

2+τ

3+τ

2

GdAl2+GdAl

3+τ

2τ3+GdAl

3+τ

2

Fe4Al

13+τ

3+(Al)

L+τ3+(Al)

(Al)+GdAl3+τ

3

l (Al)+GdAl3

650 e2

GdAl2+Fe

4Al13

+GdAl3

L+τ2+Fe

4Al

13

1105

266


MSIT®

Al–Fe–Gd

10

20

30

10 20 30

70

80

90

Gd 40.00Fe 0.00Al 60.00

Gd 0.00Fe 40.00Al 60.00


Axes: at.%

1400

1300

1200

1100

GdAl2

1000

GdAl3

900

800

700

Fe4Al13

U4

U5

U2

P1

U10

p2

e2

e1

E1

αGd2(Fe,Al)17

τ2

τ3

good glassforming area

U3

Fig. 2: Al-Fe-Gd.

Al-rich liquidus

surface [2002Hac]

20

40

60

80

20 40 60 80

20

40

60

80

Gd Fe


Axes: at.%

τ2

τ3

τ1

Fe3Al

FeAl

Fe4Al13Fe2Al5

FeAl2

Gd(Fe1-xAlx)2

GdFe3 Gd6Fe23

GdAl3

GdAl2

(αFe)

αG

d2 (Fe

1-x Al

x )17

Gd(FexAl1-x)2

GdFe2

Gd2Fe17

(Al)Fig. 3: Al-Fe-Gd.


500°C [1973Viv,

1974Oes, 1983Bus,

2002Hac]

267


MSIT®

Al–Fe–Gd

10500

600

700

800

900

1000

1100

1200

Gd 5.00Fe 0.00Al 95.00

Gd 5.00Fe 20.00Al 75.00Fe, at.%

Tem

pera

ture

, °C

10411092°C

1100°C

647638

L

L+τ3

L+Fe4Al13+τ3

L+Fe4Al13

(Al)+Fe4Al13+τ3(Al)+GdAl3+τ3

10500

600

700

800

900

1000

1100

1200

Gd 0.00Fe 5.00Al 95.00

Gd 20.00Fe 5.00Al 75.00Gd, at.%

Tem

pera

ture

, °C

L+GdAl3+τ3

L+GdAl2

L+GdAl3

L+τ3

L

(Al)+GdAl3+τ3(Al)+Fe4Al13+τ3

L+Fe4Al13

647 638

1042°C

Fig. 4: Al-Fe-Gd.

Al-rich part of the

isopleth at 5 at.% Gd

[2002Hac]

Fig. 5: Al-Fe-Gd.

Al-rich part of the

isopleth at 5 at.% Fe

[2002Hac]

268


MSIT®

Al–Fe–Ho

Aluminium – Iron – Holmium

Gabriele Cacciamani and Laura Arrighi

Literature Data

The Al-Fe-Ho system has been investigated only for x(Ho) < 0.33 and most experimental work concerned

crystal structure determination (either by X-ray and neutron diffraction) and magnetic property

measurements.

The 500°C isothermal equilibria have been investigated by [1971Rya] in the above mentioned region, by

means of X-ray diffraction and microscopy, and by [2001Yan] at the Ho2(Fe,Al)17 composition.

Binary Systems


the Fe-rich region where the ordering equilibria between the ( Fe), FeAl and Fe3Al solid solutions have

been recently investigated by [2001Ike].

The more recent assessment of the Al-Ho phase diagram [1988Gsc] shows unlikely liquidus curves,

especially around the HoAl2 and Ho2Al compositions. It is here accepted with some reserve, further

experimental investigation on this system being needed.

The Fe-Ho phase diagram is accepted from the assessment by [1993Oka] with the addition of the solubility

range reported by [2001Yan] for the Ho2Fe17 phase.

Solid Phases


The binary Laves phases HoAl2 and HoFe2 (isostructural, MgCu2 type) dissolve more than 20 at.% of the

third element. At intermediate compositions, however, a different Laves phase ( 1, MgZn2 type) is formed

[1971Oes, 1971Rya, 1973Zar, 1974Oes, 1975Dwi, 1976Gro].

Ho2Fe17 (Th2Ni17 type) also presents large Al solubility [1996Wan, 1998Yel, 2001Yan]. According to

[2001Yan], at increasing Al compositions it transforms to the related structures TbCu7 and Th2Zn17 type,

respectively. According to [1996Mao] a HoFe7 metastable phase with the TbCu7 type structure is present

in the Fe-Ho binary system.

At even higher Al content another ternary phase, with a larger Ho/M (M = Fe, Al) ratio, is formed ( 4,

ThMn12 type) studied by [1971Rya, 1974Viv, 1976Bus, 1988Sch, 2000Pai] at the composition HoFe4Al8,

and by [1980Fel, 1981Fel, 1988Che, 1998Sch] at HoFe6Al6. At this same composition [1998Sch]

determined the cell parameters at 4.2, 300 and 500 K. [2001Sch] found the same structure at HoFe7Al5;

notice however that the ThMn12 type structure is reported to be metastable in similar R-Fe-Al systems at

this composition.

Finally, with the same Ho/M ratio, another ternary phase ( 5, at the composition HoFe2Al10) was studied

by [1971Rya, 1998Thi].

Isothermal Sections

The 500°C isothermal section for x(Ho)<0.33 was first determined by [1971Rya]. It is reported in Fig. 1

with minor changes in order to be consistent with the homogeneity ranges reported in more recent structural

investigations by [1974Oes, 1981Fel, 2001Sch, 2001Yan].

Miscellaneous

Mössbauer measurements on the 1 phase at the HoFeAl composition have been carried out by [1975Dwi,

1976Gro].

269


MSIT®

Al–Fe–Ho

Magnetic properties of the phases at the Ho2(Fe,Al)17 composition have been studied by [1992Jac,

1996Wan, 1999Wan] and reviewed by [1994Liu, 2002Ram].

Magnetic properties of 4 have been investigated by low temperature Cp measurements, neutron diffraction,

etc. by [1978Bus, 1988Sch, 1989Sch, 1998Hag, 2000Hag, 2000Pai] at the HoFe4Al8 composition, by

[1981Fel, 1988Che] at HoFe6Al6 and by [2001Sch] at HoFe7Al5.

[1998Thi] investigated the low temperature magnetisation of 5.

References


Iron-Aluminium Alloys”, J. Phys. Chem. Solids, 6, 16-37 (1958) (Crys. Structure., Magn.


[1961Lih] Lihl, F., Ebel, H., “X-ray Examination fo the Constitution of Iron-Rich Alloys of the





[1971Rya] Ryabov, V.R., Zarechnyuk, O.S., Rabkin, D.M., Vivchar, O.I, “Phase Composition of Fe/Al

Welds Containing Ho” (in Russian), Izv. Akad. Nauk Ukr. SSR, 27 (4), 75-76 (1971) (Crys.

Structure, Equi. Diagram, Experimental, #, 0)

[1973Zar] Zarechnyuk, O.S., Rikhal, R.M. and Vivchar, O.I., “Laves Phases in Ternary Systems of the


Metallofiz., 46, 92-94 (1973) (Crys. Structure, Experimental, 22)

[1974Oes] Oesterreicher, H., “Constitution of Al Base Rare Earth Alloys RT2-RAl2 (R = Pr, Gd, Er ;

T = Mn, Fe, Co, Ni, Cu)”, Inorg. Chem., 13, 2807-2811 (1974) (Crys. Structure,

Experimental, 30)

[1974Viv] Vivchar, O.I., Zarechnyuk, O.S., “Compounds of the ThMn12-Type Structure in R-Fe-Al

Systems” (in Russian), Tezisy Dokl. - Vses. Konf. Kristallokhim. Intermet. Soedin., Rykhal,

R.M. (Ed.), Vol. 2, L'vov. Gos. Univ., 41 (1974) (Crys. Structure, Experimental, 0)



40, 285-291 (1975) (Crys. Structure, Moessbauer, Experimental, 8)

[1976Bus] Buschow, K.H.J., Van der Vucht, J.H.N., Van den Hoogenhof, W.W., “Note on the Crystal



[1976Gro] Groessinger, R., Steiner, W., Krec, K., “Magnetic Investigations of Pseudobinary RE(Fe,

Al)2 Systems (RE = Y, Gd, Dy, Ho)” (in German), J. Magn. Mater., 2, 196-202 (1976)

(Crys. Structure, Magn. Prop., Experimental, 20)


Aluminium Compounds (RFe4Al8)”, J. Phys. F, Met. Phys., 8, 921-932 (1978) (Magn.

Prop., 9)


RT6Al6 Type”, J. Less-Common Met., 72, 241-249 (1980) (Crys. Structure, 10)


RFe6Al6 (R = Rare Earth)”, J. Phys. Chem. Solids, 42, 369-377 (1981) (Crys. Structure,







270


MSIT®

Al–Fe–Ho



[1988Gsc] Gschneider, K.A. Jr, Caldeerwood, F.W., “Al-Ho (Aluminum-Holmium)”, Bull. Alloy

Phase Diagrams, 9(6), 684-686 (1988) (Equi. Diagram, Review, 19)




[1989Sch] Schaefer, W., Will, G., Kalvius, G.M., Gal, J., “Coexistence of Long Range Order and Spin

Glass Similar Behaviour in HoFe4Al8”, Physica B, 156/157, 751-753 (1989) (Magn. Prop.,

Experimental, 11)

[1992Jac] Jacobs, T.H., Buscow, K.H.J., Zhou, G.F., Li, X., de Boer F.R., “Magnetic Interactions in

R2Fe17-xAlx Compounds (R = Ho, Y)”, J. Magn. Magn. Mater, 116(1-2), 220-230 (1992)

(Magn. Prop., Experimental)


Alloys”, Okamoto, H. (Ed.), ASM International, Materials Park, Ohio, 12-28 (1993) (Equi.


[1993Oka] Okamoto, H., “Fe-Ho (Iron-Holmium)”, in “Phase Diagrams of Binary Iron Alloys”,

Okamoto, H. (Ed.), ASM International, Materials Park, Ohio, 179-181 (1993) (Equi.








[1994Liu] Liu, J.P., De Boer, F.R., De Chatel, P.F., Coehoorn, R., Buschow, K.H.J., “On the 4f-3d



[1996Mao] Mao, O., Yang, J., Altounian, Z., Ström-Olsen, J.O., “Metastable RFe7 Compounds

(R=Rare Earths and Their Nitrides with TbCu7 Structure)”, J. Appl. Phys., 79(8), 4605-4607


[1996Wan] Wang J.L., Tang, N., Li, W.Z., Qin W.D., Pan, H.Y., Nasunjilegal B., Yang F.M., De Boer,

F.R., “High-field Magnetic Properties of Ho2Fe15M2 Compounds (M = Al, Ga, Ni and Si)”,

J. Magn. Magn. Mater., 159, 357-360 (1996) (Crys. Structure, Magn. Prop.,

Experimental, 9)

[1997Kog] Kogachi, M., Haraguchi, T., “Quenched-in Vacansies in B2-structured Intermetallic


Experimental, 23)


Al-Fe Phases Forming in Direct-Chill (DC)-Cast Aluminium Alloy Ingots”, Calphad, 22

(2), 147-155 (1998) (Calculation, Equi. Diagram, 20)

[1998Hag] Hagmusa I.H., Brueck E., de Boer F.R., Buschow K.H.J., “Magnetic Properties of RFe4Al8Compounds Studied by Specific Heat Measurements”, J. Alloy. Compd., 278, 80-82 (1998)

(Magn. Prop., Experimental, 9)



Concentrations x = 6”, Mater. Sci. Forum, 278-281, 542-547 (1998) (Crys. Structure, Magn.




the Iron-Containing Series”, J. Mater. Chem., 8(1), 125-130 (1998) (Crys. Structure, Magn.


271


MSIT®

Al–Fe–Ho

[1998Yel] Yelon, W.B., Luo, H., Chen, M., Chang, W.C., Tsai, S.H., “A Neutron Diffraction

Structural Study of R2Fe17-xAlx(C) (R = Tb, Ho) Alloys”, J. Appl. Phys., 83(11), 6914-6916





[1999Wan] Wang, J.Y., Shen, B.G., Wang, F.W., Wen, L.X., Zhang, S.Y., Zhang, H.W., Sun, Z.G.,

Zhan, W.S., Zhang, L.G., “Magnetocrystalline Anisotropy of Ho2(Co1-xFex)15Al2Compounds”, J. Phys.: Condens. Matter, 11, 5539-5546 (1999) (Crys. Structure, Equi.

Diagram, Experimental, Magn. Prop., 33)


some RFe4Al8 Compounds (R = Ce, Pr, Nd, Dy, Ho, Tm)”, J. Alloy. Compd., 298, 77-81

(2000) (Crys. Structure, Experimental, Thermodyn., 16)

[2000Pai] Paixao, J.A., Silva, M.R., Sorensen, S.A., Lebech, B., Lander, G.H., Brown, P.J., Langridge,

S., Talik, E., Goncalves, A.P., “Neutron-Scattering Study of the Magnetic Structure of

DyFe4Al8 and HoFe4Al8”, Phys. Rev. B, 61(9), 6176-6188 (2000) (Crys. Structure,










Er) Phases”, J. Alloy. Compd., 320, 108-113 (2001) (Crys. Structure, Equi. Diagram,

Experimental, 9)

[2002Ram] Rama Rao, K.V.S., Ehrenberg, H., Markandeyulu, G., Varadaraju, U.V., Venkatesan, M.,

Suresh, K.G., Murthy, V.S., Schidt, P.C., Fuess, H., “On the Structural and Magnetic

Properties of R2Fe(17-x)(A, T)x (R = Rare Earth; A = Al, Si, Ga; T = Transition Metal)

Compounds”, Phys. Status Solidi A, 189(2), 373-388 (2002) (Crys. Structure, Magn. Prop.,

Review, 51)

[2003Pis] Pisch, A., “Al-Fe (Aluminum-Iron)” MSIT Binary Evaluation Program, in MSIT


Stuttgart, to be published, (2003) (Equi. Diagram, Crys. Structure, Assessment, 58)


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


272


MSIT®

Al–Fe–Ho

( Fe)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2, 1993Kat]


( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12



0 - 18.8 at.% Al, HT [1958Tay]

0 - 19.0 at.% Al, HT [1961Lih]

0 - 18.7 at.% Al, 25C° [1999Dub]

(Ho)

< 1474

hP2

P63/mmc

Mg

a = 357.78

c = 561.78

[Mas2]

Fe4Al13< 1160

mC102

C2/m

Fe4Al13

a =1552.7 to 1548.7

b = 803.5 to 808.4

c =1244.9 to 1248.8

=107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16 - 76.70 at.% Al [1986Gri]


at 76.0 at.% Al [1994Gri]

Fe2Al5< 1169

oC24

Cmcm

-

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [1994Bur]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75

= 73.27°

= 96.89°

at 66.9 at.% Al [1993Kat]

1102 - 1232

cI16? a = 598.0 at 61 at.% Al [1993Kat]

FeAl

< 1310

cP8

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5 - 47.5 at.% Al [1961Lih]

36.2 - 50.0 at.% Al [1958Tay]

39.7 - 50.9 at.% Al [1997Kog] 500°C

quenched in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

~24 -~37 at.% Al [2001Ike]

23.1 - 35.0 at.% Al [1958Tay]

24.7 - 31.7 at.% Al [1961Lih]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [1993Kat]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


273


MSIT®

Al–Fe–Ho

FeAl6 oC28

Cmc21FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [1993Kat]

[1998Ali]

FeAl4+x t** a = 884

c = 2160


[1998Ali]

Ho2Al

<1018

oP12

Pnma

Co2Si

a = 652.8

b = 505.3

c = 934.7

[V-C2]

Ho3Al2<994

tP20

P42nm

Gd3Al2

a = 818.2

b = 752.5

[V-C2]

HoAl

<1115

oP16

Pbcm

AlDy

a = 580.1

b = 1133.9

c = 562.1

[V-C2]

Ho(FexAl1-x)2

HoAl2<1530

cF24

Fd3m

Cu2Mg a = 781.6

0 x 0.35 (0 to 23 at.% Fe)

[1974Oes, 1975Dwi]

[V-C2]

HoAl3<1087

hR60

R3m

HoAl3

a = 605.9

c = 3586

[V-C2]

Ho(Fe1-xAlx)2

HoFe2<1285

cF24

Fd3m

MgCu2 a = 730.14

0 x 0.35 (0 to 23 at.% Al)

[1974Oes,1975Dwi]

[1993Oka]

HoFe3<1293

hR36

R3m

PuNi3

a = 510.97

c = 245.26

[1993Oka]

Ho6Fe23<1332

cF116

Fm3m

Th6Mn23

a = 120.32 [1993Oka]

Ho2(Fe1-xAlx)17

Ho2Fe17<1343

hP38

P63/mmc

Th2Ni17 a = 843.4

c = 828.4

a = 843.5 to 855.6

c = 828.8 to 838.0

a = 849.61

c = 831.45

a = 852.26

c = 832.78

a = 854.2

c = 834.1

0 x 0.3 (x(Al) = 0.0 - 0.27)

[2001Yan]

at x=0.0 [1993Oka]

at x(Al)=0.0-0.20

(from graph in [2001Yan])

at x=0.059 [1998Yel]

Ho2Fe16Al1at x=0.118 [1998Yel]

Ho2Fe15Al2at x=0.118, T=143°C

Ho2Fe15Al2 [1996Wan]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


274


MSIT®

Al–Fe–Ho

HoFe7 hP8

P6/mmm

TbCu7

a = ~487

c = ~418

metastable phase [1996Mao]

(lattice parameters from graph)

* 1, Ho(Fe1-xAli)2

HoFeAl

hP12

P63/mmc

MgZn2 a = 536.2

c = 870.6

0.375 x 0.55(25 to 36 at.% Al)

[1971Rya]

at x = 0.33 [1974Oes, 1975Dwi]

* 2, Ho2(Fe1-xAlx)17 hP8

P6/mmm

TbCu7 a = 495.0 to 496.0

c = 419.0 to 420.5

0.25 x 0.33 (x(Al) = 0.22 - 0.30)

[2001Yan]

at x(Al) = 0.21 - 0.25


* 3, Ho2(Fe1-xAlx)17 hR57

R3m

Th2Zn17 a = 859.49

c = 1256.50

a = 864.3 to 866.0

c = 1260

0.30 x 0.45(x(Al) = 0.26-0.40)

[2001Yan]

at x = 0.24 [1998Yel]

HoFe13Al4at x(Al) = 0.30-0.32


* 4, Ho(FexAl1-x)12 tI26

I4/mmm

ThMn12 a = 874.9

c = 504.9

a = 866.9

c = 500.5

a = 862.5

c = 502.3

a = 865.7

c = 504.4

a = 863.6

c = 498.5

a = 861.0

c = 499.7

0.33 x 0.50 [1971Rya]

[1981Fel, 1988Che]

at x = 0.33 [1976Bus]

HoFe4Al8neutron diffr. at RT [2000Pai]

HoFe4Al8[1988Che]

HoFe6Al6neutron diffr. at 27°C

HoFe6Al6 [1998Sch]

[1980Fel]

HoFe6Al6neutron diffr. at 20°C

HoFe7Al5 [2001Sch] (metastable?)

* 5, HoFe2Al10 oP52

Cmcm

YbFe2Al10

a = 895.3

b = 1013.7

c = 899.7

[1998Thi]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]


275


MSIT®

Al–Fe–Ho

20

40

60

80

20 40 60 80

20

40

60

80

Ho Fe


Axes: at.%

τ5

τ4

τ1

HoAl3

HoAl2

HoFe2 Ho6Fe23Ho2Fe17

FeAl

FeAl2

Fe2Al5

Fe4Al13

Fe3Al

(Fe)

τ2

τ3

?

?

HoFe3

(Al)Fig. 1: Al-Fe-Ho.


500°C

276


MSIT®

Al–Fe–La

Aluminium – Iron – Lanthanum


Literature Data

Literature data up to 1986 have been reported and discussed by [1992Gri], and in the following summarized.

[1968Zar] studied an isothermal section at 500°C up to about 33.3 at.% La, investigating 101 ternary alloys.

Alloys were arc-melted on a water cooled Cu hearth under argon using 99.98 mass% Al, 99.99 mass% Fe

and 98.9 mass% La, with 0.8% other rare earth metals. The alloys were then annealed at 500°C for 2000 h,

quenched and studied by metallographic and X-ray powder diffraction techniques. Subsequently

[1993Tan], and [1995Tan1] investigated the system in the complete range of compositions. The alloys were

repeatedly melted by arc furnace in a purified argon atmosphere. The ingots, sealed in silica ampoules under

vacuum were annealed at 500 to 900°C for several weeks and cooled in the furnace; samples were mainly

analyzed by X-ray powder diffraction analysis. Following compounds have been reported: LaFeAl by

[1968Zar, 1971Oes], LaFe4Al8 by [1974Viv] and [1976Bus], La2Fe7Al10 and LaFe6Al6 by [1982Fel],

La(Fe1-xAlx)13 by [1986Hel] and [1986Pal]. Moreover [1982Erm] reported partial and integral enthalpies

of formation of liquid alloys.

Crystal structures of some intermediate phases and a tentative phase equilibria description in the (Fe,Al)

rich region of the system was presented by [1997Sri]. Alloys of a total weight of 1-2 g were melted in an

arc furnace under argon from 99.9 mass% purity elements; cast and annealed (800°C for 120 h) alloys were

examined by X-ray powder diffraction.

Alloys with composition R6Fe11Al3 (R = La, Ce, Pr, Nd, Sm) were prepared and studied by [1992Hu]: the

samples were prepared by arc melting and annealed at 600-800°C for 120 h and quenched.

Alloys with composition LnT2Al10 (Ln = Y, La-Nd, Sm, Gd-Lu and T = Fe, Ru, Os) have been prepared

and studied by X-ray diffraction and magnetic measurement [1998Thi].

The isothermal section at room temperature suggested by [2001Rag] mainly on the basis of [1995Tan1], is

shown in Fig. 1.

Binary Systems




The other accepted binary systems are: Al-La from [2003Gro], based mainly on the papers by [1996Sac,

2000Yin, 2001Bor], and Fe-La assessed by [1997Zha]. This simple eutectic system presents an unusual

liquidus flattening.

Solid Phases

Crystal structure data of the phases identified in isothermal section determination and in the preparation of

specific alloys are given in Table 1.

[1968Zar] reported a phase ( 9) with a homogeneity range: LaFe1.4-1Al0.6-1 with unknown structure; the

existence of a phase, with unknown structure, at a composition close to LaFeAl was confirmed by

[1971Oes]. In his investigation [1995Tan1] proposed the La36Al20Fe44 (at.%) composition (see Fig. 1).

The ThMn12 type structure was investigated at the composition LaFe4Al8 [1974Viv, 1976Bus] and

LaFe3.5Al8.5 [1997Sri]; a different unknown structure was proposed for LaFe2Al10 by [1968Zar].

The Th2Zn17 structure type corresponds to 4 La2(Fe1-xAlx)17 with 0.35 x 0.41 [1968Zar], subsequently

described as a stoichiometric phase La2Fe7Al10 [1995Tan1].

The NaZn13 type cubic structure 1,La(FexAl1-x)13 has been investigated by several authors: [1968Zar,

1982Fel, 1986Hel, 1995Tan1, 1997Sri, 1999Moz]. Different ranges of composition have been proposed for

the homogeneity field of this phase, as reported in Table 1. For specific compositions data have been

277


MSIT®

Al–Fe–La

reported by [1982Fel] and [1999Moz] who studied also the occupation of N in LaFe11Al2 after

nitrogenation.

The crystal structure of 5,La6Fe11Al3 was studied by [1992Hu] as pertaining to the I4/mcm space group.

The crystal structure of 6,LaFe2Al10 was studied by [1998Thi] as pertaining to the Cmcm space group. The

crystal structure of LaFe2Al8 was studied by [2000Tam] as pertaining to the Pbam space group. The

structural transition from cubic to orthorhombic and magnetic properties of La6Fe13-xAlx (x = 6.7) were

studied by [1995Tan2].

Finally the following compounds with unknown structures have been observed: by [1968Zar] ~LaFe2Al7(possibly corresponding to LaFe2Al8 [2000Tam]), by [1995Tan1] LaFe1.2Al7.8, and by [1997Sri]

La2Fe2Al15 (possibly corresponding to 6,LaFe2Al10 [1998Thi]) and La5Fe6Al4 (possibly corresponding

to 7).

Isothermal Sections

An isothermal section in the range 0 to 33.3 at.% La at 500°C was constructed by [1968Zar]. These data

were accepted, with some changes in the compositions of some phases, in the assessment by [1992Gri].

[1992Gri] changed the homogeneity range of the La(FexAl1-x)13 (NaZn13 type phase) from

0.462 x 0.539 to 0.46 x 0.92 according to data of [1986Hel] and changed the stoichiometry of the

Al-richest Al-La phase from LaAl4 to La3Al11.

The evaluation by [2001Rag] was based on [1995Tan1]: however the isothermal section was redrawn by

[2001Rag] to agree with the binary data. On the Al-Fe edge [1995Tan1] reported only FeAl and FeAl2 as

point compounds and on the Al-La edge included La3Al which on cooling undergoes a eutectoid

decomposition [1996Sac]. The version by [2001Rag] is shown in Fig. 1.


Mössbauer measurements on the LaFe2Al8 phase have been carried out by [2000Tam] at temperature from

78 to 300 K and in applied magnetic fields up to 1.05 T.

Magnetic properties of the phase LaFe4Al8 have been studied experimentally by neutron diffraction at

temperatures between 1.5 and 240 K by [1998Sch] and theoretically, applying symmetry analysis, by

[2000Sik].

Magnetic properties of the phases La(FexAl1-x)13 have been investigated by several authors: [1986Pal] by

means of neutron diffraction and magnetostriction measurements; [1998Guo] calculating the magnetic

properties and the electronic structures for x = 0.69, 0.91, 1.0; [2000Iri] for 0.861 x 0.869 by means of

a SQUID magnetometer; [2000Moz] for x = 0.83 by means of high resolution neutron powder

diffractometry at 15 K; [2001Iri1] for x = 0.89 by means of electrical and magnetic resistivity

measurements; [2001Iri2] studying the effect of pressure on the magnetic properties; [2001Iri3] studying

the effect of the hydrogenation on the magnetic state of La(Fe0.88Al0.12)13.

The magnetic and transport properties of La6Fe11Al3 have been studied by means of SQUID magnetometer

and/or neutron diffraction by [1998Gro, 2000Wan] and [2002Jon] (La6Fe11-xAl3+x with x = 0, 1, 2).

Magnetic properties of the phase LaFe2Al10 have been investigated by [1998Thi]. This phase is Pauli

paramagnetic.

References



Experimental, 49)




[1965Bus] Buschow, K.H.J., Phillips Res. Rep., 20, 337 (1965) (Equi. Diagram, Thermodyn.,

Experimental) as quoted by [2000Yin] and by [2003Pis]

278


MSIT®

Al–Fe–La

[1968Zar] Zarechnyuk, O.S., Emes-Misenko, E.I., Ryabov, V.R., Dikiy, I.I., “Investigation of the

Phase Composition of La-Fe-Al Alloys”, Russ. Metall. (Engl. Transl.), (3), 152-154 (1968),

translated from Izv. Akad. Nauk SSSR, Met., (3), 219-221 (1968) (Crys. Structure, Equi.





Systems” (in Russian), Tezisy. Dokl. -Vses. Konf. Kristallokhim. Intermet. Soedin., R.M.

Rykhal (Ed.), Vol. 2nd, Gos. Univ., Lvov, 41 (1974) (Crys. Structure, Experimental, 0)

[1976Bus] Buschow, K.H.J., van Vucht, J.H.N., van den Haagenhof, W.W., “Note on the Crystal

Structure of the Ternary Rare Earth 3d Transition Metal Compounds of the Type RT4Al8”,

J. Less-Common Met., 50(1), 145-150 (1976) (Crys. Structure, Experimental, 2)

[1982Erm] Ermakov, A.F., Esin, Yu.O., Gel’d, P.V., “Partial and Integral Enthalpies of Formation of

Liquid Alloys of Iron Monoaluminide with Yttrium, Lanthanum and Cerium”, Russ. Metall.

(Engl. Transl.), (5), 56-58 (1982), translated from Izv. Akad. Nauk SSSR, Met., (5), 69-70

(1982) (Thermodyn., Experimental, 3)

[1982Fel] Felner, I., Nowik, I., “Magnetic Properties of RM6Al6 (R = Light Rare Earth, M = Cu, Mn,

Fe)”, J. Phys. Chem. Solids, 43(5), 463-465 (1982) (Crys. Structure, Experimental, Magn.

Prop., 4)

[1986Hel] Helmholdt, R.B., Palstra, T.T.M., Nieuwenhuys, G.J., “Magnetic Properties of

La(FexAl1-x)13 Determined via Neutron Scattering and Moessbauer Spectroscopy”, Phys.

Rev. B, Condens. Matter, B34(1), 169-173 (1986) (Crys. Structure, Experimental, 17)

[1986Gri] Griger, A., Syefaniay, V., Turmeze, T., “Crystallographic Data and Chemical Compositions

of Aluminum-Rich Al-Fe Intermetallic Phases”, Z. Metallkd., 77, 30-35 (1986) (Equi.

Diagram, Crys. Structure, Experimental, 23)

[1986Gsc] Gschneidner, K. A., Calderwood, “Intra Rare Earth Binary Alloys: Phase Relationships,

Lattice Parameters and Systematics“ F. W., Handbook of the Physics and Chemistry of Rare

Earths, Gschneidner, K.A., Eyring, L. (Eds.), Vol. 8, North-Holland Physics Publishing,

Amsterdam, pp. 1-161 (1986) (Review)

[1986Pal] Palstra, T.T.M., Nieuwenhuys, G.J., Mydosh, J.A., Helmholdt, R.B., Buschow, K.H.J.,

“Neutron Diffraction and Magnetostriction of Cubic La(FexAl1-x)13 Intermetallic

Compounds”, J. Magn. Magn. Mater., 54-57, 995-96 (1986) (Crys. Structure, Magn. Prop.,

Experimental, 5)

[1992Gri] Grieb, B., “Aluminium-Iron-Lanthanum”, MSIT Ternary Evaluation Program, in MSIT



Assessment, 9)

[1992Hu] Hu, B.P., Coey, J.M.D., Klesnar, H., Rogl, P., “Crystal Structure, Magnetism and 57Fe

Moesbauer Spectra of Ternary RE6Fe11Al3 and RE6Fe13Ge Compounds”, J. Magn. Magn.

Mater., 117, 25-231 (1992) (Crys. Structure, Experimental, Magn. Prop., Moessbauer, 14)

[1993Kat] Kattner, U.R., Burton, B.P., “Al-Fe (Aluminum-Iron)”, Phase Diagrams of Binary Iron

Alloys, Okamoto, H. (Ed.), ASM International, Materials Park, OH, 12-28 (1993) (Equi.


[1993Tan] Tang, W.H., Liang, J.K., Yan, X.H., Yie, S.S., “Subsolidus Relations of the La-Fe-Al

Ternary System and Magnetic Phase Realtion of La(FexAl1-x)13 Solid Solution”, Proc. 17th

Nat. Symp. Phase Diagrams, 4-7 (1993) (Equi. Diagram, Experimental) as quoted by

[1997Eff]


Phase with the Approximate Composition Fe2Al5”, Acta Crystallogr., B50, 313-316 (1994)


279


MSIT®

Al–Fe–La




[1995Tan1] Tang, W., Liang, J., Rao, G., Guo, Y., Zhao, Y., “Subsolidus Phase Relations of the

La-Fe-Al Ternary System” J. Alloys Compd., 218, 127-130 (1995) (Crys. Structure, Equi.


[1995Tan2] Tang, W., Liang, J., Yang, Y., Zhou, Y., Yan, X., Xie, S., “Structural Transition and

Magnetic Properties of La6Fe13-xAlx Intermetallic Compounds”, Prog. Nat. Sci., 5(6),

747-52 (1995) quoted in [C.A.] 124:182135g

[1996Sac] Saccone, A., Cardinale A., Delfino S., Ferro R., “Phase Equilibria in the Rare Earth Metals

(R)-Rich Regions of the R-Al Systems (R = La - Ce - Pr - Nd)”, Z. Metallkd., 87(2), 82-86


[1997Eff] Effenberg, G., Bodak, O.I., Petrova, L.A., Red Book. Constitutional Data and Phase

Diagrams of Metallic Systems (Summaries of the publication year 1993), MSI GmbH,

Stuttgart, Vol. 38 (1997)


compound FeAl”, Mater. Sci. Eng. A, A230, 124-131 (1997) (Crys. Structure,

Experimental, 23)

[1997Sri] Srinivasan, S., Raman, A., Ferrel, R.E.Jr., Grenier, C.G., “Lanthanum-Containing Ternary

Solid Solutions with NaZn13-, ThMn12- and Th2Zn17-Type Crystal Structures”,

Z. Metallkd., 88(6), 474-479 (1997) (Equi. Diagram, Crys. Structure, Experimental, Magn.

Prop., Review, 22)

[1997Zha] Zhang, W., Li, C., “The Fe-La (Iron-Lanthanum) System”, J. Phase Equilib., 18(3) 301-304





[1998Gro] Groot de, C.H., Buschow, K.H.J., Boer de, R.F., “Magnetic Properties of R6Fe13-xM1+x

Compounds and Their Hydrides”, Phys. Rev. B, Condens. Matter, 57(18), 11472-11482

(1998) (Crys. Structure, Experimental, Magn. Prop., 34)

[1998Guo] Guo, Y.Q., Yu, R.H., Zhang, R.L., Zhang, X.H., Tao, K., “Calculation of Magnetic

Properties and Analysis of Valence Electronic Structures of LaT13-xAlx (T = Fe, Co)

Compounds”, J. Phys. Chem. B, B102(1), 9-16, (1998) (Calculation, Magn. Prop., Electr.

Prop., 30)

[1998Lei] Leineweber, A., Jacobs, H., “Preparation of Single Crystals of LaAl and X-Ray Structure

Determination”, J. Alloys Compd., 278, L10-L12 (1998) (Crys. Structure, Experimental, 11)

[1998Sch] Schobinger-Papamantellos, P., Buschow, K.H.J., Ritter, C., “Magnetic Ordering and Phase

Transitions of RFe4Al8 (R = La, Ce, Y, Lu) Compounds by Neutron Diffractioin”, J. Magn.

Magn. Mater., 186, 21-32 (1998) (Crys. Structure, Experimental, Magn. Prop., 13)

[1998Thi] Thiede, V.M.T., Ebel, T., Jeitschko, W., “Ternary Aluminides LnT2Al10(Ln = Y, La = Nd,

Sm, Gd = Lu and T=Fe, Ru, Os) with YbFe2Al10 Type Structure and Magnetic Properties

of the Iron-Containing Series“, J. Mater. Chem., 8(1), 125-130 (1998) (Crys. Structure,





[1999Moz] Moze, O., Kockelmann, W., Liu, J.P., de Boer, F.R., Buschow, K.H.J., “Structure and

preferred site occupation of N in the compound LaFe11Al2 after nitrogenation”, J. Magn.

Magn. Mater., 195, 391-395 (1999) (Crys. Structure, Experimental, 13)

[2000Iri] Irisawa, K., Fujita, A., Fukamichi, K., “Magnetic Phase Diagram of La(FexAl1-x) 3 in the

Vicinity of the Ferromagnetic-Antiferromagnetic Phase Boundary”, J. Alloys Compd., 305,

17-20 (2000) (Crys. Structure, Experimental, Magn. Prop., 15)

280


MSIT®

Al–Fe–La

[2000Moz] Moze, O., Kockelmann, W., Liu, J.P., de Boer, F.R., Buschow, K.H.J., “Magnetic Structure

of LaFe10.8Al2.2 and LaFe10.8Al2.2N3 Cluster Compounds”, J. Appl. Phys., 87(9),


[2000Sik] Sikora, W., Schobinger-Papamantellos, P., Buschow, K.H.J., “Symmetry Analysis of the

Magnetic Ordering in RFe4Al8 (R = La, Ce, Y, Lu and Tb) Compounds (II)”, J. Magn.

Magn. Mater., 213, 143-156 (2000) (Calculation, Crys. Structure, Magn. Prop., 8)

[2000Tam] Tamura, I., Mizushima, T., Isikawa, Y., Sakurai, J., “Mössbauer Effect and Magnetization

Studies of CeFe2Al8 and LaFe2Al8”, J. Magn. Magn. Mater., 220, 31-38 (2000) (Crys.

Structure, Experimental, Moessbauer, 4)

[2000Yin] Yin, F., Su, X., Li, Z., Huang, M., Shi, Y., “A Thermodynamic Assessment of the La-Al

System”, J. Alloys Compd., 302, 169-172 (2000) (Assessment, Equi. Diagram, Thermodyn.,

14)

[2000Wan] Wang, F., Zhang, P., Shen, B., Yan, Q., “Transport Properties of R6Fe11Al3 Compounds (R

= La, Nd)”, J. Appl. Phys., 87(9), 6043-6045 (2000) (Experimental, Magn. Prop., 10)

[2001Bor] Borzone, G., Parodi, N., Ferro, R., Bros, J.P., Dubes, J.P., Gambino, M., “Heat Capacity and

Phase Equilibria in Rare Earth Alloy System. R-Rich R-Al Alloys (R = La, Pr and Nd)”,

J. Alloys Compd., 320(2), 242-250 (2001) (Equi. Diagram, Thermodyn., Experimental, 36)

[2001Iri1] Irisawa, K., Fujita, A., Fukamichi, K., Mitamura, H., Goto, T., “Magnetic Phase Transition

in the Antiferromagnetic Compound La(Fe0.89Al0.11)13”, J. Alloys Compd., 327, 17-20

(2001) (Crystal Structure, Magn. Prop., Experimental, 10)

[2001Iri2] Irisawa, K., Fujita, A., Fukamichi, K., Mitamura, H., Goto, T., “Effect of Pressure on

Magnetic Properties of La(FexAl1-x) 13 Ferromagnetic Compounds”, J. Alloys Compd., 329,

42-46 (2001) (Crys. Structure, Magn. Prop., Experimental, 24)

[2001Iri3] Irisawa, K., Fujita, A., Fukamichi, K., Yamazaki, Y., Iijima, Y., Matsubara, E., “Change in

the Magnetic State of Antiferromagnetic La(Fe0.88Al0.12)13 by Hydrogenation”, J. Alloys

Compd., 316, 70-74 (2001) (Crys. Structure, Magn. Prop., Experimental, 24)


bcc Phases in the Fe-Rich Portion of hte Fe-Al System”, Intermetallics, 9, 755-761 (2001)

(Equi. Diagram, Termodyn., Experimental, 18)

[2001Rag] Raghavan, V., “Al-Fe-La (Aluminum-Iron-Lanthanum)”, J. Phase Equilib., 22(5), 566-567

(2001) (Equi. Diagram, Crys. Structure, Review, 6)

[2002Jon] Jonen, S., Rechenberg, H.R., Campo, J., “Rare Earth Effects on the Magnetic Behavior of

R6Fe11-xAl3+x Compounds”, J. Magn. Magn. Mater., 242-245, 803-805 (2002) (Crys.


[2003Gro] Gröbner, J., “Al-La (Aluminium-Lanthanum)”, MSIT Binary Evaluation Program, in MSIT



[2003Pis] Pisch, A., “Al-Fe (Aluminium-Iron)”, MSIT Binary Evaluation Program, in MSIT



281


MSIT®

Al–Fe–La


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( La)

918-865

cI2

Im3m

W

a = 426.0 [1986Gsc]

( La)

865-310

cF4

Fm3m

Cu

a = 530.3 [1986Gsc]

( La)

< 310

hP4

P63/mmc

La

a = 377.4

c = 1217.1

[1986Gsc]

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


( Fe)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2, 1993Kat]


( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12



0 - 18.8 at.% Al, HT [1958Tay]

0 - 19.0 at.% Al, HT [1961Lih]

0 - 18.7 at.% Al, 25°C [1999Dub]

Fe4Al13

< 1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16-76.70 at.% Al [1986Gri]

at 76.0 at.% Al [1994Gri]

Fe2Al5< 1169

oC24

Cmcm

Fe2Al5

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [1994Bur]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [1993Kat]

282


MSIT®

Al–Fe–La

1232-1102

cI16? a = 598.0 at 61 at.% Al [1993Kat]

FeAl

< 1310

cP8

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5 - 47.5 at.% Al [1961Lih]

36.2 - 50.0 at.% Al [1958Tay]

39.7 - 50.9 at.% Al [1997Kog] 500°C

quenched in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

24 - 37 at.% Al [2001Ike]

23.1 - 35.0 at.% Al [1958Tay]

24.7 - 31.7 at.% Al [1961Lih]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [1993Kat]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [1993Kat]

[1998Ali]

FeAl4+x t** a = 884

c = 2160


[1998Ali]

La3Al

~520-400

hP8

P63/mmc

Ni3Sn

a = 722.8

c = 551.7

[1965Bus]

LaAl

< 873

oC16

Cmcm

CeAl

a = 945.5

b = 775.3

c = 579.1

[1998Lei]

LaAl2< 1405

La(FexAl1-x)2

cF24

Fm3m

MgCu2

a = 814.2

a = 814.7

a = 811.1

at x = 0 [1965Bus]

0 x 0.2 at 25°C [1995Tan1]

at x = 0 [1995Tan1]

at x = 0.2 [1995Tan1]

LaAlx1240-1090

hP3

P63/mmm

AlB2

a = 447.8

c = 434.7

x ≅ 2.3

[1965Bus]

LaAl3< 1170

hP8

P63/mmc

Ni3Sn

a = 666.4

c = 461.5

[1965Bus]

La3Al11

1240-915

tI10

I4/mmm

BaAl4

a = 445.6

c = 1033

[1965Bus]

La3Al11

< 915

oI28

Immm

La3Al11

a = 443.3

b = 1315

c = 1013

[1965Bus]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

283


MSIT®

Al–Fe–La

* 1, La(FexAl1-x)13 cF112

Fm3c

NaZn13

a =1197 to 1183

a =1196

a = 1173.8 to 1157.9

a = 1198.3 to 1166.8

a = 1199 to 1174

a = 1162.81

0.462 x 0.539 [1968Zar]

[1982Fel] for LaFe6Al60.46 x 0.92 [1986Hel] (range in

which the phase may be stabilized)

0.44 x 0.82 [1995Tan1]

0.425 x 0.575 [1997Sri]

[1999Moz] at x = 0.84

* 2, LaFe4Al8

LaFe3.5Al8.5

tI26

I4/mmm

ThMn12

a = 890.0

c = 507.5

a = 882

c = 519

a = 892

c = 510

[1976Bus]

[1968Zar]

A composition range included between

62 and 65 at.% Al at 800°C was shown

in a partial tentative phase diagram by

[1997Sri]

* 3, LaFe2Al8

~LaFe2Al7

oP44

Pbam

CeFe2Al8

a = 1257

b = 1445

c = 406.3

[2000Tam]

observed in La10Fe17.5Al72.5

[1968Zar]

* 4, La2(FexAl1-x)17 hR57

R3m

Th2Zn17

a = 905 to 899

c = 1313 to 1304

a = 896.2

c = 1298

a = 869.0

c = 1300

0.35 x 0.41 [1968Zar]

at x = 0.41 [1995Tan1]

at x = 0.41 [1982Fel]

* 5, La6Fe11Al3 tI80

I4/mcm

La6Co11Ga3

a = 822.3

c = 2382.1

[1992Hu]

* 6, LaFe2Al10

LaFe1.2Al7.8

La2Fe2Al15

oC52

Cmcm

YbFe2Al10

?

?

a = 905.1

b = 1024.9

c = 912.2

[1968Zar, 1998Thi]

[1995Tan1] observed as unknown

structure phase

[1997Sri] observed as unknown

structure phase

* 7, La(Fe1-xAlx)2

LaFeAl

La36Fe44Al201

La5Fe6Al4

? 0.3 x 0.5 (33.3 at.% La, 46.7-33.3

at.% Fe) [1968Zar]

x = 0.5 (33.3 at.% La, 33.3 at.% Fe)

[1971Oes]

[1995Tan1]

[1997Sri]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

284


MSIT®

Al–Fe–La

20

40

60

80

20 40 60 80

20

40

60

80

La Fe


Axes: at.%

τ6Fe4Al13

Fe2Al5

FeAl2

τ7

τ1

La3Al11

LaAl3

LaAl2

LaAl

(αFe)

(αLa)

τ2

τ4

(Al)Fig. 1: Al-Fe-La.

The isothermal section

at room temperature

suggested by

[2001Rag], mainly on

the basis of

[1995Tan1]

285


MSIT®

Al–Fe–Mg

Aluminium – Iron – Magnesium

Ibrahim Ansara†, Michael Hoch, Nigel Saunders, Eberhard E. Schmid, updated by Ibrahim Ansara

†, Yong

Du and Patrick Wollants

Literature Data

By adding Mg to liquid iron ductile iron alloys can be obtained with much improved mechanical properties.

This alkaline metal is also used as an addition in liquid steels for desulfurization, deoxidation and also for

control and modification of non-metallic inclusions. Most of the experimental phase diagram data were

determined in the aluminium-rich corner, limited by the section Fe4Al13-Mg2Al3. [1934Fus] determined the

fields of primary crystallization by metallography. [1938Bar] analyzed 34 alloys by DTA and

metallography. They observed that an as-cast alloy containing about 10.4 mass% Mg and 3.2 mass% Fe,

which had been annealed below the eutectic temperature, 435°C, was two-phase (with an Al-rich solid

solution and Fe4Al13) whereas the as-cast sample contained substantial ternary eutectic. [1938Hof] by

X-ray diffraction compared the pattern of Fe4Al13 in an alloy on the Fe4Al13-Mg2Al3 section with that of

pure Fe4Al13 and could not find any difference in the lattice parameters. Thus he concluded that, in the four-

phase equilibrium, no magnesium dissolves in Fe4Al13. [1941Phi] studied the constitution of alloys of

aluminium in detail in the composition range 0 to 5 mass% Mg and 0 to 2.5 mass% Fe, using thermal

analysis and metallography. He also redetermined the position of the monovariant line, liquidus, solidus,

solvus and invariant temperatures. The alloys were not in thermodynamic equilibrium because [1941Phi]

studied them in the as-cast state. [1958Gul], by thermal analysis, determined some liquidus temperatures

along the section Fe4Al13-Mg2Al3 as well as the microstructure for selected alloy compositions. The only

available information for the Mg-rich corner concerns the solubility in the liquid state versus temperature

which was determined by [1944Bee] and confirmed later by [1951Bak]. [1984Age] measured the solubility

of Mg in Fe-rich liquid Al-Fe alloys at 1600°C. No ternary compounds have been identified in this system.

Binary Systems

Phase diagram of the Al-Mg binary system is accepted from the evaluation by [2003Luk]. The Al-rich part

of the Al-Fe system is taken from [Mas] or from [1982Kub], whereas [1981Sch] was chosen for the Al-rich

phase boundaries of the Al-Mg system. The non-stoichiometry range of Fe4Al13 (also designated as FeAl3)

is not well defined (0.745 < xAl < 0.766) [Mas2]. The solubility range of Al (molar fraction) ranges from

0.385 to 0.403. The decomposition of Fe4Al13 at ~ 1152°C could be congruent [1986Len] but remains

uncertain.

Solid Phases

Table 1 lists the solid phases of the partial system (Al)-Mg2Al3-Fe4Al13. No ternary compounds have been

identified.


[1934Fus] and [1958Gul] consider “Fe4Al13”-Mg2Al3 to be a pseudobinary section of nearly degenerate

type. However, according to the accepted binary diagrams this is not quite the case. [1958Gul] noted

thermal arrests at approximately 650 and 550°C in addition to the 451°C eutectic arrest. No explanation was

given for the higher-temperature thermal effects.


According to [1934Fus, 1938Bar, 1938Hof, 1941Phi], there is a eutectic reaction

L (Al)+“Fe4Al13”+Mg2Al3 in the Al-rich corner whose temperature is very close to the l (Al)+Mg2Al3binary eutectic. [1938Bar] suggested that the iron content in the ternary eutectic liquid was 3.0 mass% Fe

286


MSIT®

Al–Fe–Mg

at 445°C (3 K lower than the measured binary eutectic). In later work [1934Fus] and [1958Gul] proposed

that in fact the amount of iron is much smaller. [1958Gul] refers to the solubility of “Fe4Al13” in the liquid

state of the section to Mg2Al3 as ~ 0.2% at 500°C. In the reviews of [1961Phi] and [1976Mon], the values

of the iron composition are given as 0.14 mass% and approximately 0.15 mass%, respectively. Within

experimental errors, the temperature of the ternary eutectic is indistinguishable from that of the binary

Al-Mg2Al3 eutectic. In addition, [1961Phi] quotes that the composition of the Al solid solution at the

eutectic contains ~ 15 mass% Mg and 0.05 mass% Fe. The invariant reaction is therefore considered to be

degenerate, as shown in the reaction scheme, Fig. 1.

Liquidus Surface

In his review, [1961Phi] presented the liquidus surface for the Al-rich alloys based on his earlier work

[1941Phi]. Nine alloys were analyzed by sampling the liquid after equilibrating at various fixed

temperatures between 650 and 700°C (Fig. 2). Figure 3 presents the solidus surface.

Isothermal Sections

From the solubility measurements of [1941Phi] at the eutectic temperature, the solubility of both iron and

magnesium in the Al-rich solid solution is virtually unchanged. Based on this observation, an isothermal

section at 400°C was constructed, as shown in Fig. 4.


[1941Phi] presents three isopleths (1.0 mass% Fe, 1.0 mass% Mg, 4.0 mass% Mg) for Al-rich alloys,

determined by thermal analysis. Liquidus, solidus and solvus temperatures were thus measured. Some

solidus temperatures were determined by a heating-quench method. The measured ternary eutectic

temperature is equal to 451°C, which is in agreement with [1958Gul] experiments, who used thermal

analysis for alloy compositions in the “MgAl3-Fe4Al13” section, which is nearly of a degenerate type.

However, there are inconsistencies in [1941Phi]. The limiting binary systems defined by this section are

substantially different from the accepted Al-Mg diagram. Due to these inconsistencies, no figures are

reproduced.

Miscellaneous

Solubility curves for magnesium-rich alloys were determined by [1944Bee] by sampling equilibrated liquid

alloys. His results are shown in Figs. 5 and 6. For the iron-rich corner, the solubility curve at 1600°C from

[1984Age] is presented in Fig. 7. The effect of Al on the solubility of Mg in liquid Fe at 1600°C was

measured by a vapor-molten Fe equilibration method [1996Li]. The equation lnxMg = 9.73+12.30xAl fits

the data. From these measurements the interaction coefficient (MgAl) as derived from

the-Margules-Wagner formalism is equal to 12.30. By rapid solidification and consolidation, the increase

of Mg concentration in Al-Fe-Mg alloys leads to a decrease of the maximum solid solubility extension

[1994Abr]. The maximum solubility for the Al-4Mg-Fe (at.%) alloys is 2 at.%, and for a Al-6Mg (at.%) the

maximum solubility is only equal to 1 at.% Fe [1994Abr].

References

[1934Fus] Fuss, V., “Metallography of Aluminium and its Alloys” (in German), Springer Verlag,

Berlin, 141-142 (1934), translated Anderson R.J., The Sherwood Press Inc. Cleveland,


[1938Bar] Barnick, M., Hanemann, H., “A Contribution to the Knowledge of the

Aluminium-Iron-Magnesium System” (in German), Aluminium, 20, 771-774 (1938) (Equi.


[1938Hof] Hofmann, W., “X-ray Methods for the Investigation of Aluminium Alloys” (in German),

Aluminium, 7, 865-872 (1938) (Crys. Structure, Equi. Diagram, Experimental, 19)

287


MSIT®

Al–Fe–Mg

[1941Phi] Phillips, H.W.L., “The Constitution of Alloys of Aluminium with Magnesium and Iron”,

J. Inst. Met., 67, 275-287 (1941) (Equi. Diagram, Experimental, 8)

[1944Bee] Beerwald, A., “On the Solubility of Iron and Manganese in Magnesium and in Magnesium

- Aluminium Alloys” (in German), Metallwirtschaft, 23, 404-407 (1944) (Equi.Diagram,


[1951Bak] Baker, W.A., Eborall, M.D., “Note on the Solubility of Iron in Liquid

Magnesium-Aluminium Alloys”, Metallurgia, 44, 145-146 (1951) (Experimental, 2)

[1958Gul] Gul'din, I.T., Dokukina, N.V., “The Aluminium-Magnesium-Iron-Silicon System”,

J. Inorg. Chem., 3, 359-378 (1958), translated from Zh. Neorg. Khim., 3, 799 (1958) (Equi.

Diagram, Experimental, #, 5)

[1961Phi] Phillips, H.W.L., “Equilibrium Diagrams of Aluminium Alloy Systems”, The Aluminium

Development Association, London, 84-86 (1961) (Equi. Diagram, Review, 0)

[1976Mon] Mondolfo, L.F., “Aluminium Alloys: Structure and Properties”, Butterworths,

London-Boston (1976) (Equi. Diagram, Review, Phys. Prop., Crys. Structure)

[1981Sch] Schürmann, E., Voss, H.-J., “Investigation of the Melting Equilibria of Lithium-Aluminium

Alloys. IV. Melting Equilibria of the Binary Magnesium-Aluminium System” (in German),

Giessereiforschung, 33, 43-46 (1981) (Equi. Diagram, Experimental, #, 17)

[1982Kub] Kubaschewski, O., “Iron Binary Phase Diagrams”, Springer Verlag, Berlin (1982) (Equi.

Diagram, Review)

[1984Age] Ageev, Yu.A., Archugov, S.A., “On the Solubility of Mg in Liquid Fe and Some Fe-based

Binary Liquid Alloys”, Russ. Metall., (3), 72-74 (1984), translated from Izv. Akad. Nauk

SSSR, Met., (3), 78-80 (1984) (Experimental, #, 6)

[1986Len] Lendvai, A., “Phase Diagram of the Al-Fe System up to 45 mass% Iron”, J. Mater. Sci., 5,


[1990Sau] Saunders, N., “A Review and Thermodynamic Assessment of the Al-Mg and Mg-Li

Systems”, Calphad, 14, 61-70 (1990) (Equi. Diagram, Thermodyn., Review, Theory, 59)

[1994Abr] Abramov, V.O., Sommer, F., “Structure and Mechanical Properties of Rapidly Solidified

Al-(Fe,Cr) and Al-Mg-(Fe,Cr) Alloys”, Mater. Lett., 20, 251-255 (1994) (Experimental,

Crys. Structure, Mechan. Prop., 6)

[1996Li] Li, X., Song, B., Han, Q., “Thermodynamic Properties of Liquid Fe-Mg-Al and Fe-Mg-Si

Dilute Ternary Solutions”, J. Phase Equilib., 17, 21-23 (1996) (Equi. Diagram,

Experimental, 11)




288


MSIT®

Al–Fe–Mg


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group

Prototype

Lattice Parameters

[pm]


(Al) cF4

Fm3m

Cu

a = 404.88 pure Al at 24°C [V-C]

Fe4Al13

1152

mC102

C2/m

Fe4Al13

a = 1548.9

b = 808.31

c = 1247.6

= 107.72°

[V-C]

0.745 < xAl < 0.766

Mg2Al3 cF1832

Fd3m

Mg2Al3

a = 2823.9 [V-C]

Fig. 1: Al-Fe-Mg. Reaction scheme

A-B-CFe4Al

13 - Al Al - Mg

2Al

3"Fe

4Al

13 - Mg

2Al

3"Al - Fe - Mg

l (Al)+Fe4Al

13

652 e1

l (Al)+Mg2Al3

450 e2

l Fe4Al

13+Mg

2Al

3

450 e3

L (Al)+Mg2Al

3, Fe

4Al

13450 D

(Al)+Fe4Al

13+Mg

2Al

3

289


MSIT®

Al–Fe–Mg

2

4

6

8

10

0

0

1 2 3 4 5 6

520°C

540

560

580

600

620

640

(Al)+Fe Al4 13

AlFe, mass%

Mg,mass%

Fig. 3: Al-Fe-Mg.

Solidus surface

[1961Phi]

2

4

6

8

10

0

0

1 2 3 4 5 6

Al Fe, mass%

Mg,mass%

610°C

615

620

625

630

635

640

645

650

655

67

5

700

725

750

775

800

825 850

Fe Al134

(Al)

Fig. 2: Al-Fe-Mg.

Liquidus surface

290


MSIT®

Al–Fe–Mg

10

20

30

10 20 30

70

80

90

Mg 40.00Fe 0.00Al 60.00

Mg 0.00Fe 40.00Al 60.00


Axes: at.%

Mg2Al3

(Al)

Fe4Al13

(Al)+Mg2Al3+Fe4Al13

0

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

1 2 3 4 5 6 7

Al, mass%

Fe,mass%

800°C

750

700

660

Fig. 4: Al-Fe-Mg.

Isothermal section of

the Al-rich corner at

400°C

Fig. 5: Al-Fe-Mg.

Solubility curves of

Fe in Mg-rich alloys

at constant

temperature

[1944Bee]

291


MSIT®

Al–Fe–Mg

10

90

10

Mg 20.00Fe 80.00Al 0.00

Mg 0.00Fe 80.00Al 20.00 Data / Grid: at.%

Axes: at.%

L1

L1+L2

Fe

0.010 0.02 0.03 0.04 0.05 0.06 0.07

700

750

800

Fe, mass%

Temperature,°C

7 2.7 1 0

Fig. 7: Al-Fe-Mg.

Position of the L1/

(L1+L2) phase

boundary in Fe-rich

Al-Fe-Mg alloys at

1600°C [1984Age]

Fig. 6: Al-Fe-Mg.

Solubility curves of

Fe with respect to

temperature for

selected alloy

compositions

[1944Bee]

292


MSIT®

Al–Fe–Mn

Aluminium – Iron – Manganese

Quingsheng Ran, updated by Alexander Pisch

Literature Data

This system has been the object of a number of investigations, but, partly because of the limitation in

composition ranges interested and partly because of the complicated boundary binary systems, the

constitution has not been established for the whole system. Most investigations are confined to the Fe-Mn

side and to the Al rich-corner. Solid solubilities of several binary intermediate phases, order-disorder

transition of some alloys, some magnetic and quasicrystalline phases were also investigated. The

constitution has been reviewed from time to time [1939Han, 1943Mon, 1952Han, 1961Phi, 1980Bra,

1983Riv, 1994Rag].

The most important experimental phase diagram works are [1933Koe, 1939Deg, 1943Phi, 1974Mur,

1974Shv, 1977Cha, 1981Bra, 1984Den, 1990Liu2, 1990Xu, 1992Xu, 1993Hao, 1993Liu1, 1993Liu2,

1997Mue], whereas [1944Ray, 1950Phr, 1952Han, 1959Sch, 1960Tsu, 1962Tsu, 1974Fau, 1975Urs,

1978Urs, 1987Den, 1990Liu1] provided additional information related to phase equilibria. Mostly pure Al

(~ 99.9% or higher) was used, whereas Mn and Fe were added as master alloys. Methods used are:

metallography [1933Koe, 1939Deg, 1943Phi, 1974Shv, 1977Cha, 1981Bra, 1984Den, 1990Liu2, 1990Xu,

1992Xu, 1992Liu, 1993Liu1, 1993Liu2, 1997Mue]; X-ray diffraction [1939Deg, 1974Mur, 1977Cha,

1981Bra, 1990Xu]; dilatometry [1933Koe]; thermal analysis [1939Deg, 1943Phi, 1993Hao, 1993Liu2];

electron microprobe [1984Den, 1990Liu2, 1990Xu, 1992Xu, 1992Liu, 1993Liu1, 1993Liu2] and diffusion

couples [1990Liu2, 1992Liu, 1993Liu1, 1993Liu2].

Binary Systems

The binary systems Al-Fe and Al-Mn are accepted from [2003Pis1] and [2003Pis2], respectively. The

Fe-Mn binary phase diagram has been taken from [1993Oka].

Solid Phases

The solid phases ( Fe) and ( Mn) form a continuous solid solution extended from Fe-Mn side in the

direction to the Al corner.

The solid solutions of Al in ( Fe) and ( Mn) form a continuous range of solid solutions above temperatures

1000 to 1200°C. This may also be true for lower temperatures, but there is no experimental work clarifying

this question.

The binary compound MnAl6 can dissolve a considerable amount of Fe [1939Deg, 1944Ray, 1950Phr,

1973Kow, 1975Bar, 1984Den, 1994Ser, 1995Ser, 1998Wei]. Generally these investigations agree on

solubility up to Mn0.5Fe0.5Al6. Only [1984Den] gave a value of Mn0.25Fe0.75Al6, significantly higher than

the other studies. [1944Ray] stated this as a replacement of Mn by Fe atom by atom. Lattice parameters for

the solid solutions were determined by several studies. The solubility of Fe increases with falling

temperature [1987Den].

In the Fe4Al13 phase the solubility of Mn is also due to substitution of Fe by Mn [1944Ray]. The amount of

dissolved Mn in this phase reported by [1944Ray] and [1984Den] is approximately 3 at.%. [1994Ser,

1995Ser, 1998Wei] reported a value of 5 at.% Mn at 550°C at the Al rich boundary, which is higher than

that given as “quite low” by other investigations [1939Deg, 1943Phi, 1950Phr, 1952Han, 1974Mur]. A

maximum solubility value of 9.5 at.% Mn can be reached at 550°C for lower Al contents in the ternary

[1998Wei].

[1960Tsu] and [1962Tsu] reported a ferromagnetic phase, called , with the compositions range 35 to 47.5

Mn, 40 to 47.5 Al and 10 to 17.5 at.% Fe, with the CsCl type structure.

[1969Ily] studied the MnFe2Al alloy by X-ray diffraction. After annealing at 650°C for several hours, a new

phase with the composition Mn6Fe9Al5 precipitated. Its structure was determined as Mn type. [1987Lu]

293


MSIT®

Al–Fe–Mn

obtained a precipitate with the composition Mn6Fe9Al5 from an alloy Fe-9.1 Al-29.9 Mn-2.9 mass% Cr.

This was proposed to be a ternary phase. Its crystal structure has been determined to be similar to Mn, but

not the same. The space group was given as P4332. [1975Zal] and [1977Ath] also studied the structure of

alloys of similar compositions, but suggested ordering to the CsCl type by cooling to between 700 and

750°C and another ordering to the MnCu2Al type between 500 and 600°C [1975Zal]. The structural

characteristics of alloys with this composition need still to be clarified. Earlier [1937Moe] and [1939Deg]

suggested ternary phases with unknown compositions. However, their existence was denied by later works

[1939Deg, 1944Ray].

[1964Var] reported the determination of joint solubilities of Mn and Fe in solid (Al) by X-ray analysis. The

results report Al to dissolve 1.5 mass% Mn and 1.5 mass% Fe simultaneously. This, however, is

incompatible with the accepted binary solubilities of Fe and Mn in solid (Al), which are significantly less.

(Al) should dissolve 0.62 at.% Mn and nearly no Fe, as reported by [1939Deg] and [1952Han].

Several papers deal with a decagonal phase, at a composition (Mn0.7Fe0.3)2Al7 [1986Dub, 1987Ma,

1987Wou, 1988Pau, 1988Sch]. This alloy and the alloys at compositions Mn2Al7 and Fe2Al7 are 5-fold

twins and there are 1664 atoms in an orthorhombic unit cell in 16 icosahedral clusters of 104 atoms with the

lattice parameters a = 3286, b = 3123 and c = 2480 pm [1988Pau].

[1998Wei] reported the existence of four new ternary phases in the Al-rich corner at 550°C: 1,

Mn1-xFexAl4 with unknown structure, 2, (MnxFe1-x)4Al13 being isostructural to the high temperature

modification of Fe4Al13, 3,(Mn1-xFex)3Al10 which is of the Mn3Al10 type and 4, (Mn1-xFex)Al3-x with a

Mn4Al11(HT) type structure. 4 is probably not a true ternary phase, because the binary equivalent is stable

at higher temperatures.

Mn substitution in the ordered B2 FeAl phase has been studied theoretically by [1999Mek] and

experimentally using the ALCHEMI (Atom Location by Channeling Enhanced Microanalysis) technique

by [1997And]. Conclusion could be made that Mn atoms substitute mainly on Fe sites in the phase lattice.

[1986Sch] claimed a single phase decagonal quasicrystal in an Mn18Fe2Al80 alloy.

The quasicrystalline icosahedral phase of the approximate Mn14-xFexAl86 composition with fivefold

symmetry was obtained in rapidly solidified alloys by [1993Nis, 1995Sin] and by mechanical alloying in

[1999Sch, 2000Sch].


So far two invariant equilibria have been identified [1939Deg, 1943Phi, 1950Phr, 1952Han, 1984Den,

1987Den, 1995Ser]. Different investigations agree on the temperatures and compositions of the liquid in

these reactions fairly well. [1939Deg] suggested a eutectic reaction L (Al) + Fe4Al13 + (Mn,Fe)Al6 which

was confirmed by later works and a transition reaction L + -MnAl4 (Mn,Fe)Al6 + with being an

unknown ternary phase. [1943Phi] later denied the existence of the phase and established the reaction to

be a peritectic one, L + Fe4Al13 + -MnAl4 (Mn,Fe)Al6. This has found support by later work [1950Phr,

1952Han] and is accepted in this evaluation (see also the section “Liquidus Surface”). The two reactions are

given in Table 2. The temperatures have been taken from the most recent DSC measurements by [1995Ser].

Liquidus Surface

Reports on the liquidus surface are only given for the Al corner [1939Deg, 1943Phi, 1950Phr, 1984Den,

1987Den]. Concerning the invariant reactions and univariant liquid troughs they agree with each other fairly

well, but [1939Deg] and [1943Phi] showed different extensions of the primary region of MnAl6. [1939Deg]

proposed a more extended region of primary solidification of MnAl6 and an unidentified, perhaps ternary,

phase participating in the ternary peritectic reaction. [1943Phi] however presented the MnAl6 primary

solidification closed by a trough between the ternary peritectic and the ternary eutectic reaction and denied

the existence of any ternary phases in the investigated region. The diagram proposed by [1939Deg]

demands quite improbable liquidus isotherms. The liquidus projection of [1943Phi] is supported by

[1950Phr]. Figure 1 shows the liquidus surface projection mainly based on the results of [1943Phi].

[1943Phi] also presented a projection of the surface of secondary separation.

294


MSIT®

Al–Fe–Mn

Isothermal Sections

Isothermal sections constructed are shown in Figs. 2 to 8.

Experimental results on the 1000°C section have been presented by [1974Shv, 1977Cha, 1981Bra,

1990Liu2, 1990Xu, 1992Liu, 1993Liu1, 1993Liu2], whereas [1990Liu1, 1993Liu3] gives a calculated

partial section. [1977Cha, 1981Bra, 1990Liu2] agree with a three-phase equilibrium between ( Fe, Mn),

( Mn) and ( Fe, Mn). [1990Xu] determined only two-phase equilibria between ( Fe, Mn) and

( Fe, Mn), with results in agreement with other experimental works. [1977Cha, 1981Bra, 1990Liu2] give

different Al contents for the phases in this equilibrium. The diffusion couple determination of phase

boundaries by [1990Liu2] is strongly supported by the results of metallography, X-ray analysis and electron

microprobe analysis of [1990Xu, 1992Xu] and does not contradict the measurements of [1981Bra],

although [1981Bra] gives higher Al contents of the phases at equilibrium. The highest Al contents are given

by [1977Cha]. Their results agree qualitatively with the accepted Al-Mn binary but the overall Al contents

seem to be systematically too high. The Al-Mn rich part has been estimated according to their work and the

accepted Al-Mn binary. The equilibrium between ( Mn) and ( Fe, Mn) to the Al-Mn boundary, suggested

by [1990Liu2], is in agreement with the calculation of [1990Xu]. The equilibria ( Fe, Mn)/ determined

by [1990Liu2, 1981Bra] and by [1974Shv] for 1000 to 1150°C are in good agreement. The results are

summarized in Fig. 5. Examination of several samples support the homogeneity range of ( Fe) extending

at least to 30 at.% Mn at 25 at.% Al [1988Per].

Figure 4 shows the partial isothermal section at 1100°C on the Al-poor edge, determined by [1990Liu2,

1992Liu] and [1990Xu], in agreement with the calculation of [1990Liu1, 1993Liu3] adjusted to the

accepted binary systems. The equilibrium between ( Fe, Mn) and ( Fe, Mn) at 1200°C, Fig. 3, is from

[1990Liu2, 1993Liu1] who measured over the whole region, revealing a lower Al content than [1990Xu,

1990Liu1].

[1993Liu2] presented a partial isothermal section at 1300°C with ( Fe, Mn)-L and ( Fe, Mn)-( Fe, Mn)

two phase equilibria at low Al content (Fig. 2).

Equilibria between ( Fe, Mn), ( Fe, Mn) and ( Mn) are also determined for 900 and 800°C [1990Xu,

1992Xu], 760°C [1959Sch] and 850, 750, 650°C [1974Shv], showing similar equilibrium relationships, but

with decreasing Mn contents with falling temperature for the three-phase equilibrium. Those for 760°C

[1959Sch] and for 800°C [1990Xu] are in very good agreement and are shown in Fig. 6. The ( Fe) - FeAl

order-disorder transformation was missing in the original works and has been added tentatively in Fig. 2, 5

and 6.

[1974Mur] proposed an isothermal section for 600°C from X-ray phase analysis. This work has not been

taken into account in the present evaluation due to strong deviations from the accepted binary systems.

The equilibria including the ferromagnetic phase at 700°C have been established by [1997Mue] by

metallography and optic emission spectroscopy. The phase is in equilibrium with 2 and ( Mn). The

partial isothermal section is redrawn in Fig. 7.

[1994Ser, 1995Ser, 1998Wei] determined the partial isothermal section in the Al rich corner at 550°C.

[1995Ser] claimed in their extensive study, that equilibrium is not attained even after 3000h of anneal and

that the phases and their composition depend on the solidification path. This has not been confirmed in

[1998Wei] where equilibria seem not to depend on initial conditions. There are some contradictions

between the text and the published diagram in [1998Wei]. They have been corrected according to the

accepted binaries and the solid phases table given by [1998Wei]. The modified isothermal section of

[1998Wei] is presented in Fig. 8.


A series of vertical sections have been investigated: 2 and 6 mass% Mn and 4 mass% Fe [1943Phi]; 4, 7, 10

mass% Al [1974Shv]; 2, 10, 30 mass% Al, 20 mass% Mn and 40 mass% Fe [1933Koe]; 45 at.% Al

[1975Urs, 1978Urs]. Among these only the 2 mass% Mn of [1943Phi] can be considered as acceptable; the

others contradict either the isothermal sections or the phase rule or differ strongly from the accepted binary

systems. The partial section at 2 mass% Mn is redrawn in Fig. 9, and Fig. 10 gives an amended partial

section with 4 mass% Fe.

295


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Al–Fe–Mn


[1990Wer] investigated decagonal (Mn0.7Fe0.3)Al7 and icosahedral Al80Mn20-xFex samples by Mössbauer

spectroscopy. The latter compound obeys the Hume-Rothery rule on alloy stability for x = 9. The magnetic

properties of metastable ferromagnetic Mn60-xFexAl40 thin films prepared by DC magneton sputtering have

been determined by [1991Mat]. The saturation magnetization and coercitivity increased compared to pure

Mn60Al40 with a maximum at x = 0.05 to 0.1. [2001Gon] studied the magnetic properties of the same alloys

by Mössbauer, and ac susceptibility with x ranging from 20 to 60 on samples obtained by mechanical

alloying for 48 hours. A magnetic phase diagram has been drawn at low temperature: alloys with x < 40

show paramagnetic behavior at room temperature and become ferromagnetic for x > 45. [1997Zam1,

1997Zam2, 2002Ric] measured the magnetic properties of Mn0.7-xFexAl0.3 (0.4 < x < 0.58) by means of57Fe Mössbauer spectroscopy and magnetic ac susceptibility on samples prepared either by arc melting

under Ar and annealed at 1000°C or by mechanical alloying [2002Ric]. A magnetic phase diagram has been

proposed based on the experimental results and theoretical calculations using a mean-field normalization

group method to the Ising model. [1998Abu] performed magnetization measurements on MnxFeAl1-x (0.27

< x < 0.6) samples from 85K to 300K up to 8 kOe. The compound is paramagnetic for x < 0.31 and becomes

ferromagnetic for x > 0.35 and the magnetic susceptibility obeys the Curie-Weiss law with negative

paramagnetic temperature. [2000Res1, 2000Res2] performed magnetic ordering measurements by XRD,

Mössbauer, high and low field magnetization measurements as well as magnetic susceptibility on

Mn0.1Fe0.9-xAlx alloys. A tentative magnetic phase diagram as function of temperature has been established

and compared to theoretical calculations. [2000Zam] studied the magnetic properties of a Mn0.3FexAl0.7-x

solid solution by Mössbauer spectroscopy, ac magnetic susceptibility and magnetization measurements for

0.275 < x < 0.525.

Miscellaneous

The crystallization behavior of rapidly quenched (Mn,Fe)Al6 alloys has been examined by [1986Wan]. The

Al activity of an Fe-1% Al-2% Mn alloy has been discussed by [1980Sud].

The diffusion behavior of Mn impurities through a Al-Fe layer has been studied by [1998Akd]. Mn

increases the activity coefficient of Al and tends also to increase the thickness of the reaction layer.

References

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[1937Moe] Moeckel, E., “The Al-Mg Alloys in Micrograph” (in German), Aluminium, 19(7), 433-439


[1939Deg] Degischer, E., “The Aluminium Corner of the Ternary System Aluminium - Iron -

Manganese” (in German), Aluminium-Archiv, 18, 5-19 (1939) (Equi. Diagram,

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Diagram, Review, 5)

[1943Mon] Mondolfo, L.F., “Metallography of Aluminum Alloys”, John Wiley & Sons, Inc., New York,

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[1943Phi] Phillips, H.W.L., “The Constitution of Alloys of Aluminium with Manganese, Silicon and

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[1944Ray] Raynor, G.V., “The Effect on the Compound MnAl6 of Iron, Cobalt and Copper”, J. Inst.


296


MSIT®

Al–Fe–Mn

[1950Phr] Phragmen, G., “On the Phases Occurring in Alloys of Aluminium with Copper, Magnesium,


Experimental, 67)

[1952Han] Hanemann, H., Schrader, A., Ternary Alloys of Aluminium (in German), Verlag Stahleisen

m.b.H., Düsseldorf, 103-105 (1952) (Equi. Diagram, Experimental)

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System”, J. Phys. Soc. Jpn., 15, 1534 (1960) (Equi. Diagram, Experimental, 3)

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(in Russian), Tsvet. Met., (6), 98-103 (1964) (Experimental, 7)

[1969Ily] Il'yushin, A.S., Zakharova, M.I., “Structural Changes on Disintegration of the

Supersaturated Solid Solution Fe2MnAl”, Phys. Met. Metallogr., 28(5), 204-207 (1969),

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Alloys Containing up to 2.0% Iron”, “Light Metals”, Proc. 103rd AIME Annual Meeting,

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[1974Mur] Muravyova, A.A., Zarechnyuk, O.S., Ryabov, V.R., “Investigation of the

Manganese-Iron-Aluminium System” (in Russian), Vestn. L'vov. Univ. Khim., 16, 3-4


[1974Shv] Shvedov, L.I., Goretskii, G.P., “Structure of Fe-Mn-Al Alloys” (in Russian), in “Struktura

i Svoistva Met. i Splavov”, Nauka i Tekhn., Minsk, 199-204 (1974) (Equi. Diagram,

Experimental, 6)

[1975Bar] Barlock, J.G., Mondolfo, L.F., “Structure of Some Aluminium - Iron - Magnesium -

Manganese - Silicon Alloys”, Z. Metallkd., 66, 605-611 (1975) (Equi. Diagram, Crys.


[1975Urs] Ursache, M., “Contributions to the Study of Some Magnetic Materials from the Al-Mn-Fe

System” (in Romanian), Cercet. Metal., 16, 489-500 (1975) (Experimental, 6)

[1975Zal] Zalutskiy, V.P., Nesterenko, Y.G., Osipenko, I.A., “Investigation of Ordering Processes in

the Alloy Fe2MnAl”, Phys. Met. Metallogr., 39(5), 113-119 (1975), translated from Fiz.

Met. Metalloved., 39, 1026-1032 (1975) (Crys. Structure, Experimental, 6)

[1977Ath] Athanassiadis, G., Le Caer, G., Foct, J., Rimlinger, L., “Study of Ternary Ordered Solid

Solutions Derived from Fe3Al by Substitution”, Phys. Status Solidi A, 40A, 425-435 (1977)


[1977Cha] Chakrabarti, D.J., “Phase Stability in Ternary Systems of Transition Elements with

Aluminum”, Metall. Trans. B, 8B, 121-123 (1977) (Equi. Diagram, Experimental, 13)

[1978Urs] Ursache, M., “Studies of the Possibilities of Using Some Alloys of the Al-Mn-M System for

the Fabrication of Permanent Magnets” (in Romanian), Bul. Inst. Politech. Bucuresti Chim.

Met., 40(3), 105-112 (1978) (Experimental, 9)

[1980Bra] Brandes, E.A., Flint, R.F., “Mn-Al-Fe”, in “Manganese Phase Diagrams”, Manganese

Centre, Paris, 80-81 (1980) (Equi. Diagram, Review, 4)

[1980Sud] Sudavtsova, V.S., Batalin, G.I., “Aluminium Activity in Liquid Iron Alloys” (in Russian),

Ukr. Khim. Zh., 46(3), 268-270 (1980) (Thermodyn., Experimental, 8)

297


MSIT®

Al–Fe–Mn

[1981Bra] Branco, J.R.T., Boratto, F.J.M., “The Austenite Phase Field in the Fe-Mn-Al System at

1000°C” (in Portuguese), 36th Annual Congress of ABM, Vol. 1, Recife, Mexico, 5-10 July

1981, 175-185 (Publ. 1981) (Equi. Diagram, Experimental, 12)

[1983Riv] Rivlin, V.G., “Phase Equilibria in Iron Ternary Alloys. 12: Critical Review of Constitution

of Aluminium-Iron-Manganese and Iron-Manganese-Silicon Systems”, Int. Met. Rev.,

28(6), 309-337 (1983) (Equi. Diagram, Review, 61)

[1984Den] Denholm, W.T., Esdaile, J.D., Siviour, N.G., Wilson, B.W., “Crystallization Studies in the

Aluminium-Rich Corner of the Aluminium-Iron-Manganese System”, Metall. Trans. A,

15A, 1311-1317 (1984) (Equi. Diagram, Experimental, 6)

[1986Dub] Dubois, J.-M., Janot, Ch., Pannetier, J., Pianelli, A., “Diffraction Approach to the Structure

of Decagonal Quasi-Crystals”, Phys. Lett. A, 117(8), 421-427 (1986) (Crys. Structure,

Experimental, 21)

[1986Sch] Schaefer, R.J., “The Metallurgy of Quasicrystals”, Scr. Metall., 20(9), 1183-1312 (1986) as

quoted in [1995Sin]

[1986Wan] Wang, R., Gui, J., Yao, S., Cheng, Y., Lu, G., Huang, M., “High-Temperature X-Ray

Diffraction Study of the Crystallization Process in Rapidly Quenched Al6(Mn,Fe) Alloys”,

Phil. Mag. B, 54, L33-L37 (1986) (Experimental, 7)

[1987Den] Denholm, W. T., Esdaile, J.D., Siviour, N.G., Wilson, B.W., “The Nature of the FeAl3Liquid-(FeMn)Al6 Reaction in the Al-Fe-Mn System”, Metall. Trans. A, 18A, 393-397


[1987Lu] Lu, T.-H., Liu, T.-F., Wan, C.-M., “X-Ray Structure Determination of Fe9Mn6Al5Precipitate in a Fe-Mn-Al-Cr Alloy”, “Anal. Tech. Mater. Charact.”, Proc. Int. Workshop

1987, 233-241 (Publ. 1987) (Crys. Structure, Experimental, 8)

[1987Ma] Ma, Y., Stern, E.A., “Fe and Mn Sites in Noncrystallographic Alloy Phases of Al-Mn-Fe

and Al-Mn-Fe-Si”, Phys. Rev. B, Condens. Matter, 35B, 2678-2681 (1987) (Crys. Structure,

Experimental, 22)

[1987Wou] Van der Woude, F., Schurer, P.J., “A Study of Quasi-Crystalline Al-Fe Alloys by

Mössbauer-Effect Spectroscopy and Diffraction Techniques”, Can. J. Phys., 65, 1301-1308


[1988Pau] Pauling, L., “Structure of the Orthorhombic Form of Mn2Al7, Fe2Al7 and (Mn0.7Fe0.3)2Al7that by Twinning Produces Grains with Decagonal Point-Group Symmetry”, Proc. Natl.

Acad. Sci. U.S.A., Vol. 85, 2422-2423 (1988) (Crys. Structure, Experimental, 8)

[1988Per] Perez Alcazar, G.A., Plascak, J.A., Galvao da Silva, E., “Magnetic Properties of Fe-Mn-Al

Alloys in the Disordered Phase”, Phys. Rev. B, Condens. Matter, 38B, 2816-2819 (1988)


[1988Sch] Schurer, P.J., Van Netten, T.J., Niesen, L., “The Structure of Decagonal Al7(Mn1-xFex)2

Alloys”, J. de Physique, 49, 237-241 (1988) (Crys. Structure, Experimental, 17)

[1990Liu1] Liu, X., Hao, S., “Thermodynamic Calculation on the Phase Diagram of the Fe-Mn-Al

System” (in Chinese), Proc. 6th National Symposium on Phase Diagrams, 46-48 (1990)

(Equi. Diagram, Thermodyn., Theory, 4)

[1990Liu2] Liu, X., Sun, R., Hao, S., “Study of Phase Equilibria at 1000, 1100 and 1200°C in the

System Fe-Mn-Al” (in Chinese), Proc. 6th National Symposium on Phase Diagrams,


[1990Xu] Xu, L., Guo, Y., Liang, G., LI, Y., “Experimental Investigation of the Equilibrium Diagram

of Fe Corner in Fe-Mn-Al System” (in Chinese), Proc. 6th National Symposium on Phase

Diagrams, 160-162 (1990) (Equi. Diagram, Experimental, 2)

[1990Wer] Werkman, R.D., Schurer, P.J., van der Woude, F., “Quasicrystals”, Hyperfine Interact.,

53(1-4), 241-251 (1990) (Crys. Structure, Experimental, 50)

[1991Mat] Matsumoto, M., Morisako, A., Ohshima, J., “Properties of Ferromagnetic MnAl Thin Films

with Additives”, J. Appl. Phys., 69(8), 5172-5174 (1991) (Electr. Prop., Experimental,

Magn. Prop., Mechan. Prop., 4)

298


MSIT®

Al–Fe–Mn

[1992Liu] Liu, X., Hao, S., Sun, R., “Isothermal Section at 1000 and 1100°C of Fe-Mn-Al System

Phase Diagram” (in Japanese), Acta Met. Sin.(Jinshu Xuebao) B, 28B(7), B288-B292

(1992) (Experimental, Equi. Diagram, 6)

[1992Xu] Xu, L., Guo, Y., Liang, G., Li, Y., “Determination of the Phase Diagram of Fe-Mn-Al by

Means of EPMA” (in Japanese), Cailiao Kexue Jinzhan, 6(3), 185-189 (1992)


[1993Hao] Hao, S., Chen, H., Liu, X., “Study of Transverse Section of 4 wt% Al and 8 wt% Al in

Fe-Mn-Al System Phase Diagram” (in Japanese), J. Northeast Univ. Technol (China),

14(2), 150-154 (1993) (Experimental, Equi. Diagram, 5)

[1993Liu1] Liu, X., Shiming, H., “Phase Equilibria and (bcc) Phase Region Continuity at 1000°C in

the Fe-Mn-Al System”, Scr. Metall. Mater., 28(5), 611-616 (1993) (Experimental, Phase

Diagram, 6)

[1993Liu2] Liu, X., Chen, H., Hao, Sh., “Phase Equilibria of the Fe-Mn-Al System at 1200°C and

1300°C” (in Japanese), Dongbei Gongxueyuan Xuebao, 14(3), 249-252 (1993)


[1993Liu3] Liu, X., Hao, Sh., “A Thermodynamic Calculation of the Fe-Mn-Al Ternary System”

Calphad, 17(1), 79-91 (1993) (Thermodyn., 16)

[1993Nis] Nistor, L.C., Teodorescu, V., Manaila, R., “Disorder in Al-Mn-Fe Icosahedral Alloys

Introduced by Iron”, Microscopy Res. Techniq., 25(2), 183-184 (1993) (Crys. Structure,

Experimental, 8)

[1993Oka] Okamoto, H., “Fe-Mn (Iron-Manganese)” in “Phase Diagrams of Binary Iron Alloys”

Okamoto, H. (Ed.), ASM International Materials Park, OH (USA), 203-213 (1993)

(Review, 184)

[1993Sin] Singh, A., Ranganathan, S., “Quasicrystalline and Crystalline Phases and their Twins in

Rapidly Solidified Al-Mn-Fe Alloys”, J. Non-Cryst. Solids., 153-154, 86-91 (1993) (Crys.


[1994Rag] Raghavan, V., “The Al-Fe-Mn System”, J. Phase Equilib., 15(4), 410-411 (1994) (Equi.


[1994Ser] Serneels, A., Davignon, G., Niu, X., Lebrun, P., Froyne, L., Verlinden, B., Delay, L., “An

Overview of the Research Activities in the Al-Fe-Mn System”, in “MTM-COST 507”, II,


[1995Ser] Serneels, A., Davignon, G., Verlinden, B., Delaey, L., “Experimental Investigation of

Selected Key Compositions in Order to Detemine the Al-Fe-Mn Phase Diagram” in

“IWT-COST 507”, II, 1-49 (1995) (Experimental, Equi. Diagram, 4)

[1995Sin] Singh, A., Ranganathan, S., “A Transition Electron-Miscroscopic Study of Icosahedral

Twins. 1. Rapidly Solidified Al-Mn-Fe-Alloys”, Acta Metall. Mater., 43(9), 3539-3551





[1997Mue] Mueller, C., Stadelmaier, H.H., Reinsch, B., Petzow, G., “Constitution of Mn-Al-(Cu, Fe,

Ni or C) Alloys Near the Magnetic Phase”, Z. Metallkd., 88(8), 620-624 (1997)

(Experimental, Equi. Diagram, Review, 15)

[1997Zam1] Zamora, L.E., Perez Alcazar, G.A., Bohorquez, A., Marco, J.F., “Magnetic Phase Diagram

of the FexMn0.7-xAl0.3 Alloys Series Obtained by Moessbauer Spectroscopy”, Hyperfine

Interact., 110, 177-182 (1997) (Experimental, 7)

[1997Zam2] Zamora, L.E., Perez-Alcazar, G.A., Bohorquez, A., “Magnetic Properties of the

FexMn0.70-xAl0.30 (0.40 x 0.58) Alloy Series”, J. Appl. Phys., 82(12), 6165-6169 (1997)


[1998Abu] Abu-Aljarayesh, I., Al-Khateeb, S., Said, M.R., “Magnetic Properties of the System

Fe(Al,Mn)”, J. Magn. Magn. Mater., 185(2), 220-224 (1998) (Experimental, Magn. Prop.,

Equi. Diagram, 14)

299


MSIT®

Al–Fe–Mn



Thermodyn., 55)

[1998Wei] Weitzer, F., Rogl, P., Bohn, M., “Phase Relations in the Aluminium Rich Part of the System

Aluminium-Iron-Manganese”, in “COST507, Definition of Thermochemical and

Thermophysical Properties to Provide a Database for the Development of New Light Metal

Alloys”, Vol. 1, 53-57 (1998) (Experimental, Equi. Diagram, Crys. Structure, 13)

[1999Mek] Mekhrabov, A.O., Akdeniz, M.V., “Effect of Ternary Alloying Elements Addition on

Atomic Ordering Characteristics of Fe-Al Intermetallics”, Acta Mater., 47(7), 2067-2075

(1999) (Calculation, Theory, Thermodyn., 63)

[1999Sch] Schurack, F., Eckert, J., Schultz, L., “High-Strength Al-Alloys with Nano-Quasicrystalline

Phase as Main Component”, Nanostruct. Mater., 12, 107-110 (1999) (Experimental, Crys.

Structure, 5)

[2000Sch] Schurack, F., Eckert, J., Schultz, L., “Quasicrystalline Al-Alloys with High Strength and

Good Ductility”, Mater. Sci. Eng. A, 294-296, 164-167 (2000) (Crys. Structure,

Experimental, Mechan. Prop., 6)

[2000Res1] Restrepo, J., Alcazar, P.G.A., “Magnetic Properties of Fe0.9-qMn0.1Alq Disordered Alloys:

Theory”, Phys. Rev. B, 61B(9), 5880-5883 (2000) (Magn. Prop., Theory, 15)

[2000Res2] Restrepo, J., Perez Alcazar, G.A., Ganzalez, J.M, “Magnetic Properties of Disordered

Fe0.9-xMn0.1Alx Alloys”, J. Appl. Phys., 87(10), 7425-7429 (2000) (Crys. Structure,

Experimental, Magn. Prop., Moessbauer, 10)

[2000Zam] Zamora, L.E., Perez Alcazar, G.A., Taberas, J.A., Bohorguez, A., Marco, J.F., Gonzalez,

J.M., “Magnetic Properties of FexMn0.3Al0.7-x (0.275 x 0.525) Disordered Alloys”, J.

Phys.: Condens. Matter, 12, 611-621 (2000) (Experimental, Magn. Prop., Equi. Diagram,

13)

[2001Gon] Gonzales, C., Medina, G., Greneche, J.M., Perez Alcazar, G.A., Surinach, S., Munoz, J.S.,

Baro, M.D., “Magnetic Phase Diagram of the FexMn0.60-xAl0.40 (0.20 x 0.60) Alloys

Mechanically Alloyed for 48 Hours”, Mater. Sci. Forum, 360-362, 565-570 (2001)

(Experimental, Magn. Prop., Moessbauer, Equi. Diagram, 14)

[2002Ric] Rico, M.M., Medina, G., Perez Alcazar, G.A., Munoz, J.S., Surinach, S., Baro, M.D.,

“Magnetic and Structural Properties of Mechanically Alloyed FexMn0.70-xAl0.30 (x = 0.40

and 0.45) Alloys”, Phys. Status Solidi A, 189(3), 811-816 (2002) (Crys. Structure,


[2003Pis1] Pisch, A., “Al-Fe (Aluminum-Iron)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart, to be published, (2003) (Equi. Diagram, Review, 58)

[2003Pis2] Pisch, A., “Al-Mn (Aluminium-Manganese)”, MSIT Evaluation Program, in MSIT


Stuttgart, to be published, (2003) (Equi. Diagram, Crys. Structure, Assessment, 40)

300


MSIT®

Al–Fe–Mn


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


( Fe)

1538-1394

cI2

Im3m

W

a = 293.15

dissolves up to 10 at.% Mn at 1473°C

[1993Oka]

( Fe, Mn)

< 1394-912

cF4

Fm3m

Cu

a = 364.67

a = 386.0

continuous solid solution,

pure Fe at 915°C [V-C2, Mas2],

dissolves up to 15 at.% Al at 800 C.

pure Mn [Mas2]

( Fe, Mn),

( Fe)

< 1138

cI2

Im3m

W

a = 286.65

a = 286.60 to 289.99

a = 286.60 to 290.12

a = 308.0



0-19.0 at.% Al, HT [2003Pis1]

0-18.7 at.% Al, 25°C [2003Pis1]

pure Mn

dissolves 9 at.% Fe at 1235°C [1993Oka]

( Mn)

1100-727

cP20

P4132

Mn

a = 631.52 pure Mn [Mas2]

dissolves up to 30 at.% Fe at 700°C

[1993Oka]

( Mn)

< 727

cI58

I43m

Mn

a = 891.26 pure Mn [Mas2]

dissolves up to 30 at.% Fe at 700°C

[1993Oka]

(Mn1-xFex)4Al13-i

< 1160

mC102

C2/m

Fe4Al13

a = 1552.7 - 1548.7

b = 803.5 - 808.4

c = 1244.9 - 1248.8

= 107.7°- 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

a = 1566.15

b = 799.49

c = 1245.61

= 107.6

74.16-76.70 at.% Al, x = 1 [2003Pis1]

sometimes called Fe3Al14 in the literature

at 76.0 at.% Al, x = 1 [2003Pis1]

Mn9.5Fe18Al72.5 [1998Wei]

solubilities at 550°C

0.2 < x < 0.22 and 0 < y < 2.72

Fe4Al13 (h) oB~50

Bmmm

a = 775.10 ± 0.09

b = 403.36 ± 0.05

c = 2377.1 ± 0.3

high temperature modification

by splat cooling. metastable?

[2003Pis1]

301


MSIT®

Al–Fe–Mn

(Mn1-xFex)2Al5-y

< 1169

oC24

Cmcm

-

a = 765.59

b = 641.54

c = 421.84

a = 769.03

b = 642.02

c = 421.61

at 71.5 at.% Al [2003Pis1]

Mn5.9Fe23.6Al70.5 [1998Wei]

solubilities at 550°C:

0 < x < 0.14 at y = 0

0 < x < 0.22 at y = 0.3

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [2003Pis1]

1102 - 1232

cI16? a = 598.0 [2003Pis1]

FeAl

< 1310

cP2

Pm3m

CsCl

a = 289.81 to 291.01

a = 289.76 to 190.78

39.7-50.9 at.% Al [2003Pis1] quenched

from 500°C in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

~24-~37 at.% Al [2003Pis1]

23.1-35.0 at.% Al [2003Pis1]

24.7-31.7 at.% Al [2003Pis1]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [2003Pis1]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

metastable

85.7 at.% Al [2003Pis1]

FeAl4+x t** a = 884

c = 2160


[2003Pis1]

MnAl12

< 500

cI26

Im3

Al12W

a = 747 [V-C2]

(Mn1-xFex)Al6< 705

oC28

Cmcm

MnAl6

a = 755.51

b = 649.94

c = 887.24

a = 754.5 ± 0.2

b = 649.0 ± 0.3

c = 868.1 ± 0.2

a = 754.5 ± 0.2

b = 649.0 ± 0.3

c = 868.1 ± 0.2

at x = 0 [V-C2]

at x = 0 [2003Pis2]

Mn5.4Fe8.8Al85.8 [1998Wei]

0 < x < 0.6 at 550°C

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

302


MSIT®

Al–Fe–Mn

, MnAl4< 693

hP586

P63/m

a = 2838.2

c = 1238.9

a = 2842.49

c = 1241.61

space group does not fit 100%, probably

P63 [2003Pis2]

Mn18Fe1.6Al80.4 [1998Wei]

, MnAl4< 923

hP574

P63/mmc

MnAl4

a = 1998

c = 2467.3

Mn4Al11 (LT)

< 916

aP30

P1

Mn4Al11

a = 509.5 ± 0.4

b = 887.9 ± 0.8

c = 505.1 ± 0.4

= 89.35 ± 0.04°

= 100.47 ± 0.05°

= 105.08 ± 0.06°

a = 507.11

b = 882.51

c = 505.94

= 89.89°

= 100.52°

= 105.26°

[V-C2]

Mn26.7Fe4Al73.3 [1998Wei]

Mn4Al11 (HT)

916 - 1002 Pna21

a = 1483.7

b = 1245.7

c = 1250.5

at 62.05 at.% Al, designated as MnAl3[2003Pis2]

,

< 1177

cI2Im3m

W

[2003Pis2]

1

< 1048

[2003Pis2]

2, Mn5Al8< 991

hR26

R3m

Cr5Al8

a = 1267.1

c = 793.6

a = 1261.1

c = 792.7

a = 1259.73

c = 790.23

at 63 at.% Al [2003Pis2]

at 55 at.% Al [2003Pis2]

Mn26.7Fe4Al73.3 [1998Wei]

< 1312

hP2

P63/mmc

Mg

a = 270.5 to 270.5

c = 436.1 to 438

44.2 - 44.9 at.% Al [2003Pis2]

- Mn3Al10

< 860

hP26

P63/mmc

Co2Al5

a = 754.6 ± 0.3

c = 289.5 ± 0.2

[2003Pis2]

metastable

D tP2

P4/mmm

CuAu

a = 278 to 279

c = 356 to 357

44.2 - 44.9 at.% Al metastable [2003Pis2]

ico-MnAl icosahedral

m35

80-82 at.% Al

quasicrystal, metastable [2003Pis2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

303


MSIT®

Al–Fe–Mn


deca-MnAl decagonal ~78 at.% Al

quasicrystal, metastable [2003Pis2]

* 1,

Mn1-xFex Al4

0.1 < x < 0.2 [1998Wei]

* 2,

(MnxFe1-x)4 Al13

oB~50

Bmmm

Fe4Al13 (h)

a = 784.3

b = 399.2

c = 2376.5

0.3825 < x < 0.425 [1998Wei]

* 3,

(Mn1-xFex)2Al10

hP26

P63/mcm

Mn3Al10

a = 755.21

b = 786.98

single phase at x = 0.3 [1998Wei]

ternary character not completely sure

* 4,

(Mn1-xFex)Al3-x Pna21

a = 1472.1 ± 0.9

b = 1233.9 ± 0.8

c = 1243.1 ± 0.8

Al72Mn23Fe5 [1998Wei]

* ,

Mn8Fe3Al9

ordered

CsCl

a = 296 to 297 ferromagnetic [1960Tsu]

solubility range from 35 to 47.5 at.% Mn,

40 to 47.5 at.% Al and 10 to 17.5 at.% Fe

*Mn6Fe9Al5 Mn

like

a = 631 space group P4332 [1987Lu]

ternary character not completely sure

*Mn258Fe111Al1295 o?1664 a = 3286

b = 3123

c = 2480

[1988Pau]

Mn14-xFexAl86 icosahedral

ai = 4530

ai = 4470

obtained in rapidly solidified alloys or by

mechanical alloying [1995Sin, 2000Sch]

in AlMn10Fe10 multiphase sample

[1993Sin]

in AlMn5Fe5 multiphase sample [1993Sin]


Al Fe Mn

L+Fe4Al13+ (Mn,Fe)Al6 747 P L

Fe4Al13

(Mn,Fe)Al6

97.1

75

86

1.2

25

6

1.7

0

8

L (Al)+Fe4Al13+(Mn,Fe)Al6 652 E L

(Al)

Fe4Al13

(Mn,Fe)Al6

98.8

99.75

75

86

0.8

0

25

7

0.4

0.25

0

7

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

304


MSIT®

Al–Fe–Mn

20

40

60

80

20 40 60 80

20

40

60

80

Mn Fe


Axes: at.%

(γFe, γMn)

(αFe,δMn)

L

L FeAl

Fig. 2: Al-Fe-Mn.

Partial isothermal

section at 1300°C

after [1993Liu2]

Mn 10.00Fe 0.00Al 90.00

Mn 0.00Fe 10.00Al 90.00


Axes: at.%

(Al)

(Mn,Fe)Al6

µ Fe4Al13

P

E

e

p

e

Fig. 1: Al-Fe-Mn.

Partial liquidus

surface

305


MSIT®

Al–Fe–Mn

20

40

60

80

20 40 60 80

20

40

60

80

Mn Fe


Axes: at.%

(γFe,γMn)

(αFe,δMn)

20

40

60

80

20 40 60 80

20

40

60

80

Mn Fe


Axes: at.%

(γFe,γMn)

(αFe,δMn)

(βMn)

(γMn)

Fig. 3: Al-Fe-Mn.

Partial isothermal

section at 1200°C

Fig. 4: Al-Fe-Mn.

Partial isothermal

section at 1100°C

306


MSIT®

Al–Fe–Mn

20

40

60

80

20 40 60 80

20

40

60

80

Mn Fe


Axes: at.%

(γFe,γMn)

(βMn)

ε

γ

FeAl2

FeAl

(αFe,δMn)

Fig. 5: Al-Fe-Mn.

Partial isothermal

section at 1000°C

20

40

60

80

20 40 60 80

20

40

60

80

Mn Fe


Axes: at.%

(αFe,δMn)(βMn)

(γFe,γMn)

γ2

FeAl

Fig. 6: Al-Fe-Mn.

Partial isothermal

section at 800°C

307


MSIT®

Al–Fe–Mn

40

50

60

70

10 20 30 40

30

40

50

60

Mn 80.00Fe 0.00Al 20.00

Mn 30.00Fe 50.00Al 20.00

Mn 30.00Fe 0.00Al 70.00 Data / Grid: at.%

Axes: at.%

(βMn)

γ2

κ

10

20

30

10 20 30

70

80

90

Mn 31.40Fe 0.00Al 68.60

Mn 0.00Fe 31.40Al 68.60


Axes: at.%

τ1

τ2τ3

τ4

λ

µ

Mn4Al11(LT)(Mn1-xFex)2Al5-y

γ2

(Mn1-xFex)Al6

(Mn1-xFex)4Al13-y

Fig. 7: Al-Fe-Mn.

Partial isothermal

section at 700°C after

[1997Mue]

Fig. 8: Al-Fe-Mn.

Partial isothermal

section for Al-rich

region at 550°C after

[1998Wei]

308


MSIT®

Al–Fe–Mn

600

700

800

900

Mn 1.00Fe 3.00Al 96.00

Mn 1.00Fe 0.00Al 99.00Al, at.%

Tem

pera

ture

, °C

L

(Al)+(Mn1-xFex)Al6

L+(Mn1-xFex)Al6

L+(Mn1-xFex)4Al13-y

(Al)+(Mn1-xFex)4Al13-y+(Mn1-xFex)Al6

97.0 98.0

600

700

800

900

Mn 0.00Fe 2.00Al 98.00

Mn 5.30Fe 2.10Al 92.60Mn, at.%

Tem

pera

ture

, °C

L

L+(Mn1-xFex)4Al13-y

+(Mn1-xFex)Al6

L+µ+(Mn1-xFex)4Al13-y

(Mn1-xFex)4Al13-y

L+(Mn1-xFex)4Al13-y+(Mn1-xFex)Al6

(Al)+(Mn1-xFex)Al6(Al)+(Mn1-xFex)4Al13-y

(Al)+

2.0 4.0

Fig. 9: Al-Fe-Mn.


at 2 mass% Mn

[1943Phi]

Fig. 10: Al-Fe-Mn.


at 4 mass% Fe

309


MSIT®

Al–Fe–N

Aluminium – Iron – Nitrogen

Hermann A. Jehn and Pierre Perrot, up-dated by Pierre Perrot

Literature Data

Al-Fe alloys, in the presence of N, form aluminium nitride which plays an important role in steelmaking

because of grain refining and texture development. Most of the investigations have been directed at the

solubility of N in Al-Fe melts [1960Peh, 1963Mor, 1978Wad, 1979Wad, 1982Ish] and phase boundaries in

the liquid state [1963Mor, 1964Eva, 1968Isa] and in austenite [1951Dar, 1961Isa] represented by the

solubility product of AlN [1984Rag, 1987Rag]. [1961Sta] nitrided four ternary alloys at 600°C for 20 h and

analyzed the resulting phases. A review of the Al-Fe-N system has been presented by [1987Rag] and

updated by [1993Rag]. A Calphad assessment of the Al-Fe-N system has been reported by [1992Hil].

Kinetics of precipitation of AlN in steels has been investigated by [1972Oga, 1988Lan, 1995Big]. Since the

years 1980, no more experimental determinations of the solubilities of nitrogen in Al-Fe alloys are

available. The actual trend is to use the accepted results to calculate the solubility of nitrogen in more

complex alloys, then to check the calculated solubilities with experimental observations.

This evaluation incorporates and continues the critical evaluation made by [1992Jeh] considering new

published data.

Binary Systems

The binaries Al-Fe, Al-N and Fe-N are taken from [2003Pis], [2003Fer] and [2003Per], respectively.

N is practically insoluble in Al(s). The solubility of N in liquid Al under 0.1 MPa is given by [1986Wri]:

log10 (at.% N) = 2.633 - 1157/T

The only stable phase, AlN, melts at 2800 ± 50°C under nitrogen pressure of 10 to 50 MPa. AlN sublimates

congruently, the decomposition pressure being 0.1 MPa at 2435°C. Metastable AlN9 is also reported

[1986Wri].

All Fe modifications dissolve more or less N [1976Kru, 1982Fro, 1987Wri]. The ( Fe) phase is stabilized

to lower temperatures and then decomposes eutectoidally into ( Fe) and 'Fe4N at 590°C and 8.75 at.% N.

Fe4N, stable up to 670°C transforms into , hexagonal nitride with a wide homogeneity range. Fe2N

(orthorhombic) is stable up to 500°C [H, 1976Kru]. For the Fe-rich part of the Fe-N phase diagram,

including T-c isobars, see [1976Kru]. A Calphad assessment of the Fe-N diagram has been carried out by

[1987Fri] and an extensive review presented by [1987Wri]. The solubility of nitrogen in pure liquid iron

had been determined between 1580 and 2000°C under 0.1 MPa by [1960Mae, 1960Peh, 1964Eva,

1978Wad, 1982Ish] and [1986Wad].

Solid Phases

No ternary compounds are known. According to [1961Sta], considerable amount of Al is dissolved in the

' and iron nitrides (Fig. 1). The lattice parameter of nitride containing 57 at.% Fe, 19 at.% Al and 24

at.% N (79 mass% Fe, 12.7 mass% Al, 8.3 mass% N) is slightly increased compared to binary iron nitride

of the same N content (see Table 1). The N solubility in austenite containing Al was determined by direct

chemical analysis of alloys equilibrated in gaseous nitrogen [1951Dar]. At low Al content, the N solubility

is independent of the Al content and given by the relation ((%N) in mass%, T in K):

(%N)=0.0404-1.2 10-5T. At higher Al content, the precipitation of AlN is observed. The solubility product

of AlN in Fe is represented by the equations:

log10((%Al)(%N)) = 1.95 - 7400/T ((%) in mass%, T in K) [1976Kru]

log10(cAlcN) = 2.866 - 7400/T (c in at.%, T in K).

Phase boundaries calculated from the above equations are shown in Fig. 2. Few data exist on the solubility

of N in ( Fe)-Al alloys. They have been obtained when studying the precipitation kinetics of AlN in ferrite

containing 0.19 at.% Al and 0.04 at.% N [1972Oga] or 2 at.% Al and 0.02 at.% N, the maximum amount of

310


MSIT®

Al–Fe–N

nitrogen dissolved in the ferrite matrix at 575°C [1988Lan]. An appreciable rate of precipitation was found

between 450 and 620°C; the rate was greater in cold-worked samples than in as-quenched ones.

Liquidus Surface

After early measurements by [1939Ekl], a number of investigations on the solubility of N in liquid Al-Fe

alloys were undertaken in the 1960's. [1960Mae, 1960Peh, 1964Eva] and [1982Ish] report first order

interaction coefficients to be slightly positive indicating that Al increases the activity coefficient of N in the

melt and decreases its solubility at a given N2 pressure. On the contrary, [1963Mor, 1968Isa], confirmed by

more recent work of [1978Wad], found an increase of the N solubility with the Al content of the liquid.

According to [1978Wad], the isobaric N solubility in Al-Fe melts obeys Sieverts' law (cN ~ p(N2)1/2) and

can be represented by the equation:

logcN = 0.5logp(N2)+A+BcAl+Cc2Al

Numerical data for A, B and C are given in Table 2. These results were confirmed by the model of an ideally

associated mixture proposed by [2000Yag]. The solubility product of AlN in Al-Fe melts, is given at

1580°C by [1961Isa], at 1580°C and 1675°C by [1963Mor, 1968Isa] and [1973Mok]. [1978Wad] proposed

the following equation (T in K, (%) in mass%, c in at.%):

log10((% Al)(% N)) = 6.10+5.88 10-2(%Al) - 14000/T

log10(cAl cN) = 7.016+2.84 10-2cAl - 14000/T

Figure 3 gives the liquidus isotherms under 0.1 MPa N2 and between 1550 and 1700°C according to

[1978Wad]. The solubility of N2 in liquid Al-Fe alloys calculated by [1992Hil] under 0.1 MPa pressure at

1900 K is shown in Fig. 4. A reasonable agreement is observed with experimental solubilities measured by

[1978Wad] in the iron-rich part of the diagram.

The first order interaction parameter of nitrogen for the Al-Fe liquid alloys was experimentally determined

by [1979Wad] between 1600 and 1700 K and may be represented by the following expression:

eN(Al) = d(log10 fN / d(%Al)) = - 0,81+(1426/T) with fN = (%N)pure Fe / (%N)Fe,Al alloy.

(%Al) or (%N) in the above formula represent mass%. In the liquid alloys, eN(Al) < 0, which means that the

solubility of N in liquid alloys increases with the Al content of the alloy. As shown in Fig. 3, once the

solubility product of AlN obtained, the solubility of N in liquid alloy does not increase any more, but

decreases because of the precipitation of AlN. [1982Ish] measures a positive first order interaction

parameter, which implies a decrease of the nitrogen solubility due to aluminium, result which contradicts

the well established experimental observations.

Isothermal Sections

From the phases found by [1961Sta] in four ternary alloys, a partial isothermal section at 600°C is

constructed. It is given in Fig. 1, including the composition of the four alloys and the phases observed.

[1978Tro, 1985Sch] show that the mixture AlN+Fe is thermodynamically stable at 1950°C under a N2

atmosphere, it decomposes above 1750°C under an Ar atmosphere with formation of a FeAl alloy.

Miscellaneous

[1995Big] investigated the kinetics of precipitation of AlN on internal nitriding the Fe-2 at.% Al alloy in

the temperature range 530 - 580°C. The precipitation of AlN is associated with a Gibbs energy barrier for

the formation of a precipitate of critical size and thus is controlled by nucleation and growth.

Multilayered thin films Fe-N/Al-N are currently receiving increasing attention [1991Bar, 2001Liu] due to

their excellent soft magnetic properties with large saturation magnetization of 19 kG and a high relative

permeability of 4300 at high frequency [1991Kub]. These layers are prepared by ion sputtering under a

mixture of Ar and N2 introduced under the sputtering ion source. The layers are generally oversaturated and

the thinnest (less than 12 nm) exhibits an essentially amorphous structure.

311


MSIT®

Al–Fe–N

References

[1939Ekl] Eklund, L., “The Solubility of Nitrogen in Steel” (in Swedish), Jernkontorets Ann., 123,


[1951Dar] Darken, L.S., Smith, R.P., Filer, E.W., “Solubility of Gaseous Nitrogen in Gamma Iron and

the Effect of Alloying Constituents - Aluminium Nitride Precipitation”, Trans. Metall. Soc.

AIME, 191, 1174-1179 (1951) (Equi. Diagram, Experimental, *, 12)

[1960Mae] Maekawa, S., Nagakawa, Y., “Effect of Titanium, Aluminium and Oxygen on the Solubility

of Nitrogen in Liquid Iron” (in Japanese), Tetsu to Hagane, 46, 1438-1441 (1960) (Equi.

Diagram, Thermodyn., Experimental, 8)

[1960Peh] Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron

Alloys-I-Thermodynamics”, Trans. Metall. Soc. AIME, 218, 1088-1101 (1960) (Equi.

Diagram, Experimental, Thermodyn., *, 32)

[1961Isa] Isaev, V.F., Morozov, A.N., “Conditions of Formation of AlN in Liquid Fe” (in Russian),

Sb. Nauchn.-Tehn. Trud., Nauchno-Issled. Inst. Met. Chelyab. Sovnarkhoz, (4), 12-18

(1961) (Thermodyn., Experimental, 8)

[1961Sta] Stadelmaier, H.H., Yun, T.S., “Alloys of Nitrogen and the Transition Metals Mn, Fe, Co and

Ni with Mg, Al, Zn and Cd”, Z. Metallkd., 52, 477-480 (1961) (Crys. Structure, Equi.

Diagram, Experimental, *, 22)

[1963Mor] Morozov, A.N., Isaev, V.F., Korolev, L.G., “Conditions of Nitride Formation and Solubility

of N in Alloys of Fe with Al, Ti and V” (in Russian), Izv. Akad. Nauk SSSR, Metall. i Gorn.

Delo, (4), 141-144 (1963) (Equi. Diagram, Experimental, 6)

[1964Eva] Evans, D.B., Pehlke, R.D., “The Aluminium Nitrogen Equilibrium in Liquid Iron”, Trans.

Metall. Soc. AIME, 230, 1651-1656 (1964) (Equi. Diagram, Experimental, 12)

[1968Isa] Isaev, V.F., Danilovich, Yu.A., Morozov, A.N., “Solubility of Nitrogen for the Formation

of Nitrides in Molten Alloys Based on Iron and Nickel” (in Russian), Fiz-Khim. Osn. Pro.

Stali. Publ. Nauka, Samarin, A.M. (Ed.), Nauka, Moscow, 296-301 (1968) (Equi. Diagram,

Thermodyn., Experimental, 11)

[1972Oga] Ogawa, R., Fukutsuwa, T., Yagi, Y., “Precipitation of AlN in Cold Worked High Purity

Fe-Al-N Alloys” (in Japanese), Tetsu to Hagane, 58, 872-884 (1972) (Equi. Diagram,

Experimental, 21)

[1973Mok] Mokrov, I.A., Aleshchenko, G.M., Stomakhin, A.Ya., “Thermodynamic Evaluation of

Oxides and Nitrides in Metallic Melts”, (in Russian), Izv. Vyss. Uchebn. Zaved., Chern.

Metall., (7), 63-67 (1973) (Equi. Diagram, Thermodyn., 9)

[1976Kru] Krueger, J., Kunze, H.D., Schuermann, E., “Eisen” (in German), in “Gases and Carbon in

Metals”, Fromm, E., Gebhardt, E, (Eds.), Springer, Berlin, 578-613 (1976) (Equi. Diagram,

Review, *, 241)

[1978Tro] Trontelj, M., Kolar, D., “Reactions of AlN with the Iron Group Elements”, Vestn. Sloven.

Kem. Drus., 25(2), 165-172 (1978) (Thermodyn., Eperimental, 8)

[1978Wad] Wada, H., Pehlke, R.D., “Nitrogen Solubility and Aluminium Nitride Precipitation in

Liquid Fe, Fe-Cr, Fe-Cr-Ni, and Fe-Cr-Ni-Mo Alloys”, Metall. Trans. B, 9B, 441-448

(1978) (Equi. Diagram, Thermodyn., Experimental, *, 12)

[1979Wad] Wada, H., Pehlke, R.D., “Nitrogen Solubility and Aluminium Nitride Precipitation in

Liquid Iron Alloys containing Nickel and Aluminum”, Metall. Trans. B, 10B, 409-412

(1979) (Equi. Diagram, Thermodyn., Experimental, *, 4)

[1982Fro] Fromm, E., Jehn, H., Hehn, W., Speck, H., Hörz, G., “Gases and Carbon in Metals, Pt XV,

Ferrous Metals (3), Iron - Nitrogen”, Phys. Data, Fachinformationszentrum Energie,

Physik, Mathematik, Karlsruhe, 85, 5-17 (1982) (Equi. Diagram, Review, 40)

[1982Ish] Ishii, F., Ban’ya, B., Fuwa, T., “Effect of C, Al, Si, P, Mn and Ni on the Solubility of

Nitrogen in Liquid Iron Alloys” (in Japanese), Tetsu to Hagane, 68, 1551-1559 (1982)

(Equi. Diagram, Experimental, Thermodyn., 43)

312


MSIT®

Al–Fe–N

[1984Rag] Raghavan, V., “The Al-Fe-N System”, Trans. Indian Inst. Met., 37, 411-415 (1984) (Equi.


[1985Sch] Schuster, J.C., Bauer, J., Nowotny, “Applications to Materials Science of Phase Diagrams

and Crystal Structures in the Ternary Systems Transition Metal-Aluminum-Nitrogen”, Rev.

Chim. Miner., 22(4), 546-554 (1985) (Equi. Diagram, Review, #, 20)

[1986Wad] Wada, H., Lee, S.W., Pehlke, R.D. “Nitrogen Solubility in Liquid Fe and Mn-Fe Alloys”,

Metall. Trans. B, 17B, 238-239 (1986) (Experimental, 17)

[1986Wri] Wriedt, H.A., “The Al-N (Aluminium-Nitrogen) System”, Bull. Alloy Phase Diagrams, 7,

329-333 (1986) (Equi. Diagram, Review, #, 54)

[1987Fri] Frisk, K., “A New Assessment of the Fe-N Phase Diagram”, Calphad, 11, 127-134 (1987)

(Equi. Diagram, Thermodyn., Theory, 34)

[1987Rag] Raghavan, V., “The Al-Fe-N System”, in “Phase Diagrams of Ternary Iron Alloys, Part I”,

ASM International, 1, 145-147 (1987) (Equi. Diagram, Review, 13)

[1987Wri] Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull.

Alloy Phase Diagrams, 8(4), 355-377 (1987) (Equi. Diagram, Thermodyn., Review, #, 126)

[1988Lan] Lankreijer, L.M., Somers, M.A.J., Mittemeijer, E.T., “Kinetics and Nitride Precipitation in

Fe-Al and Fe-Si Alloys on Nitriding”, Proc. Internat. Conf. High Nitrogen Steels, Lille,

Edited 1989 by the Institute of Metals, London, 108-111 (1988) (Equi. Diagram,

Experimental, 17)

[1991Bar] Barnard, J.A., Tan, M., Waknis, A., Haftek, E., “Magnetic Properties and Structure of Al/

Fe-N Periodic Multilayer Thin Films”, J. Appl. Phys., 69(8), 5298-5300 (1991) (Crys.

Structure, Magn. Prop., 8)

[1991Kub] Kubota, K., Naoe, M., “Magnetic Properties of Fe-N/Al-N Multilayerd Films Pprepared by

Ar Ion-Assist Sputtering”, J. Appl. Phys., 70(10), 6430-6432 (1991) (Crys. Structure, Magn.

Prop., 2)

[1992Jeh] Jehn, H.A., Perrot, P., “Aluminium - Iron - Nitrogen”, MSIT Ternary Evaluation Program,

in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services

GmbH, Stuttgart; Document ID: 10.14876.1.20, (1992) (Crys. Structure, Equi. Diagram,

Assessment, 23)

[1992Hil] Hillert, M., Jonsson, S., “An Assessment of the Al-Fe-N System”, Metall. Trans. A, 23A

(11), 3141-3149 (1992) (Equi. Diagram, Thermodyn., Assessment, #, 27)

[1993Rag] Raghavan V., “Al-Fe-N (Aluminum-Iron-Nitrogen)”, J. Phase Equilib., 14 (5), 617-618


[1995Big] Biglari, M.H., Brakman, C.M., Mittemeijer, E.J., Zwaag, S.V.D., “The Kinetics of the

Internal Nitriding of Fe-2 at.Pct. Al Alloy”, Metall. Mater. Trans. A, 26A, 765-776 (1995)

(Calculation, Experimental, Kinetics, Thermodyn., 41)

[2000Yag] Yaghmaee, M.S., Kaptay, G., Janosfy, G., “Equilibria in the Ternary Fe-Al-N System”,

Mater. Sci. Forum, 329-330, 519-524 (2000) (Equi. Diagram, Theory, 9)

[2001Liu] Liu, Y.-K., Harris, V.G., Kryder, M.H., “Evolutions of Magnetic and Structural Properties

of FeAlN Thin Films via N Doping”, IEEE Trans. Magn., 37(4), 1779-1782 (2001)


[2003Fer] Ferro, R., Bochvar, N., Sheftel, E., Ding, J.J., “Al-N (Aluminum-Nitrogen)”, MSIT


International Services GmbH, Stuttgart; to be published, (2003) (Equi. Diagram, Crys.

Structure, Assessment, 33)

[2003Per] Perrot, P., “Fe-N (Iron-Nitrogen)”, MSIT Binary Evaluation Program, in MSIT Workplace,

Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; to be

published, (2003) (Crys. Structure, Equi. Diagram, Assessment, 35)




313


MSIT®

Al–Fe–N


Table 2: Isobaric Nitrogen Solubility in Al-Fe Melts [1978Wad] log10cN=0.5log10pN2+A+BcAl+Cc2Al (cN,

cAl in at.%, PN2 in Pa)

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

( Fe)

912-1394

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2]

dissolves 0.1 at.% N at 912°C, 0.1 MPa

( Fe)

912

1394-1538

cI2

Im3m

W

a = 286.65 at 25°C [Mas2]

dissolves up to 54.0 at. % Al at 1102°C

dissolves 0.0166 at.% N at 912°C,

0.1 MPa

(Al)

660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C, [Mas2]

', Fe4N

680

cP5

Pm3m

Fe4N

a = 378.7 [1987Rag]

19.3 to 20.0 at.% N

, Fe3N1±x

(Fe,Al)3N1±x

hP3

P63/mmc

Fe3N1±x

a = 272.9

c = 439.2

a = 272.9

c = 440.4

a = 276

c = 442

~ 15 to ~ 33 at.%

23 at.% N

30 at.% N

Fe57Al19N24 [1961Sta]

Fe2N

500

oP12

Pbcn

Fe2N

a = 551.2

b = 482.0

c = 441.6

33.7 at.% N, [1984Rag]

AlN

< 2437.4

hP4

P63mc

ZnS- wurtzite

a = 311.14

c = 497.92

at 25°C, [1986Wri]

T [°C] A B C

1550

1600

1650

1700

- 3.859

- 3.856

- 3.852

- 3.849

+ 1.25 10-2

+ 2.34 10-2

+ 3.37 10-2

+ 4.34 10-2

+ 9.8 10-3

+ 8.2 10-3

+ 6.9 10-3

+ 5.7 10-3

314


MSIT®

Al–Fe–N

20

40

60

80

20 40 60 80

20

40

60

80

Fe Al

N Data / Grid: at.%

Axes: at.%

AlN

(γFe)

γ'+AlNε

γ',Fe4Nγ'+ε

γ'

pure ε

(γFe)+γ'

c

γ'+AlN

ε+AlN

ε+γ'+AlN

0.125

0.100

0.075

0.050

0.025

0

0 0.1 0.2 0.3 0.4

Al, at.%

( Fe)� + N2

+ AlN( Fe)�

1350°C

1200°C

1050°C

( Fe)� + AlN( Fe)�

+ AlN( Fe)�

N,at.%

+N +AlN2( Fe)�

Fig. 1: Al-Fe-N.

Partial isothermal

section at 600°C,

after [1961Sta]

Fig. 2: Al-Fe-N.

Solubility limits in the

( Fe) phase

after [1951Dar]

315


MSIT®

Al–Fe–N

0.3

0.2

0.1

00 2 4 6

Al, at.%

N,at.%

L

L +AlN

L +AlN

L +AlNL + N2

1550°C

1600°C

1650°C

1700°C

0.02

0.08

0.06

0.04

604020 80

0

100Fe Al

T = 1627°C

P(N ) = 1 bar2

Al, mass%

N,mass%

0

Fig. 3: Al-Fe-N.

Solubility limits in the

liquid phase after

[1978Wad]

Fig. 4: Al-Fe-N.

Solubility of N2 in

Al-Fe liquid alloys at

1627°C under 1 bar

N2

316


MSIT®

Al–Fe–Nd

Aluminium – Iron – Neodymium


Literature Data

First investigations in this system were undertaken by [1970Viv] who determined phase relations at 500°C

in the range up to 33.3 at.% Nd and structures of binary and ternary phases by X-ray analysis. Structures,

homogeneity ranges and magnetic properties of the phases were determined in more detail by [1971Oes1,

1971Oes2, 1975Dwi] for Nd(Fe1-xAlx)2, by [1988Hu, 1989Wei] for Nd2(Fe1-xAlx)17 and by [1974Viv,

1976Bus] for NdFe4Al8. [1990Gri, 1991Gri1] studied the Al-poor region (< 30 at.% Al) of the system by

DTA, X-ray, EDAX and optical microscopy; moreover [1992Gri] performed a complete assessment of the

system. On the basis of experimental data and thermodynamic consideration several isopleth sections were

constructed and presented together with isothermal sections and a liquidus projection.

Binary Systems




The accepted Al-Nd binary system is from [2003Leb]. The accepted Fe-Nd phase diagram, reported by

[2000Oka] is based on [1990Lan, 1991Lan], who found and studied the Nd5Fe17 phase. This is formed only

after very long heat treatments; so that it is easy to have metastable phase equilibria without the formation

of this phase.

Solid Phases

Table 1 summarizes the crystal structure data relevant to all the solid phases.

A number of linear solid solution fields (generally parallel to the Al-Fe axis) have been described. Those

based on binary phases are the following: for the NdAl2-based (cF24-MgCu2 type) a solubility up to 20 at.%

Fe [1991Gri2], for the Nd2Fe17-based (hR57-Th2Zn17 type) a solubility up to more then about 50 at.% Al

[1970Viv, 1989Wei, 1991Gri2] have been determined. A transition, at a temperature above ~800°C, to a

high temperature Nd2Fe17 form (with an unknown structure), was suggested by [1991Gri2] on the basis of

DTA results. Towards the Fe-Nd binary system the transition temperature increases above the temperature

of peritectic formation of the binary Nd2Fe17 phase. A neutron diffraction refinement of the crystal structure

of Nd2Fe17-xAlx was performed by [1996Gir, 1997Gir]. The site occupation of a number of isostructural

compounds was discussed and also related to the mixing enthalpy [1998Gir].

All the other binary phases show negligible ternary solid solutions.

Ternary phases observed by [1970Viv] are 1 NdFe4-xAl8+x (ThMn12 structure type), 2 NdFe2Al10 and 3

NdFe2-xAlx (0.35 < x < 0.8). [1974Viv, 1976Bus] refined the crystal structure of 1 to be of the CeMn4Al8type, an ordered variant of the ThMn12 type. The two papers give slightly different lattice parameters

(a = 878.2, c = 505.1 pm [1974Viv]; a = 881.3, c = 505.8 pm [1976Bus]). The structure of the 2 NdFe2Al10

was determined to be of the YbFe2Al10 type [1998Thi], an orthorhombic stacking variant of the ThMn12

type. The composition of 3 was corrected by [1991Gri1] to be Nd30Fe62-xAl8+x (0 < x < 17) with a

tetragonal structure. [1992Hu] determined the crystal structure to be of the La6Co11Ga3 type established by

[1985Sic]. Similarly as in La6Co11Ga3 the mutual substitution is almost restricted to the 16(l2) position.

Structure and nature of mutual substitution were confirmed by [1995Bre, 1997Kun, 2000Nag]. Crystal

structure data and experimental homogeneity range of 3 are well represented by the formula

Nd6Fe9Al1(Fe1-xAlx)4 (0.15 < x < 1).

Another ternary phase, 4, with a Nd:(Fe+Al) ratio of 1:2 was detected by [1991Gri1] with a small

homogeneity range for Al (2.5 to 5 at.%); its structure is unknown. [1995Bre] studied the Al-Fe substitution

317


MSIT®

Al–Fe–Nd

in the 3 and 4 phases by Mössbauer spectroscopy. They characterized the still unknown structure of 4 as

“long-period stacking of planes, typical for polytypism”.

Invariant Equilibria and Liquidus Surface

A partial not completely confirmed Scheil reaction scheme, was suggested together with a few vertical

sections and a liquidus projections by [1991Gri1, 1991Gri2]. The phase transitions during solidification of

the ternary alloys were deduced from the microstructures of arc melted alloys (cooling rate 200 to 400

Ksec-1) and DTA specimens (10 Kmin-1); the transition temperatures obtained by DTA were combined

with optical microscopic analysis to deduce the reaction sequence. The transition between the

high-temperature and room-temperature modifications of the Nd2(Fe,Al)17 compound could be given only

tentatively. The transition temperature is around 800°C at Al contents above 20 at.%. With Al content

decreasing to zero it increases above the temperature of peritectic formation of Al-free Nd2Fe17(r) phase.

The corresponding invariant equilibria could not be identified or located. Therefore in the reaction scheme

reproduced here in Fig. 1 these two modifications are not distinguished and treated as a single phase.

Furthermore missing links of the reaction scheme were tentatively completed by equilibria drawn by dashed

lines.

[1991Gri1, 1991Gri2] assumed for U2 an equilibrium L+? NdAl2+Nd2Fe17 with “?” standing for a not

determined phase. The only phase known to be stable at this high temperature and Al contents below 50

at.%, however, is ( Fe). The two-phase field ( Fe)+( Fe) forms a closed loop in the binary Al-Fe system.

As both modifications of Fe do not dissolve significant amounts of Nd (in the binary Fe-Nd system), this

closed loop forms one edge of a series of three-phase equilibria in the ternary system near the Fe corner.

Together with the binary equilibrium p1 there necessarily follows the equilibrium U1. The equilibrium

L+( Fe)+NdAl2 goes towards the Al corner, very probably over a maximum due to the high melting

temperatures of NdAl2 and ( Fe).

The equilibria U4 and U9 follow from the accepted binary systems. U4 corresponds to the most likely form,

how the phase Nd5Fe17 may participate in the reaction scheme. U9 follows from the three-phase equilibria

containing both modifications of Nd, ( Nd) and ( Nd).

[1991Gri1, 1991Gri2] postulated a maximum of the three-phase equilibrium L+( Nd)+Nd2Fe17 between

the binary Al-Fe system and U6. Nd2Fe17 here has to be replaced by Nd5Fe17. As the arguments for this

maximum are not exclusive, it is not taken into account in Fig. 1.

A partial liquidus surface presented by [1991Gri1, 1991Gri2] was classified as tentative by the authors,

especially the equilibria connected with the allotropic transformation between the two modifications of

Nd2Fe17. The most recent binary Al-Nd phase diagram at the Nd side is very different from that used by

[1991Gri1, 1991Gri2]. A trial to adjust the liquidus surface to the accepted binary Al-Nd phase diagram

seems to need too many speculative estimates regarding the compositions of liquid at the nonvariant

equilibria. Therefore this partial liquidus diagram is not presented here.

Isothermal Sections

Partial isothermal sections at 500 and at 600°C are presented in Figs. 2 and 3, respectively. Fig. 2 is taken

from [1970Viv] with compositions re-determined by [1991Gri1, 1991Gri2]. The homogeneity ranges of the

Al-Fe phases are adjusted to the accepted binary Al-Fe system. Fig. 3 is re-drawn from [1992Gri], it

represents the metastable system with suppressed Nd5Fe17 phase, as it is usually found after normal heat

treatment. Two more isothermal sections, at 750 and 900°C, were given by [1991Gri1, 1991Gri2].


[1991Gri1] gave 11 temperature-concentration sections, at constant Nd contents of 20, 30, 40, 50, 60, 70

and 80 at.% and constant Al contents of 5, 10, 20 and 30 at.%. Five of these sections were reproduced by

[1991Gri2]. In Fig. 4 the section at 70 at.% Nd is shown. At both sides this figure is adjusted to the accepted

binary systems, shown by dashed lines.

318


MSIT®

Al–Fe–Nd


Magnetic properties of ternary phases, microstructures of phases and sketched diagrams of the system are

published in [1990Gri, 1990Hen, 1990Kno, 1991Gri2].

Magnetic and/or transport properties and Mössbauer spectra of the Nd6Fe13-xAl1+x phase have been

investigated by several authors: for x = 1 [1997Kun], for x = 2 [1992Hu], [1996Zha], [1998Gro] and

[2000Wan], for x = 2.2, 3.5 [2000Nag] and for x = 3 [2002Jon].

The magnetic properties of NdFe4Al8 compound have been studied by specific heat measurements by

[1998Hag] and [2000Hag] while atomistic simulation of the lattice constants and lattice vibrations in

NdFe4Al8 have been performed by [2003Kan].

Spin rearrangement and ferromagnetic field magnetization for Nd2(Fe1-xAlx)17 (x = 0.04) have been

determined by [1995Koi], while high field magnetization and spin reorientation have been studied by

[1996Kat]; moreover anomalous thermal expansion have been measured by room temperature to 400°C by

[1995Zha].

Due to their large glass-forming ability amorphous Al-Fe-Nd alloys have been studied in the last few years.

Inoue et al. studied the thermal stability and the hard magnetic properties of Nd(70,65,60)Fe(20,25,30)Al10

[1997Ino, 1996Ino], while [2001Car] investigated microstructure, thermal stability microhardness as a

function of powder particle size in Nd5Fe5Al90 alloy obtained by gas atomization. [1997Mat] determined

by X-ray diffraction the local atomic structure of Nd(65,30,20,10)Fe(25,40,70,5)Al(10,30,10,85). Several other

authors described the magnetic properties of these phases [1999Din], [1999Phu], [1999Si], [1999Wan],

[2001Chi], [2001Dan], [2001Si], [2001Wan1, 2001Wan2], [2002Bil], [2002Hon], [2002Kon], [2002Lai],

[2002Sat], [2003Bra] and [2003Kum].

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MSIT®

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Alloys of 12 mm in Diameter Made by Suction Casting”, Mater. Trans., JIM, 37(4),

636-640 (1996) (Experimental, Magn. Prop.)

[1996Kat] Kato, H., Knide, T., Yamada, M., Motokawa, M., Miyazaki, T., “High Field Magnetization

and Spin Reorientation in Sm2(Fe1-xAlx)17 and Nd2(Fe1-xAlx)17 Single Crystals”, Sci. Rep.

Res. Inst. Tohoku Univ., A42(2), 283-288 (1996) (Experimental, Magn. Prop.)

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R6Fe12Al2 Compounds with R = Pr, Nd”, J. Alloys Compd., 239(2), 147-149 (1996)


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B234-B236, 637-639 (1997) (Crys. Structure, Experimental, 4)

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Nd-Al-TM (TM = Fe, Co, Ni or Cu) Alloys”, Mater. Sci. Eng. A, A226-A228, 393-396




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[1997Kun] Kuncser, V., Rosenberg, M., Buschow, K.H.J., Filoti, G., “Site Occupation and 57Fe

Mössbauer Spectra of RE6Fe14-xMx with RE = Nd, Pr and M = Ga, Al”, J. Alloys Compd.,

255, 60-66 (1997) (Experimental, Magn. Prop., Moessbauer, 14)

[1997Mat] Matsubara, E., Zhang, T., Inoue, A., “Distinctive Structural Features of Nd-Fe-Al

Amorphous Alloy System”, Sci. Rep. Res. Inst. Tohoku Univ., Ser. A Phys. Chem. Metall.,

43(2), 83-87 (1997) (Experimental)


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Compounds and Their Hydrides”, Phys. Rev. B: Condens. Matter, B57(18), 11472-11482

(1998) (Crys. Structure, Experimental, Magn. Prop., 34)


RFe4Al8 Compounds Studied by Specific Heat Measurements”, J. Alloys Compd., 278,


321


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[1999Din] Ding, J., Si, L., Wang, X.Z., “Magnetoresistivity and Metamagnetism of the Nd33Fe50Al17

Alloy”, Appl. Phys. Lett., 75(12), 1763-1765 (1999) (Crys. Structure, Experimental, Magn.

Prop., 12)




[1999Phu] Phuc, N.X., Dan, N.H., Ding, J., Li, Y., Wang, X.Z., “Observation of Continuos and

Step-Like Thermomagnetization in Nd-Fe-Al Amorphous Alloys”, IEEE Trans. Magn.,

35(5), 3460-3462 (1999) (Experimental, Magn. Prop., 12)

[1999Si] Si, L., Ding, J., Li, Y., Wang, L., Wang, X.Z., “A Structural, Magnetic and Mössbauer

Investigation on Melt-Spun Nd0.33(Fe0.75Al0.25)0.67 Ribbons”, J. Phys.: Condens. Matter,

11, 10557-10566 (1999) (Crys. Structure, Experimental, Magn. Prop., Moessbauer, 17)

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of Amorphous and Crystalline Nd-Fe-Al Alloys”, J. Appl. Phys., 290, 209-215 (1999)



some RFe4Al8 Compounds (R = Ce, Pr, Nd, Dy, Ho, Tm)”, J. Alloys Compd., 298, 77-81

(2000) (Crys. Structure, Experimental, Magn. Prop.,16)

[2000Nag] Nagata, Y., Kamonji, M., Kurihara, M., Yashiro, S., Samata, H., Abe, S., “Magnetism and

Transport Properties of Nd6Fe13-xAl1+x Crystals”, J. Alloys Compd., 296, 209-218 (2000)

(Crys. Structure, Electr. Prop., Experimental, Magn. Prop., 16)

[2000Oka] Okamoto, H., “Desk Handbook Phase Diagrams for Binary Alloys”, ASM International,

Materials Park, OH 44073-0002 (2000)

[2000Wan] Wang, F., Zhang, P., Shen, B., Yan, Q., “Transport Properties of R6Fe11Al3 Compounds (R

= La, Nd)”, J. Appl. Phys., 87(9), 6043-6045 (2000) (Experimental, Magn. Prop., 10)

[2001Car] Cardoso, K.R., Escorial, A.G., Lieblich, M., Botta, W.J.F., “Amorphous and

Nanostructured Al-Fe-Nd Powders Obtained by Gas Atomization”, Mater. Sci. Eng. A,

A315, 89-97 (2001) (Crys. Structure, Experimental, 20)

[2001Chi] Chiriac, H., Lupu, N., “The Magnetic and Structural Properties of the High-Coercivity

Nd50Fe40Al10 Amorphous Alloys”, J. Non-Cryst. Solids, 287, 135-139 (2001)


[2001Dan] Dan, N.H., Phuc, N.X., Hong, N.M., Ding, J., Givord, D., “Multi-Magnetic Phase

Behaviour of the Nd60Fe30Al10 Amorphous Hard Magnetic Alloy”, J. Magn. Magn. Mater.,

226-230, 1385-1387 (2001) (Experimental, Magn. Prop., 3)

[2001Goe] Goedecke, T., Sun, W., Lück, R., Lu, K., “Phase Equilibria of the Al-Nd and the Al-Nd-Ni

Systems”, Z. Metallkd., 92, 723-730 (2001) (Equi. Diagram, Experimental, *, #, 24)




[2001Si] Si, L., Ding, J., Wang, L., Li, Y.,Tan, H., Yao, B. “Hard Magnetic Properties and

Magnetocaloric Effect in Amorphous NdFeAl Ribbons”, J. Alloys Compd., 316, 260-263

(2001) (Experimental, Magn. Prop., 16)

[2001Wan1] Wang, L., Ding, J., Li, Y., Feng, Y.P., Phuc, N.X., Dan, N.H., “Model of Ferromagnetic

Clusters in Amorphous Rare Earth and Transition Metal Alloys”, J. Appl. Phys., 89(12),

8046-8053 (2001) (Experimental)

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Study of Melt-Spun Nd60Fe30Al10”, J. Magn. Magn. Mater., 224, 143-152 (2001)

(Experimental, Moessbauer, Magn. Prop., 22)

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[2002Bil] Billoni, O.V., Villafuerte, M., Urreta, S., Fabietti, L.M., “Magnetic Viscosity in

Nd60Fe30Al10 Amorphous Alloys”, Physica B, B320(1-4), 288-290 (2002) (Experimental,

Magn. Prop., 5)

[2002Hon] Hong, N.M., Dan, N.H., Phuc, N.X., “Large Unidirectional Anisotropy in Nd60Fe30Al10

Bulk Amorphous Alloys”, J. Magn. Magn. Mater, 242-245, 847-849 (2002) (Experimental,

Magn. Prop., 6)

[2002Jon] Jonen, S., Rechenberg, H.R., Campo, J., “Rare Earth Effects on the Magnetic Behavior of

R6Fe11-xAl3+x Compounds”, J. Magn. Magn. Mater., 242-245, 803-805 (2002) (Crys.


[2002Kon] Kong, H.Z., Ding, J., Dong, Z.L., Wang, L., White, T., Li, Y., “Observation of Cluster in

Re60Fe30Al10 Alloys and the Associated Magnetic Properties”, J. Phys. D: Appl. Phys.,

D35(5), 423-429 (2002) (Experimental, Magn. Prop.)

[2002Lai] Lai, J.K.L., Shao, Y.Z., Shek, C.H., Lin, G.M., Lan, T., “Investigation on Bulk Nd-Fe-Al

Amorphous/nano-Crystalline Alloy”, J. Magn. Magn. Mater., 241, 73-80 (2002)


[2002Sat] Sato Turtelli, R., Triyono, D., Groessinger, R., Michor, H., Espina, J.H., Sinnecker, J.P.,

Sassik, H., Eckert, J., Kumar, G., Sun, Z.G., Fan, G.J., “Coercivity Machanism in

Nd60Fe30Al10 and Nd60Fe20Co10Al10 Alloys”, Phys. Rev. B: Condens. Matter, B66(5),

054441-1-054441-8 (2002) (Experimental, Magn. Prop., 18)

[2003Bra] Bracchi, A., Samwer, K., Schneider, S., Loeffler, J.F. “Random Anisotropy and

Domain-wall Pinning Process in the Magnetic Properties of Rapidly Quenched

Nd60Fe30Al10”, Appl. Phys. Lett., 82(5), 721-723 (2003) (Crys. Structure, Experimental,

Magn. Prop., 13)

[2003Kan] Kang, Y., Chen, N., Shen, J., “Atomistic Simulation of the Lattice Constats and Lattice

Vibrations in RT4Al8 (R = Nd, Sm; T = Cr, Mn, Cu, Fe)”, J. Alloys Compd., 352, 26-33

(2003) (Crys. Structure, 40)

[2003Kum] Kumar, G., Eckert, J., Loser, W., Roth, S., Schultz, L., “Effect of Al on Microstructure and

Magnetic Properties of Mould-Cast Nd60Fe40-xAlx Alloys”, Scr. Mater., 48, 321-325 (2003)


[2003Leb] Lebrun, N., “Al-Nd (Aluminum-Neodymium)”, MSIT Binary Evaluation Program, in MSIT







Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

Dissolves 0.5 at.% Nd at 632°C

[1990Kon]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


323


MSIT®

Al–Fe–Nd

( Fe)

( Fe)

1538-1394

( Fe)

< 912

cI2

Im3m

W

a = 293.15

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12


[Mas2]


0-18.8 at.% Al, HT [1958Tay]

0-19.0 at.% Al, HT [1961Lih]

0-18.7 at.% Al, 25°C [1999Dub]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2, 1993Kat]


( Nd)

1021-863

cI2

Im3m

W

a = 413 at 25°C [Mas2]

Dissolves ~12 at.% Al at 690°C

[1996Sac]

( Nd)

< 863

hP4

P63/mmc

La

a = 365.82

c = 1179.66

at 25°C [Mas2]

Dissolves ~2 at.% Al at 650°C

[1996Sac]

Fe4Al13

< 1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16-76.70 at.% Al [1986Gri]


at 76.0 at.% Al [1994Gri]

Fe2Al5< 1169

oC24

Cmcm

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [1994Bur]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [1993Kat]

1102-1232

cI16? a = 598.0 at 61 at.% Al [1993Kat]

FeAl

< 1310

cP2

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5-47.5 at.% Al [1961Lih]

36.2-50.0 at.% Al [1958Tay]

39.7-50.9 at.% Al [1997Kog] quenched

from 500°C in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

~24-~37 at.% Al [2001Ike]

23.1-35.0 at.% Al [1958Tay]

24.7-31.7 at.% Al [1961Lih]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

324


MSIT®

Al–Fe–Nd

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [1993Kat]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [1993Kat]

[1998Ali]

FeAl4+x t** a = 884

c = 2160


[1998Ali]

( Nd3Al11)

1235-917

tI10

I4/mmm

BaAl4

a = 433.8

c = 999.6

lattice parameters for NdAl4(h) [V-C2]

According to [2001Goe] the

transformation temperature decreases

from 934 to 917°C increasing the Nd

content. This phase has a small range of

composition (0.5 at.%) around the

theoretical composition

( Nd3Al11)

< 934

oI28

Immm

La3Al11

a = 435.9

b = 1292.4

c = 1001.7

[V-C2]

NdAl3< 1205

hP8

P63/mmc

Ni3Sn

a = 647.0

c = 460.3

[V-C2] after an annealing of 50 hours at

800°C

Nd(Al1-xFex)2NdAl2< 1460°C

cF24

Fm3m

MgCu2 a = 800.0

0 x 0.5 [1975Dwi]

0 x 0.3 [1991Gri2]

[V-C2] after 7 days annealing at 500°C

NdAl

< 940

oP16

Pbcm

DyAl

a = 594.0

b = 1172.8

c = 572.9

a = 594.2

b = 1173.4

c = 573.3

[V-C2]

[1993Bor]

Nd2Al

< 795

oP12

Pnma

Co2Si

a = 671.6

b = 523.5

c = 965.0

[V-C2]

Nd3Al

< 780

hP8

P63/mmc

Ni3Sn

a = 696.8 to 698.5

c = 541

[V-C2] and [1996Sac]

Nd2(Fe,Al)17 (h) ? stable at higher temperature [1991Gri2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

325


MSIT®

Al–Fe–Nd

Nd2Fe17-xAlx (r)

< 1208

Nd2Fe17

hR57

R3m

Th2Zn17 a = 865.2

c = 1256.9

a = 889

c = 1290

a = 857 to 859

c = 1244 to 1248

0 x ? at 600°C [1991Gri2]

0 x 10.5 at 500°C [1970Viv]

at x = 2 [1989Wei]

at x = 8.5 [1989Wei]

at x = 0 [V-C2]

Nd5Fe17

780

hP228

P63/mcm

Nd5Fe17

a = 2021.4

c = 1232.9

[1991Lan]

* 1, NdFe4-xAl8+x tI26

I4/mmm

ThMn12

a = 881.3

c = 505.8

0 < x < 0.7 [1970Viv]

[1976Bus]

* 2, NdFe2Al10 oC52

Cmcm

YbFe2Al10

a = 900.6

b = 1020.6

c = 906.9

[1998Thi]

* 3,

Nd6Fe9Al(Fe1-xAlx)4

< 900

tI80

I4/mcm

Nd6Fe13Si

or it is ordered

variant of the

R6Fe11Ga3 type

a = 810.45

c = 2310.1

a = 814.72

c = 2307.5

a = 805.2

c = 2294

a = 809.8

c = 2294

a = 815.2

c = 2310

a = 812.8

c = 2311

0.15 x 1 [1991Gri2, 1995Bre]

at x = 0.25

at x = 0.5 [1992Hu]

at x = 0.25 [1995Bre]

at x = 0.45 [1995Bre]

at x = 0.5 [1998Gro]

at x = 0.5 [2000Wan]

* 4, Nd(Fe1-xAlx)2 ? 0.037 x 0.075 [1990Gri]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments/References

326


MSIT®

Al–Fe–Nd

Fig

. 1:

A

l-F

e-N

d.

Rea

ctio

n s

chem

e

Fe-

Nd

Al-

Nd

Al-

Fe-

Nd

(δF

e)(γ

Fe)

, l

13

94

d1

l +

(γF

e) N

d2F

e 17

12

08

p1

L+

(γF

e)(α

δFe)

+N

d2F

e 17

?U1

l +

NdA

l 2 N

dA

l

94

0p2

(γF

e)(α

Fe)

,Nd2F

e 17

91

2d2

(βN

d)

(αN

d),

l

84

3d3

l+N

d2F

e 17

Nd5F

e 17

78

0p4

l (

αNd)

+ N

d5F

e 17

68

5e 3

l +

NdA

l N

d2A

l

79

5p3

l +

Nd2A

l N

d3A

l

78

0p5

l (

βNd)

+ N

d3A

l

69

0e 2

(βN

d)

(αN

d)+

Nd3A

l

65

0e 4

L(α

Fe)

+N

dA

l 2

?e 1

L+

(αF

e)N

dA

l 2+

Nd2F

e 17

?U2

L+

NdA

l 2+

Nd2F

e 17

τ 39

00

P1

L +

τ3 +

Nd2F

e 17

τ 47

50

P2

L+

Nd2F

e 17

τ 4+

Nd5F

e 17

?U4

L+

NdA

l 2τ 3

+ N

dA

l7

20

U3

Nd

Al 2

+τ 3

Nd

Al+

Nd2F

e 17

70

0U5

L+

NdA

l N

d2A

l+τ 3

67

5U7

τ 3+

Νd

Al

Nd2A

l+N

d2F

e 17

67

0U8

L+

(βN

d)

(αN

d)+

Nd3A

l?

U9

L+

Nd2A

lτ 3

+N

d3A

l6

25

U11

L +

τ4

τ 3 +

(αN

d)

64

5U10

L+

Nd5F

e 17

(αN

d)+

τ 46

80

U6

Lτ 3

+ (

αNd)

+ N

d3A

l6

00

E1

?

L+

NdA

l 2+

Nd2F

e 17

L+

(αF

e)+

Nd2F

e 17

L+

Nd2F

e 17+

τ 3L

+N

dA

l 2+

τ 3N

dA

l 2+

Nd2F

e 17+

τ 3

L+

NdA

l+τ 3

L+

Nd2A

l+τ 3

L+

(αN

d)+

Nd3A

l

τ 3+

NdA

l+N

d2F

e 17

L+

τ 4+

τ 3

L+

τ 4+

(αN

d)L

+N

d5F

e 17+

τ 4

NdA

l 2+

(αF

e)+

Nd2F

e 17

τ 3+

Nd2A

l+N

d3A

l

(αN

d)+

τ 3+

Nd3A

l

L+

τ 3+

(αN

d)

τ 3+

τ 4+

(αN

d)

τ 4+

(αN

d)+

Nd5F

e 17

τ 3+

τ 4+

Nd2F

e 17

τ 3+

Nd2A

l+N

d2F

e 17

NdA

l+N

d2A

l+N

d2F

e 17

Nd

Al 2

+N

dA

l+τ 3

NdA

l 2+

NdA

l+N

d2F

e 17

L+

Nd2F

e 17+

τ 4

L+

τ 3+

Nd3A

l

Nd2F

e 17+

τ 4+

Ni 5

Fe 17

Nd

Al+

Nd2A

l+τ 3

327


MSIT®

Al–Fe–Nd

10

20

30

40

10 20 30 40

60

70

80

90

Nd 50.00Fe 0.00Al 50.00

Nd 0.00Fe 50.00Al 50.00


Axes: at.%

Fe4Al13

Fe2Al5

FeAlNd2Fe17-xAlx

τ1

τ2

Nd3Al11

NdAl3

NdAl2FeAl2

(Al)Fig. 2: Al-Fe-Nd.


500°C

20

40

60

80

20 40 60 80

20

40

60

80

Nd Fe


Axes: at.%

Nd3Al+τ3+(αNd)

Nd2Al+Nd3Al+τ3

τ4

Nd

2 Fe17-x A

lx (r)τ3

Nd3Al

Nd2Al

NdAl

NdAl2

Nd2Fe17-xAlx(r)+NdAl+Nd2Al

Nd2Fe17Nd5Fe17

(αNd)

?

Fig. 3: Al-Fe-Nd.


600°C from

[1991Gri2]

328


MSIT®

Al–Fe–Nd

10 20500

600

700

800

900

Nd 70.00Fe 30.00Al 0.00

Nd 70.00Fe 0.00Al 30.00Al, at.%

Tem

pera

ture

, °C

L

L+τ3 L+τ3+Nd2Al

L+τ 3+NdAl

L+NdAl

L+Nd2Al

L+Nd2Al+Nd3Al

τ3+Nd2Al+Nd3Al

τ3+(αNd)+Nd3Al

L+τ3+(αNd) L+τ3+Nd2Al

L+NdAl+Nd2Al

L+Nd5Fe17

L+Nd5Fe17+τ4

L+τ4

L+(αNd)+Nd5Fe17

L+(αNd)+τ4

(αNd)+τ3+τ4

(αNd)+Nd5Fe17+τ4

L+τ3+τ4

L+τ3+NdAl2

U6,680

U10,645 U11,625

E1,600

U7,675

U3,720

L+Nd2Fe17+Nd5Fe17

L+Nd2Fe17

(αNd)+Nd5Fe17

Fig. 4: Al-Fe-Nd.


at.% Nd = constant

329


MSIT®

Al–Fe–Ni

Aluminium – Iron – Nickel

Peter Budberg and Alan Prince,

updated by

Gabriele Cacciamani, Riccardo Ferro, Benjamin Grushko, Pierre Perrot, Rainer Schmid-Fetzer

Literature Data

The first extensive investigation of the Al-Fe-Ni ternary system was the determination of the liquidus

surface at <50 mass% Al ( 75 at.% Al). Since, a critical assessment of the system may be found in

[1980Riv] with minor amendments by [1988Ray] and an update by [1992Bud]. [1994Rag] presented

isothermal sections at 950 and 1050°C in the Al-rich part of the diagram (> 50 at.% Al), an isothermal

section at 1050°C in the Fe-rich part of the diagram (> 50 at.% Fe) and a vertical section along the

Ni3Al-Ni3Fe join. The first calculations of the whole diagram by the Calphad method has been carried out

by [1974Kau] at 1200, 1400, 1600 and 1700 K. The phase diagram calculated at 1200 K looks strongly like

the diagram proposed by [1940Bra1] which represents the structures obtained by a slow cooling method.

Microstructural observations of [1995Guh] after water quenching Fe30Ni20Al50 alloys following annealing

at 420, 620 and 820°C does not contradict phase equilibria proposed by [1980Riv]. Experimental work of

[1993Pov, 1994Gho, 1994Jia, 1999Dyb, 2000Dyb, 2002Bit] on phase equilibria together with the

apparition of quasicrystalline decagonal phases [1989Tsa, 1994Lem, 1996Yam, 1997Sai, 2002Hir,

2003Doe] adds to our knowledge of this ternary system and necessitates an updating of the earlier

assessments by [1980Riv] and [1992Bud]. More recent experimental work are summarized in Table 1. This

ternary system exhibits a continuous series of solid solutions between ,NiAl and ,FeAl (B2 structure, type

CsCl). This fact allows the system to be split into two: the Al-rich portion from 50 to 100 at.% Al and the

Fe-Ni rich region from 0 to 50 at.% Al. The solidus temperatures in the (50 at.% Al) solid solution has

been experimentally determined by [2002Bit].

The Al-rich region has been studied by [1934Fus, 1938Bra, 1940Bra1, 1942Phi, 1943Sch, 1947Ray,

1981Kha, 1982Kha, 1986Sei, 1993Pov, 2000Dyb]. Reviews have been published by [1943Mon, 1952Han,

1961Phi, 1976Mon, 1992Bud, 1994Rag].

The data on the possible constitution of liquidus surfaces in the Al-Fe3Al-Ni3Al field are given in [1934Fus,

2000Dyb]. According to [1938Bra], however, two ternary phases are formed in the composition field

mentioned above: 1(FeNiAl9) and 2(Fe3NiAl10). These data were confirmed by [1940Bra1]. The

conditions of the 1 formation were established by [1943Sch, 2000Dyb]; it crystallizes by a peritectic

reaction (P):

L + Fe4Al13 + NiAl3 1 at 809°C.

This temperature was confirmed by [1981Kha, 1982Kha, 1986Sei, 2000Dyb].

The data on the presence of two invariant transformations in the Al-rich alloys

(E2): L (Al) + 1 + NiAl3 and

(U2): L + Fe4Al13 (Al) + 1

previously obtained by [1942Phi] were also confirmed. These reactions take place at 640 and 650.2°C,

respectively [1943Sch] or at 638 [1942Phi, 1981Kha, 1982Kha, 1986Sei, 2000Dyb] and 649°C [1942Phi],

respectively.

The phase field boundaries in the Al-rich portion of the diagram at 620°C were constructed by [1943Sch]

and isothermal sections at 500 and 550°C by [1947Ray]. These data are in good agreement with each other.

[1938Bra, 1940Bra1] cooled homogenized and afterwards powdered alloys, which were then held at

different temperatures with 10 K min-1 in vacuum. The authors suggest that the section obtained probably

represents a 500°C isothermal.

The phase 1(FeNiAl9) has a homogeneity range from 4.42 to 11.11 at.% Fe and from 7.01 to 13.5 at.% Ni

at 620°C [1943Sch]. By precipitation from liquid Al-rich alloys, [1996Zho] obtains a 1 phase whose

chemical composition lies in the range FexNi2-xAl9 (1 x 1.6). The 1 phase is also easily observed by

reacting Fe-Ni alloys with liquid Al at 700°C [1999Dyb].

330


MSIT®

Al–Fe–Ni

In the reviews [1952Han, 1961Phi] the previously obtained data were generalized though [1961Phi]

virtually followed [1942Phi]. According to [1976Mon], the reactions P, E2 and U2 occur at 809, 639 and

649°C, respectively. The solubility of Ni in Fe3Al is 1.4 to 1.9 at.% and that of Fe in Ni3Al, up to 0.5 at.%.

The FeNiAl9 compound ( 1) has been given a homogeneity range from 3.0 at.% Fe and 17 at.% Ni to 7.5

at.% Fe and 11.5 at.% Ni by [1976Mon].

Using precise investigation techniques, in particular electro-magnetic separation of phases in the

liquid-solid state after annealing at 1050, 950 and 750°C for 3 h, [1981Kha, 1982Kha] established the

position of tie lines between the equilibrium phases. Isothermal sections at 750, 950 and 1050°C were

constructed after prolonged exposures for 40, 15 and 3 d, respectively. These heat treatments allowed

establishment of the formation of a new ternary phase, FeNi3Al10, besides two previously known ( 1 and

2). This phase, according to [1981Kha, 1982Kha], exists in a narrow temperature range and decomposes

at slow cooling so that it has not been found by [1938Bra, 1940Bra1, 1947Ray] and others. The solubility,

at room temperature, of Fe in Ni2Al3 and NiAl3 is 2 and 4 at.%, respectively and that of Ni in FeAl2, Fe2Al5and Fe4Al13 at 1050°C is up to 2, 2 and 10 at.%, respectively [1982Kha].

Between 1050 and 950°C an invariant reaction L + 2 Fe4Al13 + Ni2Al3 takes place [1981Kha, 1982Kha].

The formation of ternary FeNiAl5 was found in a powder sample (composition Fe14.3Ni14.3Al71.4) annealed

at 720°C for 3 h and water quenched; it has a hexagonal structure of the Co2Al5 type [1990Ell]. It is known

that 2 is also isotypic to Co2Al5. According to [1990Ell], the position of homogeneity fields corresponding

to ternary phases may be displaced along the Al isoconcentration line (exactly along FexNi0.286-xAl0.714),

dependent on the heat treatment; during this displacement an Fe to Ni substitution takes place (or a reverse

process may occur). This fact may be explained by the ease of the electron exchange between analogous

metals. In the case of the alloy quenched from 720°C, the Fe:Ni ratio is equal to 1:1; it corresponds to the

FeNiAl5 alloy, so here the FeNiAl5 phase is assumed to lie within the homogeneity range of 2.

[1986Sei] used insufficiently prolonged exposures during annealing. 72 h to 200 h were applied to

homogenize the alloys at temperatures between 1200 and 600°C followed by annealing for 50 h at 1000,

800 and 600°C and water quenching. [1981Kha, 1982Kha] used 72 h at 1050°C, 360 h at 950°C and 960 h

at 750°C, and even then stated that equilibrium was not established at 750°C. This is the reason why the

field of the 2 existence was not confirmed by [1986Sei]. [1986Sei] did also find a two-phase region

NiAl+FeAl at 650, 750, 1000 and 1150°C, which is in contradiction to the results of [1938Bra, 1940Bra1,

1951Bra, 1952Bra], the lattice parameter studies of [1939Lip] and [1972Kot] and the work of [1984Hao].

[1972Kot] found 17 single phase alloys at 950°C with the lattice parameter increasing up to 25 at.% Ni and

then constant up to NiAl. [1984Hao] also shows an ordered CsCl type phase to exist between 1150 and

850°C from the Al-Fe to the Al-Ni side.

Alloys with compositions close to the Fe-Ni side were studied in detail by [1938Bra, 1940Bra1, 1949Bra,

1951Bra, 1952Bra]. The features of the crystallization and the phase constitution of these alloys were

investigated by DTA, X-ray diffraction and metallographic analysis in a temperature range of 750°C to

melting. The position of the phase boundaries in the alloys with < 50 at.% Al is strongly dependent on the

invariant four-phase equilibrium U1 and on the minimum point (point of tangency) of the liquidus and

solidus surfaces. The temperature of the reaction:

U1: L + ' +

was established to be 1380°C [1949Bra]. Taking into account some new data on the formation of the

'(Ni3Al) phase in the binary Al-Ni system [1987Hil, 1988Bre], it must be noted that this temperature could

not exceed 1365°C. A monovariant order-disorder transformation descends from higher Al contents to the

monovariant melting trough p1-e2 (see Fig. 3a). The dotted line belongs to the liquidus concentrations

corresponding to the solidus intersecting with the order-disorder transformation between and as a

second order transformation (see Fig. 14). Older publications [1942Dan, 1949Bra] introduced a transition

type reaction at 12.5 at.% Al and 67.5 at.% Fe [1949Bra] for the liquid with the equation:

L + + , 1350°C,

assuming that the two-phase field + extends up to the liquid, but this has been revised by more recent

experiments [1984Hao], Fig. 14. [1984Hao] applied diffusion couple techniques on samples prepared from

99.95% Fe, 99.95% Ni and 99.9% Al and annealed at temperatures between 850 and 1150°C to determine

the shape of the miscibility gap between and . The exact location of the order-disorder transformation

331


MSIT®

Al–Fe–Ni

to higher Al contents is unknown; in Fig. 3a it is assumed that it contacts directly with the same

transformation in the Al-Fe binary system.

The decomposition of the ( Fe, ) solid solution to a mixture of and on cooling was investigated by

[1940Kiu, 1941Kiu1, 1941Kiu2, 1941Kiu3, 1942Dan, 1949Bra, 1951Bra, 1952Bra, 1984Hao] in detail.

Using X-ray diffraction, [1941Kiu1, 1941Kiu2, 1941Kiu3] investigated both the position of a three-phase

field + + and possible transformations in the solid state in detail. Unfortunately, this field was

incorrectly projected on the composition plane (the phase rule was violated). The position of a three-phase

field + '+ at 1000°C was refined by [1986Bra]; the ' field at 1000°C stretches to 60.9 at.% Ni though

[1949Bra] has supposed that this field stretches to 68 at.% Ni at 1050 and 950°C. The two-phase equilibrium

+ ' was calculated by the cluster variation method with the tetrahedron approximation [1991Eno] and the

results compared with experimental determinations of [1949Bra, 1951Bra]. Experimental investigations of

the - ' and - ' equilibria in the Ni rich corner of the diagram were carried out by [1994Jia] at 1100 and

1300°C using diffusion couples and electron microprobe analysis.

The Ni3Al-FeNi3 section has been studied by [1987Mas] using 99.9 mass% Ni, 99.99 mass% Al and 99.9

mass% Fe, the samples being homogenized at 1050°C for 48 h. Metallographic, X-ray and diffusion couple

techniques have been applied to examine the phase boundaries at 75% Ni. Using neutron diffraction,

[1998Gom] investigated the L12 ordering in the Ni3Al-FeNi3 section at low temperatures.

Binary Systems

The binary boundary systems Al-Ni and Al-Fe are accepted from critical assessments of [2003Sal] and

[2003Pis], respectively. The Fe-Ni binary phase diagram is taken from [1982Kub].

Solid Phases

The crystallographic data of the Al-Fe-Ni phases and their temperature ranges of stability are listed in

Table 2. In general Fe and Ni are not appreciably dissolved in Al, but form solid solutions which extend

significantly into the ternary system.

The Al-Fe based bcc solid solution extends into the ternary and its Ni concentration increases with the

increase of the Al concentration. In the binary Al-Fe system it orders in by a second order transformation

which became first order by adding Ni.

phase (CsCl-type) forms a continuous range of solid solutions between Al-Fe, Al-Ni and toward Fe.

Along the NiAl-Fe direction a miscibility gap is formed between the ordered and disordered solid

solutions. Lattice parameters and hardness measurements in the field have been carried out by [2001Tan].

Site occupancies of Fe in NiAl were first investigated by [1994Dun] by using atom-probe field-ion

microscopy. Then an exhaustive study of lattice parameters, site occupancies and vacancy concentration,

point defects, density and hardness has been carried out by [1997Pik, 2002Pik] over a wide range of

compositions and temperatures in the -region. The triple defect structure was observed across the entire

phase field. In all Al-rich compositions constitutional vacancies were observed. Thermodynamic

predictions that the Fe anti-sites are more stable than the Ni anti-sites in the Al-poor compositions were

qualitatively confirmed. The lattice parameter as a function of composition is reported in Figs. 1a and 1b.

The fcc solid solution extends from the Fe-Ni subsystem to more than 20 at.% Al. With decreasing

temperature it orders in the ' structure (AuCu3 type) at about 75 at.% Ni and forms a continuous solid

solution with the isostructural Ni3Al [1986Bra, 1987Mas, 1998Gom]. Iron can occupy both Al and Ni

sublattices, 78% of Fe atoms occupy Al sublattice for the Fe concentration of 2.5 at.%, while only 54% for

the 9.3 at.% Fe compound [1977Nic]. Dissolution of Fe to at least 7 at.% does not influence the lattice

parameter of ' [1959Gua, 1984Och].

Site occupancies in Fe3Al and, in particular, the substitution of Fe by Ni (about 3 at.%) have been

investigated by neutron diffractometry [1998Sun].

The monoclinic Fe4Al13 phase dissolves up to 12.0 at.% Ni at 800°C and NiAl3 dissolves up to 2.5 at.% Fe

[1996Gru1], Ni2Al3 can dissolve about 2, 4 and 10 at.% Fe at room temperature, 850 and 1050°C,

respectively, Fe2Al5 and FeAl2 can dissolve up to 2 at.% Ni at elevated temperatures [1982Kha].

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No ternary phases were reported in the Al-poor region. In the Al-rich region three stable ternary phases were

revealed. The 1 (Ni,Fe)2Al9 phase isostructural to Co2Al9 is formed at almost constant 82 at.% Al between

4.4 to 11.1 at.% Fe [1943Sch, 1999Dyb, 2000Dyb]. The same phase extends from 9 to 14.5 at.% Fe when

1 precipitates from melt-spun samples [1996Zho].

The hexagonal 2 Fe3NiAl10 phase of the Co2Al5 type has been observed at 1050°C in the

Al70-72.5Fe18-24.5Ni10.5-4.5 composition range [1981Kha]; it has been structurally characterized by

[1990Ell].

Quasiperiodic structures to which higher dimensional crystallography is applicable were discovered in

Al-Fe-Ni alloys since 1989. A number of different decagonal diffraction patterns have been first observed

[1989Tsa] in Al-Fe-Ni alloys prepared by melt quenching. After that decagonal phases have been studied

by several authors [1989Tsa, 1993Tan, 1994Lem, 1996Gru1, 1997Sai, 2000Fre, 2001Hir, 2002Yok,

2003Doe]. The best known is the phase 3 (periodicity of about 0.4 nm), stable between 930 and 847°C in

a range of less than 1 at.% around the Al71Ni24Fe5 composition [1994Gru, 1994Lem, 1996Gru1, 2000Dro,

2003Doe]. It probably corresponds to an unidentified phase FeNi3Al10 previously observed by [1982Kha].

The diffraction patterns of the 3-phase are very similar to those of the Ni-rich decagonal phase found in the

more extensively studied Al-Co-Ni alloy system [1996Gru2]. It was argued by [1996Gru1] that the stable

ternary 3 phase is an extension of a metastable isostructural Al-Ni phase.

Two more metastable D-phases with slightly different diffraction properties were observed by [1993Tan,

1997Sai, 2001Qia] at higher Fe content. Structural models belonging to the space groups P10m2 and

P105/mmc (or P10/mmm, according to [1993Tan]) were found to approximate the HRTEM images of

quasicrystals at Fe30-xNixAl70 with 10 < x < 17 and 17 < x < 20, respectively [1997Sai]. Disorder in these

phases has been studied by X-ray (synchrotron) and neutron diffraction experiments [2000Fre]. [2001Hir]

found that large columnar clusters of atoms with a decagonal section of about 3.2 nm in diameter exist as a

basic structural unit.

It may be noticed that owing to the experimental and interpreting difficulties, also connected to the

dependence of the sample structures on the preparation procedures, the reported description of the Al-Fe-Ni

decagonal phases may be considered still incomplete but representative of a more complex situation.


It may be supposed that a pseudobinary section exists in the system. It occurs between FeAl and NiAl which

possess isotypic structures. A series of continuous solid solutions is formed of the CsCl structure type; the

melting point of the alloys decreases monotonically from NiAl to FeAl. However, the tie lines L+ are

essentially perpendicular to that section, which renders it non-pseudobinary. A miscibility gap develops in

at lower temperatures [1986Sei]. These tie lines are again off-section and essentially in the NiAl-Fe

direction as described in more detail under Isothermal Sections.


The data on the invariant equilibria are given in Table 3 according to [1949Bra] (U1) and [1943Sch] (P, E2,

U2). The U1 temperature was corrected according to [1987Hil, 1988Bre]. The data on the eutectic

decomposition, E1, of the ternary decagonal phase 3 are accepted from [1996Gru1]. A partial reaction

scheme is given in Fig. 2.

Liquidus Surface

The projection of liquidus surfaces of portions of the ternary diagram investigated by [1949Bra] (0 to 50

at.% Al) and [1943Sch] (100 to 88 at.% Al), adapted to the accepted binaries, are given in Fig. 3a, and a

more detailed view of the Al-corner [1942Phi] in Fig. 3b. It should be noted that the position of the

minimum point of the peritectic/eutectic line, e2, at 50 at.% Fe must be above 1350°C, see Fig. 4, and below

the 1365°C of U1. It is assessed at 1360°C. The liquidus surface of is extremely flat in that range. In the

alloys with 85 to 50 at.% Al additional invariant transformations must occur in the range 850 to 1340°C

(besides the four-phase reactions already investigated) where the reactions p3, p4, p5, p6, p7, e3 and e4 of the

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Al–Fe–Ni

corresponding binary systems enter the ternary. The U-type reaction suggested at ~840°C with a liquid at

about 82 at.% Al [1992Bud] cannot be accepted in view of the firmly established three-phase equilibrium

Fe4Al13 + Ni2Al3 + NiAl3 formed in the reaction E1 at 847°C [1996Gru1].

Isothermal Sections

Isothermal sections between 1350 and 750°C, Figs. 4 - 10, were constructed on the basis of the data obtained

by [1949Bra, 1951Bra, 1981Kha, 1982Kha, 1984Hao, 1986Bra, 1996Gru1]. The location of the

order-disorder transition between and at 1350°C in Fig. 4 is not known but must occur inside the

ternary since in the binary Al-Fe that transition ends at 1310°C. This line is shown dotted in Figs. 5 and 6.

At even lower temperature, Figs. 7 - 10, the peculiar horn-shape develops. This indicates the change from

the second order transition along a single line to the first order transition with a two-phase field + , that

exists only in the ternary. This miscibility gap, taken essentially from [1984Hao] is in qualitative agreement

with the data of [1941Kiu3]. The plotted phase boundaries of [1941Kiu3], however, do not show the

horn-shape with the necessary tricritical point and are therefore not reproduced.

The position of the three-phase field + + ' at 1050 and 950°C in Figs. 7 and 8 was refined based on the

data of [1986Bra] at 1000°C. The data obtained by diffusion couple technique at 1300 and 1100°C [1994Jia]

essentially agree with that, although they show a somewhat different curvature of the phase boundaries. The

'/ + ' and / + ' boundaries of [1994Jia] are curved towards higher Al-content. All sources agree on the

important distribution of Fe in the three phases, showing a decreasing Fe-content in the phase sequence

- '- [1949Bra, 1986Bra, 1994Jia].

The position of phase fields in the Al-rich alloys are given according to [1981Kha, 1982Kha, 1996Gru1].

At 1050 and 950°C, the 2 phase field can be seen; the decagonal phase 3, stable between 930 and 847°C

[1996Gru1], is given in Fig. 9 with other partial equilibria; at 750°C, the 1 phase already exists. The

isothermal section at 620°C of the Al-rich portion of the diagram is shown in Fig. 11 [1943Sch].

The general distribution of phase fields in the whole composition triangle is given in Fig. 12; the data were

obtained by cooling the alloys with a rate of 10°C h-1 from 900°C (for Al-rich alloys, from 600°C) in

[1938Bra, 1940Bra1, 1940Bra2]. Early calculations of isothermal sections for 927, 1127, 1327 and 1427°C

are given by [1974Kau], at that time without modeling the bcc ordering. The - ' phase boundaries have

been calculated in [1991Eno] by cluster variation method using tetrahedron approximation and the

phenomenological Lennard-Jones pair potentials. The results are in a fair agreement with the experimental

data from [1949Bra, 1951Bra].


Two vertical sections parallel to the Fe-NiAl section with some Ni-excess are shown in Figs. 13 and 14, and

the Fe-NiAl section in Fig. 15. The Ni-excess sections may be approximately considered as pseudobinary

sections. By contrast, Fig. 15 is absolutely not pseudobinary with the + tie lines virtually perpendicular

to the section. It is important to note that minute changes of the phase limits in the isothermal sections

correspond to drastic changes in these vertical sections. In this context, the agreement between the sections

reported by [1951Bra, 1984Hao] for Fig. 14 or [1951Bra, 1951Iva] may be considered to be fair. As an

example in Fig. 15, [1951Bra] reports a small three-phase field + + around 80 at.% Fe and 750-850°C,

whereas [1951Iva] reports a continuous single phase field connecting ( Fe) and ( Fe), as shown dashed

in Fig. 15. These alternatives are probably within the experimental error of the phase limit in the

corresponding isothermal sections. It is thus not considered helpful to reproduce the additional vertical

sections reported by [1951Bra] for the Al-excess sections or by [1952Bra] for the sections parallel to Al-Fe.

A similar reasoning applies to the vertical sections reported in the early work of [1933Koe, 1941Kiu3].

The vertical section Ni3Al-Fe3Al [1987Mas] displayed in Fig. 16 is also supported by the data of [1994Jia]

on the Fe-poor + ' equilibrium. The data of [1998Gom] indicate a lower / + ' boundary but are

unacceptably low for the Ni3Al limit.

The + miscibility gap is due to both chemical and magnetic ordering effects. It has been tried to separate

these effects in a Calphad-type calculation, suggesting that the (metastable) miscibility gap in the

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Al–Fe–Ni

magnetically and chemically disordered state is at much lower temperature compared to the stable gap along

a vertical section Fe97.5Al2.5 - Ni49.5Al50.5 [1994Gho].

Thermodynamics

The temperature and the enthalpy of fusion of the decagonal phase Fe5Ni24Al71 prepared by inductively

melting the pure metals, water cooling, then annealing 300h at 880°C has been respectively determined in

967 ± 5°C and 13.0 ± 0.4 kJ·mol-1 of atoms [1999Hol]. The standard enthalpy of formation of the phase

at different compositions has been measured by Al solution calorimetry by [1993Zub] and, with very good

reproducibility, by [2001Bre]. Their results are reported in Table 4.


Fe is one of the most important constituent of Ni-base superalloys because the B2-type of NiAl phase has a

high melting temperature, high thermal conductivity and high resistance to oxidation. The lack of high

temperature strength may be overcome by the use of Fe or other minor additions such as Ga or Mo

[2002Alb] and a systematic study of correlation between point defects and Fe precipitates has been

undertaken [1998Ko, 2002Alb], together with the influence of iron on physical, mechanical (grain size,

yield strength) and magnetic properties of NiAl [2002Ban, 2002Mun]. Indeed, these compounds would be

of higher practical interest if their attractive high temperature behavior could be combined with good room

temperature formability. This aim may be achieved by introducing a substantial amount of disorder in their

crystal lattice. Several techniques have been proposed like melt spinning, ion irradiation, mechanical

alloying [1991Kos, 1995Gaf, 2001Sur] or introduction of dopants such as carbon [2002Kim].

Nanostructured materials show significant kinetics of reordering even at 300°C. However, complete

reordering could not be achieved, even after long annealing time at 600°C [2002Joa]. Al-Fe-Ni alloys are

good precursors for the preparation of Fe-Ni powders with high surface area and interesting catalyst

properties [1981Kha]. Ternary alloys with nominal compositions Ni30Fe5Al65 and Ni15Fe10Al75 prepared

by mechanical alloying were used to obtain Fe-Ni Raney-type catalysts by leaching aluminium with an

alkaline aqueous solution [2000Zei].

New materials may be obtained through thermal explosion reaction as an alternative to combustion

synthesis. The order of reaction n and the activation energy E of thermal explosive reaction for

Fe30Ni50Al20 (in mass%) has been respectively measured as n = 0.37 and E = 152 kJ·mol–1 [2002He]. The

maximum reaction temperature is 657°C, higher than eutectic temperature between Al and NiAl3, so that

the thermal explosion consists of both liquid and solid state reactions.

Al-Fe-Ni alloys present a shape memory effect in the + field [1992Kai]. The control of the Ms

(Martensite start) temperature, difficult to achieve in Al-Ni alloys because of the very sensitive dependence

on the Al content, is, on the other hand, very easily achieved in the ternary two-phase alloy by manipulating

the composition of the phase through appropriate choice of annealing temperatures.

Miscellaneous

Crystallographic features of decagonal structures are presented in [1996Yam, 2002Hir] and formation rules

for Al-Fe-Ni quasicrystals were pointed out in [2001Qia]. A number of different decagonal diffraction

patterns have been first observed [1989Tsa] in Al-Fe-Ni alloys prepared by melt quenching in the

composition ranges from 9 to 16 at.% Ni, 9 to 21 at.% Fe, in good agreement with the composition range

Fe20-xNi10+xAl70 (0 x 10) more recently proposed by [1993Tan, 1997Sai]. However, more precise

investigations show the possible existence of at least 3 decagonal phases. Quasicrystals Fe20-xNi10+xAl70

were found by the convergent-beam electron diffraction (CBED) method to belong to the

noncentrosymmetric space group P10m2 for 0 x 7 [1993Tan, 1997Sai] and to the centrosymmetric

group P10/mmm for 7 x 10 [1993Tan] and to present periods along the tenfold axis which are multiple

of 0.4 nm [1997Yam]. It is probable that these structures correspond actually to the phases

D1, Fe14.5Ni13Al72.5 and D2, Fe9.83Ni19.34Al70.83 whose structure has been described by [2001Qia].

D1, Fe14.5Ni13Al72.5 is observed to coexist with 2, FeNiAl5. Decagonal phases reveal higher positron

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Al–Fe–Ni

lifetime than crystalline compounds [1995Wue], which implies higher concentration of structural

vacancies. A characteristic feature of these structures, isotypic with decagonal phases encountered in

Al-Co-Ni and Al-Co-Cu systems [1994Gru] is that they consist of 2 nm clusters with pentagonal symmetry.

The superstructure is due to chemical ordering in the central part of the 2 nm clusters. Star-shaped and

butterfly-shaped tiles observed in quasicrystals are well understood from observations of [2002Yok].

Diffuse scattering from X-rays (synchrotron) and neutrons [2000Fre] shows disordered layers

perpendicular to the unique tenfold axis.

The diffusion experiments, carried out at 1002°C in the B2 ( NiAl) domain of the ternary system presents

anomalous behavior [1976Moy], the interactions among the various components being strongly

composition dependent. This is explained [1997Kai] by the fact that NiAl has a wide composition range and

exhibits two types of structural imperfections depending on the nature of deviation from stoichiometry. In

NiAl, iron was observed to substitute preferentially aluminium atoms whatever the Al/Ni ratio [1994Dun,

2002Ban]. The substitution (up to 10 at.%) of Al by Fe in NiAl decreases the lattice parameter and increases

the Young’s modulus [1991Mas]. More generally, the introduction of Fe increases the hardness of the Al

rich alloys and decreases the hardness in the Ni rich alloys [1997Pik, 2001Tan]. This softening is attributed

to the replacement of Ni anti-site defects with Fe defects on the Al sublattice. On the other hand, the site

preference of Ni in ordered iron aluminide has been determined using ALCHEMI technique (Atom

Location by Chaneling-Enhanced Microanalysis), first in the Fe50Ni5Al45 alloy [1997And], then in the

whole domain (40 to 52 at.% Al) [2002Pik]. Ni was found to occupy the Fe sites exclusively, displacing

Fe to Al anti-sites [2002Ban, 2002Pik]. The influence of Ni on the formation and growth characteristics of

Fe based aluminide diffusion layers has been modelled [1998Akd, 1999Mek] by mean of a quasichemical

method combined with an electronic theory in the pseudopotential approximation; the influence of Fe on

the lattice parameter and hardening of NiAl has been modelled [2002Liu] by first principle quantum

mechanical calculations. The site preference in various solid solutions (FexNi50-x/2Al50-x/2, FexNi50-xAl50

FexNi50Al50-x) have also been modelled [2002Boz] via Monte-Carlo simulation. A phenomenological

model for multicomponent diffusion in the (B2 ordered) phase was presented by [1999Hel] and calculated

diffusion paths were compared with experimental ones given by [1976Moy]. The OTL (ordering tie-line)

approach [2000Ama] confirms the preceding observations showing that, while Ni segregates preferentially

to the Fe sublattice in Al depleted FeAl, Fe segregates preferentially to the Al sublattice in Al depleted NiAl.

The presence of iron improves the fatigue behavior under cyclic accumulated strain [1991Har]. Fracture

thoughness and yield strength of ,NiAl and ,Fe20Ni45Al35 is improved by mechanical alloying with

additions of small amounts of Y2O3 which allows the achievement of fine grain sizes [1991Kos].

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[1988Ray] Raynor, G.V., Rivlin, V.G., “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals,

London, 107-121 (1988) (Equi. Diagram, Review, #, 32)



[1989Tsa] Tsai, An-P., Inoue, A., Masumoto, T., “New Decagonal Al-Ni-Fe and Al-Ni-Co Alloys

Prepared by Liquid Quenching”, Mater. Trans., JIM, 30(2), 150-154 (1989) (Crys.


[1990Ell] Ellner, M., Röhrer, T., “On the Structure of the Ternary Phase FeNiAl5” (in German), Z.

Metallkd., 81(11), 847-849 (1990) (Equi. Diagram, Crys. Structure, *, #, 23)

[1991Eno] Enomoto, M., Harada, H., Yamazaki, M., “Calculation of `/ Equilibrium Phase

Compositions in Nickel-Base Superalloys by Cluster Variation Method”, Calphad, 15(2),

143-158 (1991) (Assessment, Calculation, Equi. Diagram, #, 34)

[1991Har] Hartfield-Wuensch, S.E., Gibala, R., “Cyclic Deformation of B2 Aluminides”, Mater. Res.

Soc. Symp. Proc.: High-Temp. Order. Intermet. Alloys IV, 213, 575-580 (1991) (Crys.

Structure, Experimental, Mechan. Prop., 12)

[1991Kim] Kim, Y.D., Wayman, C.M., “Transformation and Deformation Behavior of Thermoelastic

Martensite Ni-Al Alloys Produced by Powder Metallurgy Method” (in Korean), J. Korean

Inst. Met. Mater., 29(9), 960-966 (1991) (Mechan. Prop., Experimental, 15)

[1991Kos] Kostrubanic, J., Koss, D.A., Locci, I.E., Nathal, M., “On Improving the Fracture Toughness

of a NiAl-Based Alloy by Mechanical Alloying”, MRS Symp. Proc.: High-Temp. Order.

Intermet. Alloys IV, 213, 679-684 (1991) (Experimental, Phys. Prop., 17)

[1991Mas] Maslenkov, S.B., Filin, S.A., Abramov, V.O., “Effect of Structural State and Alloying of

Transition Metals on the Degree of Hardening of Ternary Solid Solutions Based on Nickel

Monoaluminide”, Russ. Metall., (1), 115-118 (1991) translated from Izv. Akad. Nauk SSSR,

Met., (1), 111-115 (1991) (Crys. Structure, Experimental, Mechan. Prop., 10)

[1991Pat] Patrick, D.K., Chang, K.-M., Miracle, D.B., Lipsitt, H.A., “Burgers vector Transition in

Fe-Al-Ni Alloys”, Mater. Res. Soc. Symp. Proc.: High-Temp. Order. Intermet. Alloys IV,

213, 267-272 (1991) (Mechan. Prop., Experimental, 10)

[1991Yav] Yavari, A.R., Baro, M.D., Fillion, G., Surinach, S., Gialanella, S., Clavaguera-Mora, M.T.,

Desre, P., Cahn, R.W., “L12 Ordering in Disordered NiAlFe Alloys”, Mater. Res. Soc.

Symp. Proc.: High-Temp. Order. Intermet. Alloys IV, 213, 81-86 (1991) (Crys. Structure,


[1992Bud] Budberg, P., Prince, A., “Aluminium - Iron - Nickel”, MSIT Ternary Evaluation Program,

in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services

GmbH, Stuttgart; Document ID: 10.10205.1.20 (1992) (Crys. Structure, Equi. Diagram,

Assessment, 32)

[1992Kai] Kainuma, R., Ishida, K., Nishizawa, T., “Thermoelastic Martensite and Shape Memory

Effect in B2 Base Ni-Al-Fe Alloy with Enhanced Ductility”, Metall. Trans. A, 23A(4),

1147-1153 (1992) (Mechan. Prop., Experimental, 24)


B2->7R Martensitic Transformation in a Ni-37.0 at.%Al Alloy”, Mater. Trans., JIM, 33(3),


[1993Kat] Kattner, U.R. and Burton, B.P., “Al-Fe (Aluminum-Iron)“, in “Phase Diagrams of Binary

Iron Alloys”, Okamoto, H. (Ed), ASM International, Materials Park, OH 44073-0002, 12-28


339


MSIT®

Al–Fe–Ni

[1993Kha] Khadkikar, P.S., Locci, I.E., Vedula, K., Michal, G.M., “Transformation to Ni5Al3 in a

63.0 at.% Ni-Al Alloy”, Metall. Trans. A, 24A(1), 83-94 (1993) (Equi. Diagram, Crys.


[1993Pov] Povarova, K.B., Filin, S.A., Maslenkov, S.B., “Phase Equilibria in the Ni-Al-Me (Me = Co,

Fe, Mn, Cu) Systems in Vicinity of -Phase at 900 and 1100°C”, Russ. Metall. (Engl.

Transl.), (1), 156-169 (1993), translated from : Izv. Akad. Nauk SSSR, Met., (1), 191-205

(1993). (Crys. Structure, Experimental, Equi. Diagram, 19)

[1993Tan] Tanaka, M., Tsuda, K., Terauchi, M., Fujiwara, A., Tsai, A., Inoue, A., “Electron

Diffraction and Electron Microscope Study on Decagonal Qusicrystals on Al-Ni-Fe

Alloys”, J. Non-Cryst. Solids, 153-154, 98-102 (1993) (Crys. Structure, Experimental, 7)

[1993Zub] Zubkov, A.A., Emel’yanenko, L.P., Ul’yanov, V.I., “Enthalpy of Formation of -Phase in

Iron-Alloyed Nickel-Aluminum System”, Russ. Metall. (Engl. Transl.), (3), 35-38 (1993),

translated from Izv. Akad. Nauk SSSR, Met., (3), 39-42 (1993) (Experimental, Thermodyn.,

17)

[1994Bur] Burkhardt, U., Grin, J., Ellner, M., Peters, K., Structure Refinement of the Iron-Aluminum

Phase with the Approximate Composition F2Al5”, Acta Crystallogr., Sect. B: Struct.


[1994Dun] Duncan, A.J., Kaufman, M.J., Liu, C.T., Miller, M.K., “Site Occupation of Iron in

Intermetallic NiAl”, Appl. Surface Sci., 76-77(1-4), 155-159 (1994) (Crys. Structure,

Experimental, 17)

[1994Gho] Ghosh, G., Olson, G.B., Kinkus, T.J., Fine, M.E., “Phase Separation in Fe-Ni-Al and

Fe-Ni-Al-Cr Alloys”, “Solid Solid Phas. Transform.” Proc. Int. Conf. Solid-Solid Phase

Transform. Inorg. Mater., 359-364 (1994) (Calculation, Thermodyn., Experimental, #, 13)

[1994Gri] Grin, J., Burkhardt, U., Ellner, M., Peters, K., “Refinement of the F4Al13 Structure and its

Relationship to Quasihomological Homeotypical Structures”, Z. Kristallogr., 209, 479-487


[1994Gru] Grushko, B., Urban, K., “A Comparative Study of Decagonal Quasicrystalline Phase”,

Philos. Mag. B, 70B(5), 1063-1075 (1994) (Crys. Structure, Experimental, 26)

[1994Jia] Jia, C.C., Ishida, K., Nishizawa, T., “Partition of Alloying Elements Between (A1), `

(L12) and (B2) Phases in Ni-Al Base Systems”, Metall. Mater. Trans. A, 25A, 473-485

(1994) (Crys. Structure, Experimental, Equi. Diagram, #, 25)

[1994Lem] Lemmerz, U., Grushko, B., Freiburg, C., Jansen, M., “Study of Decagonal Quasicrystalline

Phase Formation in the Al-Ni-Fe Alloy System”, Philos. Mag. Lett., 69(3), 141-146 (1994)


[1994Rag] Raghavan, V., “The Al-Fe-Ni System”, J. Phase Equilib., 15(4), 411-413 (1994) (Equi.


[1995Ell] Ellner, M., “Polymorphic Phase Transformation of Fe4Al13 Causing Multiple Twinning

with Decagonal Pseudosymmetry”, Acta Crystallogr., Sect. B: Struct. Crystallogr. Crys.

Chem., B51, 31-36 (1995) (Crys. Structure, Experimental, 28)

[1995Gaf] Gaffet, E., “Structural Investigation of Mechanicall Alloyed (NiAl)1-x(M)x (M = Fe, Zr)

Nanocrystalline and Amorphous Phases”, NanoStruct. Mater., 5(4), 393-409 (1995) (Crys.

Structure, Mechan. Prop., Experimental, 58)

[1995Guh] Guha, S., Baker, I., Munroe, P.R., “The Microstructures of Multiphase Ni-20Al-30Fe and

its Constituent Phases”, Mater. Charact., 34, 181-188 (1995) (Experimental, Equi.

Diagram, #, 11)

[1995Wue] Wuerschum, R., Troev, T., Grushko, B., “Structural Free Volumes and Systematics of

Positron Lifetimes in Quasicrystalline Decagonal and Adjacent Crystalline Phases of

Al-Ni-Co, Al-Cu-Co, and Al-Ni-Fe Alloys”, Phys. Rev. B, 52B(9), 6411-6416 (1995) (Crys.

Structure, Experimental, Equi. Diagram, 37)

[1996Gru1] Grushko, B., Lemmerz, U., Fischer, K., Freiburg, C., “The Low-Temperature Instability of

the Decagonal Phase in Al-Fe-Ni”, Phys. Status Solidi A, 155A, 17-30 (1996)


340


MSIT®

Al–Fe–Ni

[1996Gru2] Grushko, B., Holland-Moritz, D., “High-Ni Al-Ni-Co Decagonal Phase”, Scr. Mater.,

35(10), 1141-1146 (1996) (Experimental, Crys. Structure, 19)


Ni1+xAl1-x”, Acta Crystallogr., Sect. A : Found. Crystallogr., A52, C319 (1996) (Crys.


[1996Vik] Viklund, P., Häußermann, U., Lidin, S., “NiAl3: a Structure Type of its Own?”, Acta

Crystallogr., Sect. A: Found. Crystallogr., A52, C321 (1996) (Crys. Structure,


[1996Yam] Yamamoto, A., “Crystallography of Quasiperiodic Crystals”, Acta Crystallogr., Sect. A:

Found. Crystallogr., A52, 509-560 (1996) (Calculation, Crys. Structure, Review, 211)

[1996Zho] Zhongtao, Z., Yinyan, L., Qihua, Z., Zhengxin, L., Ruzhang, M., “Mössbauer Study of

Precipitates in Rapidly Solidified Al-Fe-Ni Alloys”, Z. Metallkd., 87(1), 40-44 (1996)

(Experimental, Moessbauer, Phase Configurations, 12)

[1997And] Anderson, I.M., “Alchemi Study of Site Distributions of 3d-Transition Metals in

B2-Ordered Iron Aluminides”, Acta Mater., 45(9), 3897-3909 (1997) (Calculation, Crys.




[1997Kai] Kainuma, R., Ikenoya, H., Ohnuma, I., Ishida, K., “Pseudo-Interface Formation and

Diffusion Behaviour in the B2 Phase Region of NiAl-Base Diffusion Couples”, Def. Diffus.

Forum, 143-147, 425-430 (1997) (Crys. Structure, Experimental, Equi. Diagram, Phys.

Prop., 10)

[1997Pik] Pike, L.M., Chang, Y.A., Liu, C.T., “Solid-Solution Hardening and Softering by Fe

Additions to NiAl”, Intermetallics, 5, 601-608 (1997) (Crys. Structure, Mechan. Prop.,

Experimental, 18)

[1997Poh] Pohla, C., Ryder, P.L., “Crystalline and Quasicrystalline Phases in Rapidly Solidified Al-Ni

Alloys”, Acta Mater., 45, 2155-2166 (1997) (Crys. Structure, Experimental, 48)

[1997Pot] Potapov, P.L., Song, S.Y., Udovenko, V.A., Prokoshkin, S.D., “X-ray Study of Phase

Transformations in Martensitic Ni-Al Alloys”, Metall. Mater. Trans. A, 28A, 1133-1142


[1997Sai] Saiton, K., Tsuda, K., Tanaka, M., “Structural Models for Decagonal Quasicrystals with

Pentagonal Atom-Cluster Columns”, Philos. Mag. A, 76A(1), 135-150 (1997) (Crys.


[1997Yam] Yamamoto, A., Weber, S., “Superstructure and Color Symmetry in Quasicrystals”, Phys.

Rev. Lett., 79(5), 861-864 (1997) (Crys. Structure, Experimental, 20)



Thermodyn., 55)


Al-Fe Phases Forming in Direct-chill (DC)-cast Aluminium Alloy Ingots”, Calphad, 22,

147-155 (1998) (Calculation, Equi. Diagram, #, 20)

[1998Gom] Goman’kov, V.I., Tret’yakova, S.M., Monastyrskaya, E.V., Fykin, L.E., “Structural

Diagrams of Quasi Binary Alloys Ni3Fe-Ni3Al, Ni3Mn-Ni3Al, and Ni3Mn-Ni3Ga”, Russ.

Metall., (6), 125-131 (1998), translated from Izv. Akad. Nauk SSSR, Met., (6), 104-108

(1998) (Experimental, Equi. Diagram, #, 15)

[1998Ko] Ko, H.-S., Park, H.-S., Hong, K.-T., Lee, K.-S., Kaufman, M.J., “The Effects of the Point

Defects on Precipitation in NiAlFe Alloys”, Scr. Mater., 39(9), 1267-1272 (1998)




57B(2), 862-869 (1998) (Thermodyn., Theory, Calculation, 43)

341


MSIT®

Al–Fe–Ni

[1998Sun] Sun, Z.Q., Yang, W.Y., Shen, L.Z., Huang, Y.D., Zhang, B.S., Yang, J.L., “Neutron

Diffraction Study on Site Occupation of Substitution Elements at Sub Lattices in Fe-Al

Intermetallics”, Mater. Sci. Eng. A, 258A, 69-74 (1998) (Crys. Structure, Experimental,

Magn. Prop., Mechan. Prop., 19)


“Experimental Study of Thermal Expansion and Phase Transformations in Iron-rich Fe-Al

Alloys”,Calphad, 23(1), 69-84 (1999) (Equi. Diagram, Experimental, 15)

[1999Dyb] Dybkov, V.I., “Physicochemical and Structural Investigations of Materials. Phase

Formation at an Interface Beetween Aluminium and an Iron-Nickel Alloy”, Powder Metall.

Met. Ceram., 38(11-12), 590-596 (1999) (Experimental, Mechan. Prop., Equi.

Diagram, #, 10)

[1999Hel] Helander, T., Agren, J., “Diffusion in the B2-B.C.C. Phase of the Al-Fe-Ni System -

Application of a Phenomenological Model”, Acta Mater., 47(11), 3291-3300 (1999)

(Assessment, Calculation, Thermodyn., Diffusion, #, 20)

[1999Hol] Holland-Moritz, D., Lu, I.-R., Wilde, G., Schroers, J., Grushko, B., “Melting Entropy of

Al-Based Quasicrystals”, J. Non-Cryst. Solids, 250-252, 829-832 (1999) (Experimental,

Thermodyn., 17)




[2000Ama] Amancherla, S., Banerjee, R., Banerjee, S., Fraser, H. L., “Ordering in Ternary B2 Alloys”,

Inter. J. Ref. Met. Hard Mater., 18(4-5), 245-252 (2000) (Calculation, Experimental, Magn.

Prop., Equi. Diagram, Thermodyn., 23)

[2000Dro] Drobek, T., Heckl, W.M., “Scanning Probe Microscopy Studies of the Surface of Decagonal

Quasicrystals in Ambient Conditions”, Mater. Sci. Eng. A, 294A-296A, 878-881 (2000)


[2000Dyb] Dybkov, V.I., “Interaction of Iron-Nickel Alloys with Liquid Aluminium Part II. Formation

of Intermetallics”, J. Mater. Sci., 35, 1729-1736 (2000) (Experimental, Equi. Diagram, #, 9)

[2000Fre] Frey, F., “Disorder Diffuse Scattering of Decagonal Quasicrystals”, Mater. Sci. Eng. A,

294A-296A, 178-185 (2000) (Crys. Structure, Experimental, 15)

[2000Zei] Zeifert, B.H., Salmones, J., Hernandez, J.A., Reynoso, R., Nava, N., Reguera, E.,

Cabanas-Moreno, J.G., Aguilar-Rios, G., “X-Ray Diffraction and Moessbauer

Characterization of Raney Fe-Ni Catalysts”, J. Radioanal. Nucl. Chem., 245(3), 637-639

(2000) (Crys. Structure, Moessbauer, 10)

[2001Bre] Breuer, J., Gruen, A., Sommer, F., Mittemeijer, E.J., “Enthalpy of Formation of B2-Fe1-xAlxand B2-(Ni,Fe)1-xAlx”, Metall. Mater. Trans. B, 32B, 913-918 (2001) (Experimental,

Thermodyn., 18)

[2001Hir] Hiraga, K., Ohsuna, T, “The Structure of an Al-Ni-Fe Decagonal Quasicrystal Studied by

High-Angle Annular Detector Dark-Field Transmission Electron Microscopy”, Mater.

Trans., JIM, 42, 894-896 (2001) (Crys. Structure, Experimental, Equi. Diagram, 31)


BCC Phases in the Fe-rich Portion of the Fe-Al System”, Intermetallics, 9, 755-761 (2001)

(Equi. Diagram, Experimental, Mechan. Prop., 18)

[2001Qia] Qiang, J.-B., Wang, D.-H., Bao, C.-M., Wang, Y.-M., Xu, W.-P., Song, M.-L., Dong, Ch.,

“Formation Rule for Al-Based Ternary Quasi-Crystals: Example of Al-Ni-Fe Decagonal

Phase”, J. Mater. Res., 16(9), 2653-2660 (2001) (Crys. Structure, Experimental, Equi.

Diagram, 31)

[2001Sav] Savin, O.V., Stepanova, N.N., Akshentsev, Yu.N., Rodionov, D.P., “Ordering Kinetics in

Ternary Ni3Al-X Alloys”, Scr. Mater., 45(8), 883-888 (2001) (Crys. Structure, Electr.

Prop., Experimental, Kinetics, 18)

[2001Sur] Suryanarayana, C., “Mechanical Alloying and Milling”, Prog. Mater. Sci., 46(1-2), 1-184

(2001) (Crys. Structure, Experimental, Kinetics, Equi. Diagram, Review, Thermodyn., 932)

342


MSIT®

Al–Fe–Ni

[2001Tan] Tan, Y., Shinoda, T., Mishima, Y., Suzuki, T., “Stoichiometry Splitting of Beta Phase in

Ni-Al-Mn, Ni-Al-Co and Ni-Al-Fe Ternary Systems”, Mater. Trans., JIM, 42(3), 464-470

(2001) (Crys. Structure, Experimental, Mechan. Prop., Equi. Diagram, 16)

[2002Alb] Albiter, A., Bedolla, E., Perez, R., “Microstructure Characterization of the NiAl

Intermetallic Compound with Fe, Ga and Mo Additions Obtained by Mechanical Alloying”,

Mater. Sci. Eng. A, 328A, 80-86 (2002) (Crys. Structure, Mechan. Prop., Experimental, 14)

[2002Ban] BanerJee, R., Amancherla, S., Banerjee, S., Fraser, H.L., “Modeling of Site Occupancies in

B2 FeAl And NiAl Alloys with Ternary Additions”, Acta Mater., 50, 633-641 (2002)

(Calculation, Crys. Structure, Experimental, Equi. Diagram, 21)

[2002Bit] Bitterlich, H., Loeser, W., Schultz, L., “Reassessment of Al-Ni and Ni-Fe-Al Solidus

Temperatures”, J. Phase Equilib., 23(4), 301-304 (2002) (Experimental, Equi. Diagram, 18)

[2002Boz] Bozzolo, G. H., Khalil, J., Noebe, R. D., “Modeling of the Site Preference in Ternary

B2-Ordered Ni-Al-Fe Alloys”, Comput. Mater. Sci., 24(4), 457-480 (2002) (Calculation,


[2002He] He, X., Han, J., Zhang, X., “Kinetic Parametres of the Thermal Explosion Reaction of

Ni-Al-Fe System”, Key Eng. Mater., 217, 51-54 (2002) (Experimental, Kinetics, 7)

[2002Hir] Hiraga, K., “The Structure of Quasicrystals Studied by Atomic-Scale Observations of

Transmission Electron Microscopy”, Adv. Imag. Electr. Phys., 122, 1-86 (2002) (Review,


[2002Joa] Joardar, J., Pabi, S.K., Fecht, H.-J., Murty, B.C., “Stability of Nanocrystalline Disordered

NiAl Synthesized by Mechanical Alloying”, Philos. Mag. Lett., 82(9), 469-475 (2002)

(Experimental, Kinetics, 16)

[2002Kim] Kim, S.H., Kim, M.C., Lee, J.H., Oh, M.H., Wee, D.M., “Microstructure Control in

Two-Phase (B2 + L12) Ni-Al-Fe Alloys by Addition of Carbon”, Mater. Sci. Eng. A,

329A-331A, 668-674 (2002) (Experimental, Equi. Diagram, Mechan. Prop., 20)

[2002Liu] Liu, C.T., Fu, C.L., Pike, L.M., Easton, D.S., “Magnetism-Induced Solid Solution Effects

in Intermetallic”, Acta Mater., 50, 3203-3210 (2002) (Calculation, Crys. Structure,

Experimental, Mechan. Prop., 21)

[2002Mun] Munroe, P.R., George, M., Baker, I., Kennedy, F.E., “Microstructure, Mechanical

Properties and Wear of Ni-Al-Fe Alloys”, Mater. Sci. Eng. A, 325A, 1-8 (2002)

(Experimental, Mechan. Prop., Equi. Diagram, 35)

[2002Pik] Pike, L.M., Anderson, I.M., Liu, C.T., Chang, Y.A., “Site Occupancies, Point Defect

Concentrations, and Solid Solution Hardening in B2 (Ni, Fe)Al”, Acta Mater., 50(15),

3859-3879 (2002) (Calculation, Crys. Structure, Experimental, Mechan. Prop., 38)

[2002Yok] Yokosawa, T., Saitoh, K., Tanaka, M., Tsai, A.P., “Structural Variations in Local Areas of

an Al70Ni15Fe15 Decagonal Quasicrystal and the Interpretation by the 1-nm Column-Pair

Scheme”, J. Alloys Compd., 342, 169-173 (2002) (Crys. Structure, Experimental, 10)

[2003Doe] Doeblinger, M., Wittmann, R., Grushko, B., “Initial Stages of the Decomposition of the

Decagonal Phase in the System Al-Ni-Fe”, J. Alloys Compd., 360, 162-167 (2003) (Crys.




Stuttgart; to be published, (2003) (Equi. Diagram, Assessment, 58)



International Services GmbH, Stuttgart; to be published, (2003) (Equi. Diagram, Review,

164)

343


MSIT®

Al–Fe–Ni

Table 1: Recent Investigations of the Al-Fe-Ni System

Reference Experimental Technique Temperature/ Composition/ Phase Range

Studied

[1989Tsa] New decagonal phases prepared by liquid

quenching

9 to 21 at.% Fe, 9 to 16 at.% Ni,

[1990Ell] Crystal structure FeNiAl5

[1991Har] Texture measurements, cyclic deformation Fe60Al40 and Fe20Ni50Al30

[1991Kos] Fracture toughness, grain size effects,

strain-stress measurements

Fe20Ni45Al35

[1991Pat] Transition in Burgers’ vector (FexNi1-x)60Al40 (0 x 1)

[1991Mas] Crystal structure, Hardness, Young’s

modulus

FexNi50Al50-x (0 x 10)

[1991Yav] Magnetization of ' alloys obtained by cold

working or melt spinning

10 to 13 at.% Fe, 16 to 17.4 at.% Al

[1992Kai] Shape memory effect, stress-strain curves,

Ms temperature

Fe57Ni25Al18, 1000-1300°C

[1993Pov] Phase equilibria, Electron microprobe

analysis, X-ray analysis

> 50 at.% Al, 900-1100°C

[1993Zub] Enthalpies of formation, enthalpies of

dilution in liquid Al

0 to 10 at.% Fe, 40 to 50 at.% Ni, 800°C

[1994Dun] Crystal structure, atom probe field-ion

microscope

Fe0.3Ni50Al49.7 and Fe2.2Ni47.8Al50

[1994Gho] Spinodal decomposition by transmission

electron microscopy, field-ion microscopy

Fe-23.3 mass% Ni-9.4 mass% Al, water

quenched from 1300°C

[1994Jia] Equilibria - ' and - ', diffusion couples,

electron microprobe analysis

< 6 mass% Fe, < 22 mass% Al,

1100-1300°C

[1994Lem] Stability of the decagonal phase 23 to 24.6 at.% Ni, 4.3 to 5.3 at.% Fe,

800 to 940°C ( 3 phase)

[1995Gaf] Mechanical alloying, crystal structure NiAl-Fe join, room temperature

[1995Wue] Structural vacancies, positron lifetimes

measurements

< 25 at.% Fe, 20-25 at.% Ni

[1996Gru1] Decagonal phase, Stability Fe5Ni24Al71, inductive melting then

annealing 340h at 880°C ( 3 phase)

[1996Zho] Crystal structure, Mössbauer FexNi2-xAl9 (1 x 1.6) ( 1 phase)

[1997Pik] Lattice parameters, bulk density, hardness

measurements

0 to 12 at.% Fe, 40 to 52 at.% Al

water quenched from 1000°C

[1997Sai] Decagonal phases, Crystal Structure,

Convergent-beam electron diffraction

Fe30-xNixAl70 (10 x 17) (D1 phase)

[1998Gom] Neutron diffraction, Order-disorder

equilibrium

FeNi3-Ni3Al join, 500-1000°C

[1998Sun] Crystal structure, neutron diffraction study Fe72Ni3Al25

[1999Dyb] Interface Al-intermetallic layers by electron

probe microanalysis

Reaction between liquid Al and Fe-Ni alloys

at 700°C

344


MSIT®

Al–Fe–Ni

[1999Hol] DTA investigation, Melting point and

enthalpy of fusion of quasicrystals

Fe5Ni24Al71 quenched from the melt then

annealed 300h at 880°C ( 3 phase)

[2000Dro] Scanning electron microscopy, atomic

force microscopy

Fe5Ni23.5Al71.5 quenched from the melt,

then annealed 51 h at 900°C ( 3 phase)

[2000Dyb] Liquidus surfaces, phase field in the solid

state

> 60 mass% Al, < 800°C

[2000Fre] Diffuse scattering of X-rays and neutrons in

decagonal phase

Fe5Ni23.5Al71.5 ( 3 phase)

[2001Bre] Enthalpies measurements, differential

solution calorimetry

FexAl1-x and FexNiyAlz (x = 0-0.6, y =

0-0.55, z = 0.35-0.50), 800°C

[2001Hir] Crystal structure, atomic scale observation

by scanning transmission electron

microscopy

4.7 at.% Fe, 23.7 at.% Ni,

[2001Sav] Crystal structure, Order-disorder transition,

electrical resistivity

Fe8Ni71Al21, 1000-1850°C

[2001Tan] Crystal parameters and hardness measured

in the domain

< 60 at.% Al, powder homogenized 1h at

850°C

[2002Bit] Solidus determination, high temperature

differential thermal analysis

NixAl100-x (45 < x < 47) and FeyNi50-yAl50

(0 < y < 50), 1259-1681°C

[2002Joa] Nanostructured alloy, kinetics of reordering Fe20Ni40Al40, 300-600°C

[2002Mun] Microstructure, tensile and compressive

strength, hardness and wear tests

Fe-NiAl join (0 to 44 at.% Fe), 500-900°C

[2002Pik] Hardness, Vacancy concentration, Atomic

site occupancy in the domain, ALCHEMI

technique

40 to 52 at.% Al, samples quenched from

700 and 1000°C

[2001Qia] Decagonal phases, crystal structures Fe14.5Ni13Al72.5 and Fe12Ni17.5Al70.5 (D1

and D2 phases)

[2002Yok] Crystal structure of decagonal phase,

high-angle annular dark-field scanning

transmission electron microscope

Fe15Ni15Al70, prepared with a single roller

melt-spinning apparatus (D1 phase)

Reference Experimental Technique Temperature/ Composition/ Phase Range

Studied

345


MSIT®

Al–Fe–Ni


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 dissolves 0.03 at.% Fe at 652°C and

0.025 at.% Ni at 640°C [L-B]

, Fe1-x-yNixAly

( Fe)

1394-912

(Ni)

< 1455

cF4

Fm3m

Cu

a = 352.40

a = 364.67

at x = 0, 0 y 0.013

at y = 0, 0 x 1

at x + y = 1, 0 y 0.02

at x = 0, y = 0 and 915°C [V-C2, Mas2]

at x = 1, y = 0 and 20°C [V-C2, Mas2]

(at y = 0 and 20°C a vs x is not linear and

has a maximum for x 0.4)

, Fe1-x-yNixAly

( Fe)

1538-1394

( Fe)

<912

cI2

Fm3m

W

a = 286.65

a = 293.22

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12

at x = 0, 0 y 0.045

at y = 0, 0 x 0.055 ( Fe)

at y = 0, 0 x 0.035 ( Fe)

at x = 0, y = 0 and 25°C [V-C2]

at x = 0, y = 0 and 1394°C [V-C2]

at x = 0, 0 y 0.019, 20°C [1958Tay]

at x = 0, 0 y 0.019, 20°C [1961Lih]

at x = 0, 0 y 0.010, 20°C [1999Dub]

, (Fe1-xNix)1+yAl1-y

FeAl

< 1310

NiAl

< 1638

cP2

Pm3m

CsCl a = 290.90

a = 290.17

a = 289.77

a = 289.66

a = 289.53

a = 288.7

a = 288.0

at x = 0, 0.10 y 0.54 (FeAl)

at x = 1, 0.16 y 0.38 (NiAl)

at x = 0, y = 0 (50 at.%Al)

at x = 0, y = 0.124 (43.8 at.%Al)

at x = 0, y = 0.182 (40.9 at.%Al)

at x = 0, y = 0.234 (38.3 at.%Al)

x = 0, y = 0.276 (36.2 at.%Al) [1958Tay]

at x = 1, y = 0 (50 at.% Al)

at x = 1, y = 0.08 (46 at.%Al) [1996Pau]

(see also Figs. 1a and 1b)

Fe4Al13

< 1157

mC102

C2/m

Fe4Al13

a = 1549.2(2)

b = 807.8(2)

c = 1247.1(1)

= 107.69(1)°

a = 1543.7

b = 810.9

c = 1243.0

= 107,66°

74.5-76.6 at.% Al at 0 at.% Ni [2003Pis]

at 76.0 at.% Al [1994Gri]

[1982Kha] at 10 at.% Ni

dissolves

12 at.% Ni at 800°C [1996Gru1]

10 at.% Ni at 950°C [1982Kha]

6 at.% Ni at 1050°C [1982Kha]

Fe2Al5< 1169

oC24

Cmcm

Fe2Al5 a = 765.59

b = 641.54

c = 421.84

70-73 at.% Al at 0 at.% Ni [1993Kat]

at 71.5 at.% Al [1994Bur]

dissolves 2 at.% Ni at 1050°C [1982Kha,

1993Pov]

346


MSIT®

Al–Fe–Ni

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

66-66.9 at.% Al at 0 at.% Ni [1993Kat]

at 66.9 at.% Al [1973Cor]

dissolves 2.5 at.% Ni at 1050°C

[1982Kha]

1102 - 1232

cI16? a = 578.0 at 61 at.% Al [1933Osa]

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.98

a = 579.30 to 578.86

a = 579.98

a = 579.30 to 578.92

~24 - ~37 at.% Al in Al-Fe [2001Ike]

Extends less than 10 at.% Ni into the

ternary [1940Bra2]

at 24.35 at.% Al [1998Sun]

23.1-35.0 at.% Al [1958Tay]

at 25 at.% Al and 3 at.% Ni

neutron diffr. [1998Sun]

24.7-31.7 at.% Al [1961Lih]

O-Fe4Al13 oC~50

Cmmm

Fe4Al13

a = 2377.1

b = 775.10

c = 403.36

Metastable (?)

Described by the authors in terms of the

Bmmm group. It was suggested that

multiple twinning of this structure

exhibits decagonal pseudo-symmetry

[1995Ell]

Fe2Al9 mP22

P21/a

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

Metastable [1977Sim]

FeAl6 oC28

Cmc21

MnAl6

a = 646.4

b = 744.0

c = 877.9

Metastable [1965Wal]

FeAl4+x t** a = 884

c = 2160


[1998Ali]

I(Al-Fe) Icosahedral, Metastable [1984She]

',(Ni3Al)

< 1372

(FeNi3)

< 517

cP4

Pm3m

AuCu3

a = 358.9

a = 356.32

a = 357.92

a = 355.25

73 to 76 at.% Ni at 0 at.% Fe [Mas2]

dissolves up to 15 at.% Fe [1986Bra,

1993Pov]

63-85 at.% Ni at 0 at.% Al and 350°C

[1982Kub]

complete solid solution with FeNi3 at

T<500°C [1987Mas]

at 75 at.% Ni, 0 at.% Fe [1993Kha]

disordered [1998Rav]

ordered [1998Rav]

at 75 at.% Ni, 0 at.% Al, 20°C [L-B]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

347


MSIT®

Al–Fe–Ni

Ni3Al4< 580

cI112

Ia3d

Ni3Ga4

a = 1140.8 [1989Ell, V-C]

Ni2Al3< 1138

hP5

P3m1

Ni2Al3 a = 402.8

c = 489.1

36.8 to 40.5 at.% Ni at 0at.% Fe [Mas2]

[1997Bou, V-C]

dissolves 2 at.% Fe at 20°C

and 10 at.% Fe at 1050°C [1982Kha]

NiAl3< 856

oP16

Pnma

NiAl3

a = 661.3

b = 736.7

c = 481.1

[1996Vik]

dissolves 4 at.% Fe [1982Kha]

Ni2Al hP3

P3m1

CdI2

a = 407

b = 499

Metastable [1993Kha]

NixAl1-x martensite tP4

P4/mmm

AuCu

m**

a = 383.0

c = 320.5

a = 379.5

c = 325.6

a = 375.1

c = 330.7

a = 379.9 to 380.4

c = 322.6 to 323.3

a = 371.7 to 376.8

c = 335.3 to 339.9

a = 418

b = 271

c = 1448

= 93.4°

Metastable 0.60 < x < 0.68

[1993Kha]

at 62.5 at.% Ni [1991Kim]

at 66.0 at.% Ni [1991Kim]

at 64 at.% Ni [1997Pot]

at 65 at.% Ni [1997Pot]

[1992Mur]

Ni2Al9 mP22

P21/a

Co2Al9

a = 868.5

b = 623.2

c = 618.5

= 96.50°

Metastable [1997Poh]

FeNi tP4

P4/mmm

CuAu

a = 358.23

c = 358.22

Metastable(?) [L-B]

Fe3Ni c** a = 357.5 Metastable(?) [L-B]

D1, Fe14.5Ni13Al72.5 P10m2 aD = 713.4

cD = 818

Metastable in the ternary at

Al70Ni10-17Fe20-13 [1997Sai, 2001Qia]

Metastable in the Al-Fe binary [1986Fun]

D2,

Fe9.83Ni19.34Al70.83

P10/mmm

or P105mc

aD = 712

cD = 409

Metastable in the ternary at

Al70Ni17-20Fe13-10 [1997Sai, 2001Qia]

* 1, FeNiAl9forms between 850

and 750°C

mP22

P21/a

Co2Al9

a = 859.8

b = 627.1

c = 620.7

= 94.66°

at Al82Ni11.7Fe6.3 [1982Kha]

7.3 to 12.7 at.% Ni, 10.4 to 4.7at.% Fe at

620°C [1943Sch], confirmed by

[1999Dyb, 2000Dyb]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

348


MSIT®

Al–Fe–Ni


Table 4: Thermodynamic Data

* 2, FeNi3Al10

~850 < T < 1110

hP28

P63/mmc

Co2Al5

a = 770.3

c = 766.8

[1990Ell] at FeNiAl5Al70-72.5Fe18-24.5Ni10.5-4.5 at 1050°C

[1981Kha]

* 3, Fe5Ni24Al71

847 < T < 930

aD 378

cD 411

aD = 373.3

cD = 407.3

Decagonal phase with small solubility

range [1994Lem, 1996Gru].

Diameter of the decagonal section ~3200

pm [2001Hir]

Metastable in Al-Ni binary system

at 24-30 at.% Ni [1997Poh]


Al Fe Ni

L + ' + ~1365 U1 L 23 4 73

3 Fe4Al13 + Ni2Al3 +

NiAl3

847 E1 3

Fe4Al13

Ni2Al3NiAl3

~71

~75

~61

75

~5

~15

~2

~2

~24

~10

~37

~23

L + Fe4Al13+ NiAl3 1 809 P L 87.06 2.11 10.83

L + Fe4Al13 (Al) + ( 1) 650 U2 L 98.42 0.795 0.786

L (Al) + NiAl3 + 1 638 E2 L 96.72 0.105 3.175

Reaction or

Transformation

Temperature

[°C]

Quantity per Reaction

[J, mole, K]

Comments

xFe( ) + yNi( ) + zAl(liq)

FexNiyAlz( )

800 fH = –42780 ± 280

fH = –48730 ± 220

fH = –54420 ± 240

fH = –60860 ± 230

fH = –65740 ± 270

fH = –39870 ± 230

fH = –45740 ± 050

fH = –51920 ± 140

fH = –58070 ± 110

fH = –63110 ± 060

fH = –65380 ± 100

fH = –30920 ± 240

fH = –35460 ± 310

fH = –51520 ± 290

x = 0.42, y = 0.08, z = 0.50

x = 0.34, y = 0.16, z = 0.50

x = 0.25, y = 0.25, z = 0.50

x = 0.16, y = 0.34, z = 0.50

x = 0.08, y = 0.42, z = 0.50

x = 0.46, y = 0.09, z = 0.45

x = 0.37, y = 0.18, z = 0.45

x = 0.275, y = 0.275, z = 0.45

x = 0.18, y = 0.37, z = 0.45

x = 0.09, y = 0.46, z = 0.45

x = 0.0, y = 0.55, z = 0.45

x = 0.59, y = 0.06, z = 0.35

x = 0.53, y = 0.12, z = 0.35

x = 0.145, y = 0.505, z = 0.35

Al solution calorimetry [2001Bre]

xFe( ) + yNi( ) + zAl(liq)

FexNiyAlz( )

25 fH = –58000 ± 3000

fH = –56800 ± 2300

fH = –54100 ± 2100

fH = –48400 ± 2400

x = 0.0, y = 0.50, z = 0.50

x = 0.02, y = 0.50, z = 0.48

x = 0.05, y = 0.50, z = 0.45

x = 0.10, y = 0.40, z = 0.50

Al solution calorimetry [1993Zub]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

349


MSIT®

Al–Fe–Ni

291

286

287

288

289

290

0 6010 20 30 40 50

FeAl

NiAl

50 at.% Al

40 at.% Al

Latticeparameter(pm)

Ni, at.%

Fig. 1a: Al-Fe-Ni.

Lattice parameter of

-phase, (Fe,Ni)Al as

a function of

composition at

constant Al contents

[2002Pik]

291

286

287

288

289

290

40 5242 44 46 48 50

Latticeparameter(pm)

Al, at.%

0

1/4

1

4

�

Fig. 1b: Al-Fe-Ni.

Lattice parameter of

-phase, (Fe,Ni)Al as

a function of

composition at

constant Fe:Ni ratio

(0 - for NiAl, - for

FeAl) [2002Pik]

350


MSIT®

Al–Fe–Ni

Fig

. 2:

Al-

Fe-

Ni.

Par

tial

rea

ctio

n s

chem

e

Al-

Fe

Fe-

Ni

Al-

Ni

Al-

Fe-

Ni

l +

αδ

γ1

513

p1

l +

βε

12

32

p3

L +

γ´

γ +

βca

.13

65

U1

l +

γγ´

13

72

p2

Lβ

+ γ

ca.1

360

e 2

lε

+ F

e 2A

l 5

11

65

e 3

l +

Fe 2

Al 5

Fe 4

Al 13

11

60

p4

l +

Fe 2

Al 5

FeA

l 2

11

56

p5

εβ

+ F

eAl 2

11

02

e 4

l (

Al)

+ F

e 4A

l 13

65

5e 5

lγ´

+ β

13

69

e 1

l +

β N

i 2A

l 3

11

38

p6

l +

Ni 2

Al 3

NiA

l 3

85

6p7

Ni 3

Al

+ β

Ni 5

Al 3

72

3p8

β +

Ni 2

Al 3

Ni 3

Al 4

70

2p9

l (

Al)

+ N

iAl 3

64

4e 6

D1

Fe 4

Al 13+

Ni 2

Al 3

+N

iAl 3

84

7E1

L+

Fe 4

Al 13+

NiA

l 3τ 1

80

9P

L +

Fe 4

Al 13

(A

l) +

τ1

65

0U2

L (

Al)

+ N

iAl 3

+ τ1

63

8E2

γ +

γ´ +

β

L+

τ 1+

Fe 4

Al 13

L+

NiA

l 3+

τ 1

L+

(Al)

+τ 1

(Al)

+N

iAl 3

+τ 1

Fe 4

Al 13+

(Al)

+τ 1

Fe 4

Al 13+

NiA

l 3+

τ 1

L+

Fe 4

Al 13+

NiA

l 3

Fe 4

Al 13+

Ni 2

Al 3

+N

iAl 3

αδ

β

351


MSIT®

Al–Fe–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

γ

β

αδ

p1

p2

e1

U1

1400

1400

1400

1450

1450

1450

1500

155016001350

e2

order-disordertransformation

γ'

PFe4Al13NiAl3

(Al)

E2

e6e5

τ1

Fe 3.50Ni 0.00Al 96.50

Fe 0.00Ni 3.50Al 96.50


Axes: at.%

τ1

e6

U2

Fe4Al13

NiAl3

(Al)

E2

e5 656

654652

650

646

648

658

720

700

680

660

710

690

675

665655

Fig. 3a: Al-Fe-Ni.

Partial liquidus

surface [1949Bra,

1943Sch]

Fig. 3b: Al-Fe-Ni.

Partial liquidus

projection of

Al-corner

352


MSIT®

Al–Fe–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

L

L+β

β

γ

β+γγ´

β+γ´

γ´+γ

αδ

αδ+β+γαδ+γ

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

L

β

L+β

β+γ

γ

γ´β+γ´

γ´+γ

αδ

Fig. 5: Al-Fe-Ni.


1250°C [1949Bra].

The dotted

order-disorder line is

added

Fig. 4: Al-Fe-Ni.


1350°C [1949Bra].

Note that

order-disorder limit

between + is not

shown and must occur

inside the ternary

353


MSIT®

Al–Fe–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

β

β+γ

γ

β+γ´γ´

γ´+γ

αδ+β+γ

β+γ+γ´

αδ

αδ+γ

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

αδ

γ

αδ+β

αδ+γ+β

β+γ

β

γ+γ'

γ'β+γ'

β+γ+γ'

L

τ2

FeAl2

Fe4Al13Fe2Al5

Ni2Al3

Fig. 6: Al-Fe-Ni.


1150°C [1949Bra]

below 50 at.% Al

Fig. 7: Al-Fe-Ni.


1150°C [1949Bra]

below 50 at.% Al

354


MSIT®

Al–Fe–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

β

γ

αδβ+γαδ+β γ+γ'

γ'

β+γ'

Ni2Al3

L

Fe4Al13

Fe2Al5

FeAl2

τ2

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

β

αδ

αδ+β

β+γ

γ

γ´

γ+γ´

β+γ´

Ni2Al3

NiAl3Fe4Al13

τ2 τ3

L

Fig. 8: Al-Fe-Ni.


950°C, Al-rich

[1982Kho], Al-poor

[1951Bra, 1984Hao]

Fig. 9: Al-Fe-Ni.

Partial isothermal

section of Al-Fe-Ni at

850°C [1951Bra,

1996Gru1]

355


MSIT®

Al–Fe–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

αδαδ+β

β

β+γβ+γ+γ'

γ+γ'

γ'

β+γ'

L

NiAl3Fe4Al13

τ1

γ

?

10

20

10 20

80

90

Fe 30.00Ni 0.00Al 70.00

Fe 0.00Ni 30.00Al 70.00


Axes: at.%

Fe4Al13NiAl3

τ1

(Al)+τ1

Fe4Al13+NiAl3+τ1

(Al)+NiAl3 +τ

1

(Al)+Fe 4Al13+τ1

(Al)

Fig. 10: Al-Fe-Ni.

Partial isothermal

section at 750°C:

Al-rich [1982Kho],

Al-poor [1951Bra]

Fig. 11: Al-Fe-Ni.

Partial isothermal

section at 620°C

[1943Sch]

356


MSIT®

Al–Fe–Ni

20

40

60

80

20 40 60 80

20

40

60

80

Fe Ni


Axes: at.%

γ

γ+γ'

αδ

αδ+β

β+γ

Fe3Al

β

Ni2Al3

NiAl3

τ1

Fe2Al5

FeAl2 τ2

Fe4Al13

αδ+γ

90 80 70 60 50 40 30 20 100

250

500

750

1000

1250

1500

1750

2000

Fe 95.00Ni 0.00Al 5.00

Fe 0.00Ni 47.50Al 52.50Fe, at.%

Tem

pera

ture

, °C

L

β

αδ+β

L+αδ L+β

αδ

Fig. 12: Al-Fe-Ni.

Solid phases in alloys

cooled at 10 K/h

[1938Bra, 1940Bra1,

1940Bra2]

Fig. 13: Al-Fe-Ni.

Vertical section

parallel to Fe-NiAl,

Fe95Al5-Ni47.5Al52.5

[1951Bra]

357


MSIT®

Al–Fe–Ni

90 80 70 60 50 40 30 20 100

250

500

750

1000

1250

1500

1750

2000

Fe 97.50Ni 0.00Al 2.50

Fe 0.00Ni 48.75Al 51.25Fe, at.%

Tem

pera

ture

, °C

L

αδ β

L+αδ L+β

αδ+β

magnetic transition

90 80 70 60 50 40 30 20 10500

750

1000

1250

1500

1750

Fe Fe 0.00Ni 50.00Al 50.00Fe, at.%

Tem

pera

ture

, °C

β

L L+β

L+αδ+β

γ

L+αδ

αδ

γ+αδ

αδ

αδ+β

magnetic transition

Fig. 14: Al-Fe-Ni.

Vertical section

parallel to Fe-NiAl,

Fe97.5Al2.5 -

Ni48.75Al51.25

[1984Hao]

Fig. 15: Al-Fe-Ni.

Vertical section

Fe-NiAl [1951Bra,

1951Iva]

358


MSIT®

Al–Fe–Ni

20 100

250

500

750

1000

1250

1500

Fe 25.00Ni 75.00Al 0.00

Fe 0.00Ni 75.00Al 25.00Fe, at.%

Tem

pera

ture

, °C

γ'(ordered)

γ+γ'

γ(disordered)

L1430°C

Fig. 16: Al-Fe-Ni.

Vertical section

Ni3Al-FeNi3[1987Mas]. The tiny

L+ '+ around

1369°C close to

Ni3Al is not shown

359


MSIT®

Al–Fe–Si

Aluminium – Iron – Silicon

Gautam Ghosh

Literature Data

The system contains many technologically important alloys, such as foil and sheet products for food

packaging, capacitors, lithographic printing sheets, magnetic alloys for transformer. Furthermore, iron and

silicon, originating from bauxite ore and anode material, are present in nearly all industrial Al-alloys.

Metallurgical grade silicon also contains, among others, aluminum and iron as impurities. Due to these

reasons, there are numerous experimental studies on the phase equilibria of the ternary system, the results

of which have been reviewed from time to time [1934Fue, 1937Ser, 1943Mon, 1950Gme, 1952Han,

1959Phi, 1968Dri, 1981Riv, 1981Wat, 1985Riv, 1987Pri, 1988Ray, 1992Gho, 1992Zak, 1994Rag,

2002Rag]. The system is characterized by a large number of ternary phases, both stable and metastable, and

at least nineteen ternary invariant reactions during solidification which impart difficulties in establishing the

phase equilibria of the system. The difficulties are further augmented by the effects of metastability,

impurity elements, incomplete reactions, undercooling, and many solid-state reactions which are not well

understood.

Earlier works by [1923Dix, 1923Han, 1923Wet, 1924Fus, 1934Roe, 1941Pan] were mostly on the

observation of microstructures of dilute Al-alloys. [1951Ran] determined the phase boundaries of the

Al-corner at 475°C by diffusional anneal technique. Due to extensive results [1927Gwy, 1933Nis, 1936Jae,

1937Ura, 1943Phi, 1951Hol, 1951Now, 1967Mun, 1987Gri1, 1987Ste], the phase equilibria of the

Al-corner are well established.

The first comprehensive study of phase equilibria of the entire system was performed by [1940Tak]. They

used electrolytic iron, pure aluminium and metallic silicon (unspecified purity). Over 150 ternary alloys

were prepared using master alloys of selected compositions in an arc furnace, under hydrogen atmosphere

with NaCl as flux on the molten surface of the alloys, followed by cooling at a rate of 2 to 3 K per 5 to 10

sec. In some cases, in order to confirm and identify solid-state reactions, the cooling curves were

supplemented by heating runs. [1940Tak] employed metallography, thermal, X-ray, magnetic and

dilatometric analyses to establish the phase equilibria. They reported six ternary phases, and all form by

peritectic reactions. They also presented an extensive set of several vertical sections from 500°C up to the

liquidus temperature. Based on these results, [1981Riv] constructed a probable isothermal section at 600°C.

The Fe-corner was extensively studied by [1968Lih] up to 50 at.% Al and 35 at.% Si by DTA,

thermo-magnetometry, microhardness and X-ray diffraction. The phase equilibria involving ordered and

disordered phases in Fe-rich alloys were determined by [1982Miy] and [1986Miy] in the temperature range

of 450 to 700°C using transmission electron microscopy.

Recent investigations of the Al-corner, for alloys up to 14 at.% Si and 35 at.% Fe, are due to [1987Gri1] and

[1987Ste]. They used thermal analysis, X-ray diffraction and electron probe microanalysis to establish the

liquidus surface, and isothermal sections at 570 and 600°C. These results were slightly modified by

[1987Pri] to make them consistent with the thermodynamic rules of phase diagram construction.

[1981Zar] reported ten ternary phases, and an isothermal section at 600°C. [2001Kre] determined a partial

isothermal section at 550°C. About 100 alloys, containing up to 50 at.% Fe and 50 at.% Si, were used. The

phase equilibria were established by extensive use of X-ray diffraction, EDS analysis of the phases, and

optical metallography.

Thermodynamic datasets of the ternary system were assessed by [1994Ang, 1998Kol, 1999Liu].

Binary Systems

The Al-Si binary phase diagram is accepted from [2003Luk]; the Al-Fe binary phase diagram is accepted

from [2003Pis]; and the Fe-Si binary phase diagram is accepted from [1982Kub]. In the Al-Fe system, it

has been reported that Fe4Al13 melts congruently at 1152°C [1986Len] which confirms earlier finding by

[1960Lee].

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Solid Phases

As far as the binary intermediate phases are concerned, only those appearing in the equilibrium phase

diagrams are considered here. For example, direct chill-cast of commercially pure Al-alloys are reported to

contain Al-Fe intermediate phases that are not present in the equilibrium phase diagram [1977Sim,

1982Wes, 1985Don2, 1986Liu1, 1986Liu2, 1987Cha, 1987Skj1, 1987Skj2, 1987Ste, 1988Cha, 1988Liu2].

Therefore, they are not considered in constructing the ternary phase diagrams.

At 550°C, the solubility of Fe and Si in (Al) is less than 1 at.% [2001Kre], and that of Fe and Al in (Si) is

extremely small.

The Fe4Al13 phase is reported to dissolve 0.8 mass% Si [1955Arm], 0.2 mass% Si [1967Sun], 1.0 mass%

Si [1984Don], 2.9 mass% Si [1987Skj1], up to 6.0 mass% Si at 600°C [1987Ste], and 4 at.% Si at 550°C

[2001Kre]. This is associated with an increase in the a-lattice parameter and a decrease in the b-lattice

parameter; whereas no significant changes in the c-lattice parameter and were detected [1987Ste]. The

composition dependence of a- and b-lattice parameters in Fe4Al13 is expressed by [1987Ste] as

a (in pm) = 1505.0+1.14 WFe-0.41 WSi

b (in pm) = 862.8-1.41 WFe-1.3 WSi

where WFe and WSi are the mass% of Fe and Si, respectively. A detailed crystallographic analysis of the

Fe4Al13 phase, by means of convergent beam electron diffraction and high resolution electron microscopy,

has been performed by [1987Skj3]. Lattice images revealed that the Fe4Al13 crystals are divided into tiny

domains (few thousand pm) which are separated by lattice displacements such as stacking faults [1987Skj2,

1987Skj3].

At 550°C, FeAl2 dissolves about 1 at.% Si, and Fe2Al5 dissolves about 2 at.% Si [2001Kre].

Initial studies showed that the FeSi2(h) phase dissolves up to about 0.5 mass% Al [1961Sab, 1965Sab,

1965Skr, 1968Sab1, 1968Sab2] which is accompanied by a small increase in both the a- and c-lattice

parameters. However, later it was found that FeSi2 dissolves up to 10 at.% Al [1994Ang, 1995Gue3]. The

FeSi phase also dissolves substantial amount of Al [1996Szy, 1998Dit], and at 550°C it is about 10 at.%

with Al substituting Si [2001Kre]. The ambient temperature lattice parameters of FeSi, FeSi2(h) and

FeSi2(r) as functions of Al-content were reported by [1996Szy]:

For FeSi: a (in pm) = 448.1+5.4xAl

For FeSi2(h): a (in pm) = 269.1+17.9xAl

c (in pm) = 515.7+30.2xAl

For FeSi2(r): a (in pm) = 986.6+7.3xAl

b (in pm) = 778.7+10.3xAl

c (in pm) = 782.1+27.6xAl

where xAl is the atomic fraction of Al.

The Fe3Al and Fe3Si phases form a continuous solid solution. The lattice parameter of the alloys along

Fe3Al-Fe3Si and Fe73Al27-Fe73Si27 sections and also for the commercial SENDUST and ALSIFER 32

alloys were determined systematically and accurately by [1979Cow]. The composition dependence of the

lattice parameter can be expressed as:

Along the Fe3Al-Fe3Si section

a (in pm) = 565.54+12.846 W+1.896 W2-0.7245 W3 = 565.54+12.776 C+1.9522 C2-0.7094 C3

where W = mass fraction of Fe3Al and C = mole fraction of Fe3Al.

Along the Fe73Al27-Fe73Si27 section

a (in pm) = 564.462+11.964 W +5.3929 W2-2.5 W3 = 564.462+11.915 C +5.3183 C2-2.321 C3

where W = mass fraction of Fe73Al27 and C = mole fraction of Fe73Al27.

[1979Cow] attributed a small, but consistent deviations from the linear dependence on composition, along

both sections, to the incomplete ordering as Al is replaced by Si. [1979Bur] also reported limited lattice

parameter data along Fe3Al-Fe3Si section which are in reasonable agreement with those of [1979Cow], but

[1979Bur] assumed a linear dependence of lattice parameter on composition (see also [1977Nic1],

[1977Nic2]). [1968Lih] reported lattice parameters of ternary alloys up to 30 at.% Si and 47 at.% Al at 20,

500, 600 and 900°C. [1946Sel] also measured the lattice parameter of ternary alloys up to 18 mass% Si and

13 mass% Al. The lattice parameter of Fe3(Al,Si) containing about 10 mass% Al and 5 mass% Si is reported

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to be 570 ± 3 pm [1978Xu]. The lattice parameter of an Fe-5.5 mass% Al-9.7 mass% Si alloy is reported to

be 568.4 pm after water quenching and 568.54 pm after annealing for 24 h at 600°C.

The complexity of phase equilibria of the Al-Fe-Si system is primarily due to the occurrence of many

ternary phases, and the associated metallurgical reactions during solidification and during heat treatments.

While some of these ternary phases are stable, many are metastable. In recent years, detailed

crystallographic characterization of the stable phases have been performed; however, the current

crystallographic data of many metastable ternary phases are far from being complete. The difficulties of

complete crystallographic characterization of these phases are due to (i) the occurrence of several phases

over a relatively narrow composition range in the Al-corner, (ii) the complex crystal structure along with

the presence of high density of planar defects in ternary phases, (iii) the order-disorder reactions in the

Fe-corner, (iv) many invariant reactions which under normal experimental conditions (both during

solidification and during heat treatments) do not undergo completion, and (v) the effect of heterogeneous

nucleation on the phase selection during solidification. In the past seven decades a large number of ternary

phases in the Al-Fe-Si system have been reported. A chronological survey of these ternary phases is given

in Table 1, where it may be noted that some of the results are still controversial.

Nine ternary phases are accepted for the construction of phase diagrams. These are labeled as 1 to 10.

Among these, [1940Tak] reported six ternary phases, four of which ( 2, 4, 5, and 6) could be identified

without much difficulty. Their investigation was mainly based on thermal analysis and microstructural

examination, supplemented by limited X-ray diffraction. Single crystal structure determinations have been

carried out for 1 [1996Yan], 3, [1989Ger2], 4, [1969Pan, 1995Gue1], 6, [1994Rom], 7, [1995Gue2]

and 10, [1989Ger1]. The details of the crystal structures and lattice parameters of the solid phases are listed

in Table 2. The composition ranges of the equilibrium ternary phases reported by different authors are

plotted in Fig. 1. It may be noted that while most of the composition ranges are isolated from each other,

there are overlapping composition ranges among 2, 3 and 10 phases.

The 1-phase has monoclinic structure, and its composition has been corrected from Fe3Al3Si2 to Fe3Al2Si3[1996Yan]. [2001Kre] established that the previously reported 1 and 9 [1992Gho] are actually the same

phase. The 1-phase corresponds to the K1-phase of [1940Tak] and the E-phase of [1981Zar], and 9

corresponds to the D-phase of [1981Zar]. [2001Kre] also confirmed triclinic structure [1996Yan] of 1/ 9.

At 550°C, 1/ 9 coexists with Fe2Al5, Fe4Al13, 2, FeSi, 2, 3, 7, 10, and possibly 8 [2001Kre].

[1981Zar] represented the homogeneity range of 2-phase (the K-phase) as Fe22Al52-63Si15-26, which most

likely corresponds to the K3-phase of [1940Tak]. [2001Kre] represented its homogeneity range as

Fe(Al1-xSix)7, with 0.2 x 0.33. As seen in Table 2, three crystal structures of 2 have been reported.

[2001Kre] indexed the X-ray diffraction pattern of 2 using the monoclinic unit cell proposed by

[1967Mun]. At 550°C, 2 coexists with Fe4Al13, 1/ 9, 3, 4, 5, 6 and 7 [2001Kre].

The 3-phase corresponds to the K2-phase of [1940Tak] and the G-phase of [1981Zar], and it has negligible

homogeneity range [2001Kre]. The composition of 3 is represented as FeAl2Si [1981Zar], but EDS

analysis of [2001Kre] gave Fe25Al56±1Si19±1, or Fe(Al1-xSix)3, with x = 0.25. On the other hand,

[1989Ger2] reported its composition as Fe(Al1-xSix)3, with x=0.33 based on XRD analysis. [2001Kre]

suggested that it is impossible to detect such a small difference in Al/Si-ratio based on XRD analysis. Its

structure has been confirmed to be orthorhombic [1974Mur, 1981Zar, 1989Ger2, 2001Kre]; however, there

is a scatter in the lattice parameter values. At 550°C, 3 coexists with Fe4Al13, 1/ 9, 2 and 10 [2001Kre].

The 4-phase corresponds to the K4-phase of [1940Tak] and the A-phase of [1981Zar]. It is single phase at

the composition Fe(Al0.6Si0.4)5 [2001Kre]. The tetragonal structure of the 4 phase was first reported by

[1936Jae], and subsequently confirmed by several others [1950Phr, 1969Pan, 1974Mur, 2001Kre]. At

550°C, 4 coexists with (Si), 2, 6 and 7 [2001Kre].

The 5-phase corresponds to the K5-phase of [1940Tak] and the M-phase of [1981Zar]. Often, it is also

designated as -AlFeSi. Its stoichiometry may be described as Fe46(Al0.875Si0.125)200-x, with x = 7

[2001Kre]. The hexagonal structure of the 5 phase was first reported by [1953Rob], and subsequently

confirmed by [1967Mun, 1975Bar, 1977Cor, 1977Hoi, 1987Gri2, 1997Vyb, 2001Kre]. Earlier studies

[1950Phr, 1952Arm, 1955Arm, 1967Coo] reported a cubic structure of 5, but it was attributed to traces

( 0.3 mass%) of dissolved transition metals such as Mn or Cu that might have stabilized the cubic symmetry

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at the expense of the hexagonal structure [1967Sun, 1967Mun]. At 550°C, 5 coexists with (Al), Fe4Al13,

2, and 6 [2001Kre].

The 6-phase corresponds to the K6-phase of [1940Tak] and the L-phase of [1981Zar]. Often, it is also

designated as -AlFeSi. Its stoichiometry is FeAl4.5Si. Despite numerous studies, the crystal structure of 6

is still controversial. While the X-ray diffraction studies reported its structure to be monoclinic [1950Phr,

1954Spi, 1955Obi, 1975Bar, 1994Mur, 1994Rom, 1996Mur, 1997Vyb, 2001Kre], convergent beam

electron diffraction studies found that 6 is orthorhombic [1993Car, 2000Zhe]. In fact, [2000Zhe] did not

find any monoclinic phase in their electron microscopic investigation. They concluded that the

misinterpretation of X-ray diffraction data indexed by a monoclinic cell may be due to intergrowth of

different phases, and a high density of planar defects. At 550°C, 6 coexists with (Al), (Si), 2, 4 and 5

[2001Kre].

[1951Pra1] correlated the formation of 5 and 6 with the electron-to-atom ratio. [1979Mor] analyzed the

composition of the intermetallic phases by electron microprobe technique and grouped them into two

categories based on the size and Fe/Si ratios which can be matched with the 5 and 6 phases. However,

[1979Mor] reported 'indeterminate' particles having intermediate size and Fe/Si ratios between 2.75 and

2.25. [1977Igl] postulated that the 5 phase is metastable and can replace the 6 phase at cooling rates

greater than 200 K/min. [1985Suz] and [1987Nag] reported Mössbauer spectra of the 5 and 6 phases, the

former gave a relatively complex spectrum, and the latter gave a simpler one.

The 7-phase corresponds to the B-phase of [1981Zar], and it has negligible homogeneity range [2001Kre].

Based on the EDS data, the stoichiometry of 7 is Fe25Al45Si30, or Fe(Al1-xSix)3, with x = 0.4 [2001Kre].

On the other hand, based on XRD data [1995Gue2] proposed the stoichiometry of 7 as Fe2Al3Si3, or

Fe(Al1-xSix)3, with x = 0.5, which reflects a discrepancy in Al/Si-ratio. Nevertheless, the monoclinic

structure of 7 reported by [1995Gue2] was also confirmed by [2001Kre]. The observation of Fe5Al8Si7[1994Ang] most likely corresponds to 7 [2001Kre], based on the assumption of a composition shift similar

to 1, even though [1994Ang] did not report its crystal structure. At 550°C, 7 coexists with (Si), 1/ 9, 2,

4 and 8 [2001Kre].

The 8-phase corresponds to the C-phase of [1981Zar]. Its stoichiometry may range from Fe(Al1-xSix)2,

with x = 0.5 [1981Zar] to Fe(Al1-xSix)2, with x = 0.67 [1996Yan]. It has orthorhombic structure [1996Yan,

2001Kre]. The observation of Fe5Al5Si6 [1994Ang] most likely corresponds to 8 [2001Kre], based on the

assumption of a composition shift similar to 1, even though [1994Ang] did not report its crystal structure.

The 10-phase corresponds to the F-phase of [1981Zar] with stoichiometry Fe25Al60Si15. [1981Zar]

reported that its structure in as-cast alloy is different from annealed condition, which was later confirmed

by [1987Ste]. The hexagonal structure of 10 is prototypical of either Co2Al5 or Mn3Al10. [1989Ger1]

reported Mn3Al10-type structure of 10 annealed at 600°C, while [2001Kre] reported the same structure in

as-cast alloy. At 550°C, 10 coexists with Fe4Al13, 1/ 9 and 3 [2001Kre].

Recent investigations of precipitates in commercial Al alloys, by means of TEM/STEM, EDAX, and high

resolution electron microscopy, have revealed a wide variety of precipitate crystal structures, lattice

parameters and compositions [1982Wes, 1984Don, 1985Don1, 1985Don2, 1985Gri, 1985Liu, 1986Liu1,

1986Liu2, 1987Cha, 1987Czi, 1987Skj1, 1987Ste, 1987Tur, 1988Ben2, 1988Cha] which can not be

grouped together (for details see Table 1). In this assessment, these phases are considered to be metastable.

In the absence of detailed crystallographic data, a classification of these metastable phases based on the

crystal system is proposed in Table 3. [1987Nag] and [1987Tur] found that the compositions of the

intermediate phases and the phase transformations that take place during high temperature annealing depend

on the Fe/Si ratio of the alloy. [1986Liu2] reported three different kinds of precipitates, in dilute Al-Fe-Si

alloys, formation of which is reported to be a function of Fe/Si ratio, alloy purity, solidification rate and heat

treatment. These factors probably explain the occurrence of so many ternary phases as reported by different

authors. The principles governing the substitution of Al by Si in the ternary intermediate phases have been

described by [1989Tib].

The composition ranges of the metastable phases are plotted in Fig. 2. Compared to the equilibrium ternary

phases, the scenario here is much more complex. Virtually all metastable phases have overlapping

composition range between 25 to 35 mass% Fe and 0 to 11 mass% Si. Besides crystalline metastable phases,

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the formation of amorphous phases in a number of Al-Fe-Si alloys has also been reported [1986Dun,

1987Ben, 1988Ben1].

Order-Disorder Phase Transitions

There have been extensive studies of order-disorder transitions of Fe-rich ternary alloys, both

experimentally and theoretically. Mutual solid solubility between Fe3Al and Fe3Si is well-established. The

solid solubility and the magnetic behavior of Fe3(Al, Si) was correlated with electron-atom ratio [1977Nic1]

and [1977Nic2]. The existence of the ordered phases 1 (Fe3Al and Fe3Si which have D03 or BiF3 type

order) and 2 (FeAl and FeSi which have B2 or CsCl type order) along the Fe3Al-Fe3Si section was studied

[1969Pol, 1973Kat] by means of high temperature X-ray diffraction and recording the disappearance of D03

superlattice {111} and {200} reflections as a function of temperature and composition. [1946Sel] measured

the lattice parameter of alloys up to 13 mass% Al and 18 mass% Si and observed an inflection point in the

lattice parameter vs composition curve which was attributed to the ordering reaction and the formation of

Fe3(Al,Si) having D03 superstructure. This was further supported by specific heat measurements as a

function of Si/Al ratio by [1951Sat], who found the reaction is accompanied by a small change in Gibbs

energy suggestive of a second-order reaction. However, with the addition of Si in Fe3Al the ordering

energies increase monotonically [1973Kat]. The order-disorder transitions along Fe3Al-Fe3Si was further

studied by transmission electron microscopy (TEM) [1982Cha] and by magnetic method [1986Tak].

However, there is still some controversy regarding the sequence of ordering transitions along this section.

Previous studies by [1969Pol] and [1973Kat] indicate that the sequence of ordering reaction (on cooling) is

always ( Fe) 2 1 along Fe3Al-Fe3Si section. However, recent studies by [1982Cha] and [1986Tak]

indicate that substitution of more than 50% of the Al atoms by Si atoms ( Fe) transforms directly into D03

structure. [1984Mat] studied two kinds of processes of ordering with phase separation, 2 ( Fe+ 1) and

1 ( Fe+ 1), in an Fe-6Fe-9Si (at.%) alloy using X-ray diffraction and transmission electron microscopy.

Single phase 1 and 2 structures were retained by quenching the alloy from 700 and 900°C, respectively.

The results of [1969Pol] and [1973Kat] indicate that addition of Si in Fe3Al increases the 1 2 transition

temperature while that of 2 ( Fe) increases with up to about 12.5 at.% Si beyond which it levels off. The

initial increase in ordering temperatures is consistent with the observation of [1977Nic1], and also

confirmed by [1987For]. A recent study of magnetic measurements [1986Tak] indicate that the ( Fe) 2

and 2 1 transition temperatures vary non-monotonically with increasing Si-content as shown in Fig. 3.

Minor adjustments have been made in Fig. 3 to comply with the accepted Al-Fe binary phase diagram, and

also by taking into account the results of [1982Cha] that the ( Fe) 1 ordering temperature of

Fe3(Al0.392Si0.608) is greater than 1050°C. Even though the effect of Si on the ordering induced phase

separation around Fe3Al has not been investigated in detail, it is important to note that [1996Mor] observed

( Fe)+ 1 microstructure in an Fe-17Al-1Si(at.%) alloy in the temperature range of 400 to 600°C. It is

expected that the topology of the phase boundaries involving ordered ( 1, 2) and disordered phases ( Fe)

near Fe3Al will follow the general features of phase diagrams associated with multicritical points [1982All].

Due to these reasons, several amendments are proposed in Fig. 3, shown by dotted lines, in the vicinity of

Fe3Al.

Even though, in general the nucleation and growth of 1 domain in 2 domain is easier than in ( Fe) matrix,

the direct ( Fe) 1 transformation in certain composition range has been attributed to the lowering of

atomic potential energy when Al atoms are substituted by Si atoms. This causes the formation of different

types of anti-phase boundaries and the corresponding changes in dislocation configuration leads to double

dissociation of superlattice dislocations [1982Cha]. Depending on the composition of the alloy, nucleation

of the ordered phases can also take place directly from the melt. TEM and Mössbauer spectroscopy study

[1983Gle] of an Fe-5.4Al-9.6Si(mass%) alloy revealed that the B2 type of ordering takes place directly

from the melt which subsequently undergoes D03 ordering. Also, [1969Pol] observed that the D03

superlattice reflections persist up to the melting point in an alloy of Fe3Al+12 at.% Si. A similar conclusion

was also made by [1954Gar] who investigated the order-disorder transition, after quenching from different

temperatures, in an Fe-9.7Si-5.5Al(mass%) alloy. By rapid quenching an Fe-5.4 mass% Al-9.6 mass% Si

alloy, [1983Gle] observed that excess vacancies are introduced which occupy ordered sublattice positions,

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giving rise to a new crystallographic superstructure of the D03-type. Such type of vacancy-induced long

range ordering, from one crystal structure to another, has also been observed at other composition

[1988Liu1].

Mössbauer spectroscopy study of Fe73Al11Si16 (ALSIFER27) and Fe68Al22Si10 (ALSIFER32), by

[1977Suw], revealed that excess diamagnetic atoms preferentially occupy particular D03 lattice sites which

is not observed from X-ray diffraction. They argued that powder methods used in X-ray diffraction may not

represent the ordering reactions in the bulk materials. Also, Mössbauer study of Fe3Al1-xSix, for 0 x 1,

indicates that 'order-annealing' treatment is accompanied by a separation of Fe3Al and Fe3Si types of local

surroundings [1983Sch]. However, this has only weak influence on the physical properties and the

predominant factor being the composition of the sample. [1987Dob] determined the atom locations in

Fe3-xAlxSi alloys with x=0.1, 0.2 and 0.3 having D03 structure, where Al atoms are confirmed to occupy the

Fe-sites.

[1996Mor] studied the kinetics of ordering and phase separation in an Fe-17 at.% Al-1 at.% Si alloy in the

temperature range of 400 to 600°C, where they monitored the evolution of + 1 microstructure. They found

that partial substitution of Al by Si improves microstructural stability against coarsening, most probably due

to decrease diffusivity and a reduction in misfit strain.

A theoretical study of ordering process in Fe0.5(Al1-xSix)0.5 [1999Mek] predicts an increase in

order-disorder temperature. Furthermore, they predicted that Si preferentially substitute Fe in

Fe0.5(Al1-xSix)0.5.


[1931Fus] and [1934Fue] proposed a pseudobinary section Si-Fe4Al13 with a peritectic reaction

L + Fe4Al13 Fe2Al6Si3 at about 920°C and a eutectic reaction between (Si) and Fe2Al6Si3 at 850°C and

32 mass% Si. However, later works failed to confirm the presence of such a pseudobinary section and

consequently it is disregarded.


At least nineteen invariant equilibria, in the solidification range of Al-Fe-Si alloys, have been reported

which are listed in Table 4. The assessed compositions of the liquid phase, after [1927Gwy, 1936Jae,

1937Ura, 1940Tak, 1951Now, 1960Spe], for the ternary invariant reactions are listed in Table 4. [1940Tak]

proposed nineteen ternary invariant reactions for the solidification of the Al-Fe-Si alloys. However, they

reported that some of these reactions take place in a very narrow range of temperature, thus, difficult to

resolve by thermal analysis. For example, [1940Tak] proposed the following two reactions:

L + 2 + FeAl2 at 1120°C

L + FeAl2 2 + Fe2Al5 at 1115°C.

These two reactions could not be distinguished clearly and a temperature interval of 5°C was assumed

[1940Tak]. Also, they reported that it was difficult to distinguish FeAl2 from Fe2Al5 by etching. Instead of

the above two reactions, the following invariant reaction is assumed in the present evaluation:

L + 2 + Fe2Al5 at 1120°C.

Ignoring the solubility of Si in FeAl2 and Fe2Al5, thermodynamic calculations [1998Kol, 1999Liu] give

following three reactions:

+ Fe2Al5 FeAl2, L (degenerate binary reaction)

L + 2 + FeAl2 at 1125°C [1998Kol], at 1127°C [1999Liu]

L + FeAl2 2 + Fe2Al5 at 1062°C [1998Kol], at 1073°C [1999Liu].

Among these, the first reaction was not explicitly mentioned by the authors. Since the solubility of Si in

FeAl2 and Fe2Al5 phases are not considered in thermodynamic modelling, the temperature of the

three-phase equilibrium + Fe2Al5 + FeAl2 in the ternary is connected with the Si-content of by a

"generalized Raoult's law". In the Al-Fe system, the eutectic temperature of L + Fe2Al5 is very closely

above the temperature of + Fe2Al5 FeAl2. For the three-phase equilibria going down from these

temperatures into the ternary a "generalized Raoult's law" is valid, due to which the two three-phase

equilibria meet and form the above mentioned four-phase equilibrium. This meeting happens very near to

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the binary Al-Fe system. The amount of liquid participating in the four-phase equilibrium roughly

corresponds to the ratio of Si-solubility in and liquid phases.

[1981Riv] did not consider the participation of the L 2 + Fe2Si binary invariant reaction in the

solidification process of the ternary alloys. Also, they did not consider Fe2Si to be a primary crystallization

product in the ternary regime. To alleviate these drawbacks, an invariant reaction with highest temperature

must be assumed near the Fe-Si side. It is labelled as U1, and assumed to take place around 1150°C

[1992Gho]:

L + Fe2Si 2 + FeSi

In fact, the likelihood of U1 is also predicted in recent thermodynamic assessments of [1998Kol, 1999Liu].

Thermodynamic modeling also confirmed the existence of following invariant reactions: P1, U3, U4, U5, P2,

U7, U8, P5, U10, U11, U12 and E1.

It should be noted that Fig. 4 represents only a partial reaction scheme. It considers participation of six

ternary phases, 1, 2, 4, 5, 6 and 7, during solidification. The composition domain of liquid alloy where

3 is the primary crystallization product should be close to that of 2, but the available thermal analysis data

[1940Tak] are insufficient to differentiate them. The reaction scheme does not account for the experimental

observation of several three-phase fields, such as 2+ 5+ 6 at 600°C [1987Ste] and at 550°C [2001Kre],

2+ 4+ 6 at 550°C [2001Kre], 2+ 4+ 7 at 550°C [2001Kre]. These may originate from the invariant

reactions L + 2 5 + 6 around 650°C [1952Arm, 1967Mun], L + 2 + 4 6 around 700°C [1927Gwy,

1940Tak], and L + 7 3 + 4, respectively. However, to account for all experimentally observed

three-phase fields at 600 [1992Gho] and 550°C [2001Kre], including those involving 8 and 10, it is

necessary to introduce too many speculative invariant reactions. Therefore, no attempt was made to propose

a complete reaction scheme. Nevertheless, further careful experiments are needed to establish the invariant

reactions during solidification and also in the solid state.

Liquidus Surface

Figure 5 shows the liquidus surface of the Al-corner calculated by the dataset of [1999Liu], which

reproduces well those of [1927Gwy, 1943Phi, 1946Phi1]. The general form of the liquidus surface has been

confirmed by other investigators [1933Nis, 1936Jae, 1937Ura, 1951Now, 1967Mun, 1987Gri1, 1988Zak].

Nevertheless, some disagreement exists over the temperature contours. [1967Mun] reported that the cooling

rate is an important factor. On the other hand, [1967Sun] using a variety of cooling rates confirmed the data

of [1927Gwy] and [1943Phi] and proposed that the nucleation is the decisive factor. [1977Igl] claimed a

marked sensitivity of cooling rate not only on the temperature arrest, but also on the final product. In this

assessment, the data of [1927Gwy] and [1943Phi] are considered to be representative of normal equilibrium

condition and more complete compared to those reported by others [1933Nis, 1937Ura, 1951Now].

Figure 6 shows the liquidus surface of the whole Al-Fe-Si system [1940Tak], depicting the melting grooves

separating 15 different areas of primary crystallization. Since the invariant reaction U1 has not been

experimentally confirmed, part of the univariant lines formed by the 2, FeSi and Fe2Si crystallization

surfaces have been shown dashed. Nevertheless, the U1 reaction complies with all the binary invariant

reactions and experimental ternary phase diagrams. The calculated liquidus surfaces [1998Kol, 1999Liu]

look similar, except in the Al-corner where they differ by several at.% in composition and up to 30°C in

temperature compared to that of [1940Tak].

Approximate isotherms at 50°C interval are superimposed in Fig. 6. In both Al-Fe and Fe-Si binary systems,

depending on the alloy composition, either ( Fe) or 2 may be the primary crystallization product. In the

ternary system, as an approximation, the composition domains of ( Fe) and 2 as primary crystallization

products are delineated by the linear extrapolation between the composition limits of two binary edges. This

is shown by a dashed line in Fig. 6. In the Fe-Si system, 1 is the primary crystallization product during

solidification of alloys containing 27.5 to 32 at.% Si. However, the extension of this composition range into

the ternary system is not known. In the a comprehensive study of liquidus surface of the Al-corner, up to 70

mass% Fe, by [1937Ura] agrees reasonably well with the results of [1940Tak]. The liquidus temperatures

of [1936Jae] are few tens of degrees higher than [1940Tak], and could be due to inadequate experimental

arrangements.

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Isothermal Sections

Figure 7 shows the isothermal section at 1000°C [1981Riv], drawn from the polythermal sections of

[1940Tak]. At 1000°C, only one ternary phase, 1, is stable which is also expected from the reaction scheme

in Fig. 4. Also, in Fig. 7, the boundary between ( Fe) and 2 is shown by a dashed line which is a linear

interpolation between the composition limits of two binary edges. The extension of the binary intermediate

phases into the ternary regime is given as approximate only. Figure 8 shows the isothermal section of the

Al-corner at 640°C [1959Phi]. [1987Ste] reported the phase equilibria in a set of commercial Al-based alloy

after heat treating the as-cast samples for one month between 570 and 600°C. The heat treated state was

referred to as “quasi-equilibrium” condition [1987Ste]. The phase equilibria of the Al-corner at 600°C is

shown in Fig. 9, after [1987Pri] who amended the isothermal section reported by [1987Gri1] and [1987Ste].

It is to be noted that the (Al)+ 6 and (Al)+ 6+(Si) phase fields were derived from the measurements on

samples annealed at 570°C. So the existence of these phase fields is consistent with the reaction scheme in

Fig. 4, giving the temperature for E1 as 573°C. Also, [1987Ste] reported that three ternary compounds

-FeAlSi ( 5), -FeAlSi ( 6) and -FeAlSi ( 2), the details of which are given in Table 2, crystallize from

the liquid. This is also consistent with the proposed reaction scheme in Fig. 4. During heat treatment of the

as-cast samples, the Fe4Al13, 5 and (Si) phases react to form 6 phase, but this reaction does not go to

completion [1987Ste].

Figure 10 shows the assessed isothermal section at 600°C. The Fe-corner involving the ordered phases is

taken from [1986Miy], but at certain composition ranges the ordered phase regions are still doubtful, and

they are shown as dashed. The isothermal section at 600°C reported by [1981Zar] has undergone several

amendments. Previously reported [1992Gho] 1 and 9 phases are treated as one phase [2001Kre]. The

composition of 8 is accepted from [1996Yan]. Figure 11 shows the partial isothermal section at 550°C

[2001Kre]. Even though temperature difference is only 50°C, there are important differences between Figs.

10 and 11. For example, Fig. 10 shows the presence of (Al)+(Si)+ 4 phase field which is not accounted for

by the reaction scheme, while Fig. 11 shows the presence of (Al)+(Si)+ 6 phase field which is consistent

with the reaction scheme in Fig. 4. Figure 10 shows the presence of 10+Fe2Al5+Fe4Al13 phase field, while

Fig. 11 shows the presence of 1/ 9+Fe2Al5+Fe4Al13 phase field. In Fig. 11, several phase boundaries

involving 8 are uncertain. [2001Kre] reported that the tie-triangles involving 8 will depend on its

composition, which was not determined. As a results, some of the phase boundaries in 8 are shown dotted.

Figure 12 shows the partial isothermal section at 500°C proposed by [1984Don] in which the phase

boundaries have shifted to the right, compared to [1943Phi, 1946Phi1, 1946Phi2], in order to account for

the observation of various phases as well as the amount of Si in solid solution in the (Al) matrix in

industrially pure Al.

Figures 13, 14, 15, 16 show the isothermal sections of the Fe-corner at 700, 650, 550 and 450°C,

respectively, after [1986Miy] who studied ternary alloys, containing up to 40 at.% solute atoms (Al+Si), by

means of transmission electron microscopy. These figures depict the states of different kinds of order in

ternary Fe-rich alloys as a function of composition and temperature. [1986Miy] reported two types of phase

separation 1(D03)+ 2(B2) and ( Fe)+ 1(D03) in the ternary alloys connecting Fe-10 to 14 at.% Si with

Fe-20 to 25 at.% Al and also near Fe-30 at.% Si alloy. The morphology of the <100> modulated structure

in Fe-Si and Al-Fe-Si alloys differs from that of the Al-Fe system [1986Miy]. X-ray diffraction data and

TEM observations of [1971Gle] concerning various order-disorder reaction in the ternary alloys

qualitatively agree with those of [1986Miy]


Figures 17, 18 and 19 show polythermal sections of the ternary system at 0.7 mass% Fe [1949Cru, 1959Phi],

at 4.0 mass% Fe [1959Phi] and at 8.0 mass% Si [1959Phi], respectively. There are no published data for the

solidus projection of the entire system, even though a number of polythermal projections are available

[1927Gwy, 1932Nis, 1933Nis, 1940Tak, 1946Phi1]. The solidus projection of the Fe-corner was reported

[1968Lih], but their results differ substantially along the Al-Fe binary edge, so they are not accepted here.

Since Al-rich solid solutions can dissolve only about 0.052 mass% Fe, the solidus of the Al-corner

[1961Phi] of the Al-Fe-Si system is shown in Fig. 20 on an enlarged scale.

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Al–Fe–Si

Thermodynamics

Thermodynamic properties of ternary alloys have been investigated a number of times by measuring the

heat of formation of solid alloys [1937Koe, 1937Oel], activity measurements in liquid alloys [1969Bed,

1970Mit, 1973Nag, 1973Per, 1980Sud, 1984Ber, 1985Cao, 1989Bon], and the standard heat of formation

of ternary intermetallics [1997Vyb, 2000Li1, 2000Li2]. The energetics of chemical ordering in the ternary

system has been described by [1991Fuk] and [1994Koz]. Besides, thermodynamic modeling of the ternary

system has also been carried out by the CALculation of PHase Diagram (CALPHAD) method [1994Ang,

1995Gue3, 1998Kol, 1999Liu], where the Gibbs energies of the relevant phases are described by simple

analytical functions.

[1969Bed] determined the activity coefficients at several constant mole fraction ratios (xSi/xFe) at 1627°C.

The Al activities in the temperature range of 800 to 1100°C were reported by [1973Nag], and at 900°C by

[1973Per]. [1980Sud] reported Al activity in an Fe-1 mass% Al-1 mass% Si alloy at 1485 and 1546°C.

Further experiments were carried out by [1984Ber] and [1989Bon]. The latter authors measured the

chemical potential of Al in alloys containing up to 11.8 at.% Fe and 23.7 at.% Si by the concentration cell

method in the temperature range of 577 to 1027°C. The activities of Al show a negative deviation from ideal

behavior. The results of [1984Ber] also show a similar trend.

The heat of mixing of solid alloys was measured by pouring liquid Al-Si alloy and liquid Fe into a water

calorimeter [1937Koe,1937Oel]. However, the state of equilibrium in these experiments is uncertain

[1999Liu]. The standard heat of formation of ternary intermetallics, except 7, has been determined by

solution calorimetry by [1997Vyb], [2000Li1] and [2000Li2]. [1997Vyb] used 99.99% Al, 99.9% Fe and

99.99% Si to prepare single phase 5 and 6 samples by annealing cast ingots either at 550°C ( 5) or at

600°C ( 6) for 1 month. They used an aluminum bath at 1070°C for solution calorimetry. Li et al [2000Li1,

2000Li2] used 99.99% Al, 99.999% Fe and 99.999% Si, and prepared ingots by levitation melting followed

by annealing, the conditions of which were varied to obtain single phase alloys of 5, 10, 1 and 9

[2000Li1], and 6, 2, 3, 8 and 4 [2000Li2]. Unlike [1997Vyb], Li et al used an aluminum bath at a lower

temperature of 800°C for solution calorimetry. There are differences between the results of [1997Vyb] and

[2000Li1, 2000Li2]. For example, [1997Vyb] reported that the standard heat of formation of 5

(Fe19.2Al71.2Si9.6) and 6 (Fe15.4Al69.2Si15.4) are –34.3±2 and –24.5±2 kJ/atom, respectively. The

corresponding values reported by Li et al are –24.44±1.39 kJ/mol for 5 at Fe18Al72Si10 [2000Li1] and

–20.209±0.926 kJ/mol for 6 at Fe15Al70Si15 [2000Li2]. Even though the 5 and 6 compositions of

[1997Vyb] and [2000Li1, 2000Li2] are not identical, large differences in heat of formation are unexpected.

Apparently, Li et al [2000Li1, 2000Li2] were unaware of the results of [1997Vyb], and they did not discuss

this discrepancy. Nevertheless, it is not clear if a higher bath temperature (causing oxidation) and relatively

impure starting materials used by [1997Vyb] compared to Li et al have contributed to more negative heat

of formation.

[1994Ang] determined the enthalpy of fusion of FeAl3Si2 ( 4) and Fe5Al8Si7 ( 7).

[1949Cru] reported calculated solubility isotherms of Fe and Si in solid (Al). They suggested the formation

of a ternary compound Fe2Al7Si which is close to the 5 phase at low Si content. On the other hand their

calculation seems to suggest the ternary phase FeAl5Si which is close to the 6 phase [1981Riv]. Calculation

of the liquidus surface from a purely thermodynamic approach [1946Phi2] seems to produce good result

near the binary edges. However, their approach can neither predict the composition of the precipitating

phase nor calculate the solidus curves.

[1994Ang] employed the CALPHAD technique and calculated two vertical sections corresponding to

xAl/xSi=3/1 and at xSi=0.85. [1995Gue3] calculated two partial isothermal sections at 600 and 900°C, and a

vertical section at xSi=0.78 by the CALPHAD method. They considered only two ternary phases: FeAl3Si2( 4) and Fe2Al9Si2 ( 6).

[1991Fuk, 1994Koz] performed a theoretical analysis of phase separation involving Fe, 2 and 1 phases.

The free energy of ternary alloys is evaluated statistically using a pair-wise interaction up to second nearest

neighbor. Both chemical and magnetic interactions based on Bragg-Williams-Gorsky model were used. The

calculated phase diagrams are found to be consistent with the experimental ones.

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Al–Fe–Si

[1998Kol] and [1999Liu] carried out detailed thermodynamic assessments of the ternary system by the

CALPHAD method. According to our classification, [1998Kol] considered six ternary phases 1, 2, 3, 4,

5 and 6, whereas [1999Liu] considered seven ternary phases: 1, 2, 3, 4, 5, 6, and 7, called 1, , 23,

, , , , respectively. [1999Liu] argued that 2 and 3 have very similar Fe contents, and wondered, if they

are the same phase with a small homogeneity range. This view was also accepted by [2002Rag]. However,

as summarized in Table 2, 2 and 3 have different crystal structures. [1999Liu] computed the liquidus

surface, isothermal sections at 600 and 1000°C, and vertical sections at 1.3, 2, 5, 10% Fe and 2% Si (mass).


[1951Oga1, 1951Oga2, 1983Sch] reported the ferromagnetic behavior of Fe3Al-Fe3Si alloys. [1968Aru1,

1968Aru2, 1970Aru] reported that the occupation of ordered sites by all three Al, Fe and Si atoms

accompanied with a minimum in electrical resistivity at Fe75Al18Si7 and Fe6(Al,Si). [1996Szy] reported

that dissolved Al in FeSi2(r) increases its magnetic susceptibility, and both FeSi and FeSi2(r) exhibit Van

Vleck paramagnetism even at very low temperature (up to 4.2 K). [1996Fri] and [1998Dit] studied the

metal-insulator transition in Al doped FeSi. [1998Dit] reported lattice constant, thermoelectric effect, Hall

effect, electrical conductivity, magnetic susceptibility, specific heat and magnetoresistance in FeSi1-xAlx,

with 0 x 0.08. All these properties confirm a metal to insulator transition of FeSi, which is otherwise

a Kondo insulator. [1999Oht] has reported that doping of FeSi2(r) with 3 at.% Al improves its

thermoelectric figure of merit. The magnetic properties of ternary alloys have been discussed in detail by

[1986Tak] and [1988Dor].

[1993Sch] investigated the plastic deformation of single-crystal Al20Fe75Si5 alloy as a function of

temperature. The critical resolved shear stress exhibits a non-monotonic behavior with a maximum around

530°C. The non-monotonic behavior was correlated with the temperature-dependent dislocation mobility

rather than a decrease in D03 long-range order parameter. [1996Cho, 2001Cho] reported the microstructure,

hardness and tensile properties of Al-5Fe-16Si(mass%) alloy, processed by powder metallurgy up to 520°C.

[1948Jen] demonstrated a relationship between the constitutional diagram and the susceptibility to cracking

of the Al-Fe-Si alloys. A key factor in determining the corrosion behavior of Al-rich alloys is the Fe/Si ratio.

Low Fe/Si ratio in ternary alloys exhibit better corrosion resistance in both industrial and marine

environment [2000Bha].

Miscellaneous

In recent years, the solidification of Al-rich ternary alloys has been investigated rather extensively

[1983Per, 1991Don, 1991Lan, 1995Bel, 1995Gue3, 1996All, 1997All, 1997Sto, 1997Can, 1999Cho,

1999Tay, 2000Dut, 2001Hsu, 2001Sha, 2002Mer]. [1983Per] discussed the effect of metastable liquid

miscibility gaps, metastable eutectic and metastable peritectic on the rapid solidification processing and

alloy design. Addition of up to 0.11 mass% Si in a Al-0.5 mass% Si alloy is reported to favor the formation

of the metastable phase FeAl6 [1978Suz].

[1995Bel] proposed a non-equilibrium solidification method to analyze the cast microstructure of ternary

alloys. This method utilizes equilibrium phase diagram, but assumes that the peritectic reactions are

suppressed and the eutectic reactions occur according to the equilibrium phase diagram. Cantor and

co-workers [1996All, 1997All, 1997Can] have discussed the role of heterogeneous nucleation on the phase

selection and solidification.

[1997Sto] studied the effect of cooling rate and solidification velocity on the microstructure selection of

Al-3.5 mass% Fe-(1 to 8.5) mass% Si alloys by wedge chill casting and Bridgman directional solidification

techniques. In the latter case, the front growth velocity was in the range of 0.01 to 2 mm/s under a

temperature gradient of 15°C/mm. Also, at front velocities greater than 1 mm/s, the primary intermetallics

were suppressed. The results of Al-3.5 mass%Fe-8.5 mass% Si were summarized in terms of a kinetically

based solidification microstructure selection diagram. [1999Tay] applied Scheil equation to predict the

defect-onset (porosity) during solidification of Al-rich alloys as a function of Fe and Si contents. They found

that a defect-free casting can be obtained if the solidification proceeds directly to the invariant reaction E1

(L 6+(Al)+(Si)), whereas poor casting may result when the solidification proceeds via the (Al)- 6 eutectic

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Al–Fe–Si

valley. The critical Fe-content at which the porosity is minimized is a function of Si-content in the alloy.

[2001Sha] also carried out Bridgman directional solidification of a model 6xxx alloy (Al-0.3 mass% Fe-0.6

mass% Si-0.8 mass% Mg), and obtained solidification front velocity in the range of 5 to 120 mm/min. They

observed two ternary phases, -FeAlSi ( 5) and -FeAlSi ( 6), of which the latter is metastable. At low front

velocity, such as 30 to 60 mm/min, -FeAlSi dominate the microstructure, while at high front velocity, such

as 120 mm/min, -FeAlSi dominates the phase selection.

Figure 21 shows the surface of secondary crystallization of the Al-corner after [1943Phi]. It should be noted

that the data relate to slowly-cooled alloys in a non-equilibrium state.

Since both the Al-Fe and Fe-Si binary systems form -loops, a ternary -loop is expected. [1931Wev]

reported the coordinates of the phase boundaries of the ternary -loop which are listed in Table 5.

[1960Voz] reported the effect of impurities on the solid solubility of Al alloys by means of electrical

resistivity. [1972Ere] studied the dissolution kinetics of Fe in Al-Si melts at 700, 750 and 800°C, the

kinetics of which was correlated with the formation of various intermediate phases.

[2000Sri] reported synthesis of bulk ternary intermetallics using elemental powder mixture by

self-propagating high temperature synthesis. They used cold compacted powder mixtures that were heated

to 650°C in a vacuum furnace. Both stable ( 2, 5 and 6) and metastable phases were obtained in this

process. They also reported hardness of the intermetallics.

[1998Akd] proposed that the value of activity coefficient of Al in -(Fe,Al,Si) alloys has a strong influence

on the formation and growth kinetics of interfacial diffusion layer. [1999Oht] has discussed the sintering

mechanism of Al-Fe-Si alloys, particularly the role of liquid phase, in the context of fabricating an Al-doped

FeSi2(r) phase. [2001Jha] has discussed the diffusion path of Al in ternary bcc alloys.

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MSIT®

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MSIT®

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J. Korean Inst. Met., 34(2), 230-235 (1996) (Experimental, 11)

[1996Fri] Friemelt, K., Ditusa, J.F., Bucher, E., Aeppli, G., “Coulomb Interactions in Al Doped FeSi

at Low Temperatures”, Ann. Phys., Leipzig, 5(2), 175-183 (1996) (Crys. Structure,

Experimental, 25)

[1996Mor] Morris, D.G., Gunther, S., “Order-Disorder Changes in Fe3Al Based Alloys and the

Development of an Iron-Base - `` Superalloy”, Acta Mater., 44(7), 2847-2859 (1996)


[1996Mul] Mulazimoglu, M.H., Zaluska, A., Gruzleski, J.E., Parray, F., “Electron Microscopy Study of

Al-Fe-Si Intermetallics in 6021 Aluminum Alloys”, Metall. Mater. Trans. A, 27A, 929-936


378


MSIT®

Al–Fe–Si

[1996Mur] Murali, S., Raman, K.S., Murthy, K.S.S., “Al-7Si-0.3Mg Cast Alloy: Formation and Crystal

Structure of -FeSiAl5 and (Be-Fe)-BeSiFe2Al8 Phases”, Mater. Sci. Forum, 217-222,


[1996Szy] Szymanski, K., Baas, J., Dobrzynski, L., Satula, D., “Magnetic and Mössbauer Investigation

of FeSi2-xAlx”, Physica B (Amsterdam), 225, 111-120 (1996) (Crys. Structure,

Experimental, 20)

[1996Yan] Yanson, T.I., Manyako, M.B., Bodak, O.I., German, N.V., Zarechnyuk, O.S., Cerny, R.,

Pacheko, J.V., Yvon, K., “Triclinic Fe3Al2Si3 and Orthorhombic Fe3Al2Si4 with New

Structure Types”, Acta Crystallogr., Sect. C: Cryst. Struct. Commun., C52, 2964-2967


[1997All] Allen, C.M., O`Reilly, K.A.Q., Cantor, B., Evans, P.V., “Heterogeneous Nucleation of

Solidification of Equilibrium and Metastable Phases in Melt-Spun Al-Fe-Si Alloys”, Mater.

Sci. Eng. A, A226-A228, 784-788 (1997) (Experimental, Phys. Prop., 10)

[1997Can] Cantor, B., “Impurity Effects on Heterogenous Nucleation”, Mater. Sci. Eng. A,

A226-A228, 151-156 (1997) (Crys. Structure, Experimental, 38)

[1997Sto] Stone, I.C., Jones, H., “Effect of Cooling Rate and Front Velosity on Solidification

Microstructure Selection in Al-3.5 wt.% Fe-0 to 8.5 wt.% Si Alloys”, Mater. Sci. Eng. A,

A226-A228, 33-37 (1997) (Equi. Diagram, Experimental, 10)

[1997Vyb] Vybornov, M., Rogl, P., Sommer, F., “The Thermodynamic Stability and Solid Solution

Behavior of the Phases 5-Fe2Al7.4Si and 6-Fe2Al9Si2”, J. Alloys Compd., 247, 154-157

(1997) (Crys. Structure, Equi. Diagram, Experimental, Review, 7)



Thermodyn., 55)

[1998Dit] Ditusa, J.F., Friemelt, K., Bucher, E., Aeppli, G., Ramirez, A.P., “Heavy Fermion

Metal-Kondo Insulator Transition in FeSi1-xAlx”, Phys. Rev. B, B58(16), 10288-10301


[1998Kol] Kolby, P., “System Al-Fe-Si”, in “COST 507, Thermochemical Database for Light Metal

Alloys”, Vol. 2, Ansara, I., Dinsdale, A.T., Rand, M.H. (Eds), Office for official publications

of the European Communities, Luxembourg, 319-321 (1998) (Assessment, Thermodyn.)

[1999Cho] Choi, Y.S., Lee, L.S., Kim, W.T., Ra, H.Y., “Solidification Behavior of Al-Si-Fe Alloys and

Phase Transformation of Metastable Intermetallic Compound by Heat Treatment”, J. Mater.

Sci., 34(9), 2163-2168 (1999) (Equi. Diagram, Experimental, 14)

[1999Liu] Liu, Z.-K., Chang, A., “Thermodynamic Assessment of the Al-Fe-Si System”, Metall.

Mater. Trans. A., 30A(7), 1081-1095 (1999) (Calculation, Thermodyn., 56)




[1999Oht] Ohta, Y., Miura, S., Mishima, Y., “Thermoelectric Semiconductor Iron Disilicides Produced

by Sintering Elemental Powders”, Intermetallics, 7, 1203-1210 (1999) (Equi. Diagram,

Experimental, Thermal Conduct., 19)

[1999Tay] Taylor, J.A., Schaffer, G.B., St. John, D.H., “The Role of Iron in the Formation of Porosity

in Al-Si-Cu-Based Casting Alloys: Part II. A Phase-Diagram Approach”, Metall. Mater.

Trans. A, 30A, 1651-1655 (1999) (Calculation, Crys. Structure, Experimental, 12)

[2000Bha] Bhattamishra, A.K., Chattoraj, I., Basu, D.K., De, P.K., “Study on the Influence of the Si/Fe

Ratio on the Corrosion Behavior of Some Al-Fe-Si Alloys”, Z. Metallkd., 91(5), 393-396

(2000) (Corrosion, Experimental, 23)

[2000Dut] Dutta, B., Rettnmayr, M., “Effect of Coolig Rate on the Solidification Behavior of Al-Fe-Si

Alloys”, Mater. Sci. Eng. A, A283, 218-224 (2000) (Equi. Diagram, Experimental, 23)

[2000Li1] Li, Y., Ochin, P., Quivy, A., Telolahy, P., Legendre, B., “Enthalpy of Formation of Al-Fe-Si

Alloys ( 5, 10, 1, 9)”, J. Alloys Compd., 298, 198-202 (2000) (Experimental,

Thermodyn., 20)

379


MSIT®

Al–Fe–Si

[2000Li2] Li, Y., Legendre, B., “Enthalpy of Formation of Al-Fe-Si Alloys II ( 6, 2, 3, 8, 4)”,

J. Alloys Compd., 302, 187-191 (2000) (Experimental, Thermodyn., 21)

[2000Sri] Sritharan, T., Murali, S., Hing, P., “Synthesis of Aluminium-Iron-Silicon Intermetallics by

Reaction of Elemental Powders”, Mater. Sci. Eng. A, A286, 209-217 (2000) (Crys.


[2000Zhe] Zheng, J.G., Vincent, R., Steeds, J.W., “Crystal Structure of an Orthorhombic Phase in

beta-(Al-Fe-Si) Precipitates Determined by Convergent-Beam Electron Diffraction”,

Philos. Mag. A, A80(2), 493-500 (2000) (Crys. Structure, Experimental, 11)

[2001Cho] Cho, H.S., Kim, K.S., Jeong, H.G., Yamagata, H., “Microstructure and Mechanical

Properties of Extruded Rapidly Solidified Al-16Si-5Fe Based Alloys”, Key Eng. Mater.,

189-191, 479-483 (2001) (Experimental, Mechan. Prop., 5)

[2001Hsu] Hsu, G., O´Reilly, K.A.Q., Cantor, B., Hamerton, R., “Non-Equilibrium Reactions in 6xxx

Series Al Alloys”, Mater. Sci. Eng. A, A304-A306, 119-124 (2001) (Equi. Diagram,

Experimental, 14)

[2001Jha] Jha, R., Haworth, C.W., Argent, B.B., “The Formation of Diffusian Coatings on Some

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Coatings”, Calphad, 25(4), 651-665 (2001) (Calculation, Equi. Diagram, 9)

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Aluminium-Iron-Silicon, und Aluminium-Iron-Manganese-Silicon”, Tezisy Inst. Phys.

Chem. Univ., Vienna, 2001 (Crys. Structure, Equi. Diagram, Experimental, #, *, 83)

[2001Sha] Sha, G., O´Reilly, K., Cantor, B., Worth, J., Hamerton, R., “Growth Related Metastable

Phase Selection in a 6xxx Series Wrought Al Alloy”, Mater. Sci. Eng. A, A304-A306,


[2002Mer] Meredith, M.W., Worth, J., Hamerton, R.G., “Intermetallic Phase Selection During

Solidification of Al-Fe-Si(-Mg) Alloys”, Mater. Sci. Forum, 396-402, 107-112 (2002)


[2002Rag] Raghavan, V., “Al-Fe-Si (Aluminium-Iron-Silicon)”, J. Phase Equilib., 25(4), 107-112





[2003Luk] Lukas, H.L., “Al-Si (Aluminum-Silicon)”, MSIT Binary Evaluation Program, in MSIT


Stuttgart; to be published, (2003) (Assessment, Equi. Diagram, Crys. Structure, 29)

Table 1: Chronological Survey of Ternary Phases in the Al-Fe-Si System

Author Phase Designation Composition (mass%)Comments

Fe Al Si

[1927Gwy] , , , - - - Ternary alloys up to ~20%Fe and 30%Si

(mass%) were studied. The -phase reported to

be solid solution of Fe, Al and Si.

[1928Dix] (Fe-Si)

(Fe-Si)

30.0

27.0

62.0

68.0

8.0

15.0

Ternary alloys up to 41%Fe and 29%Si(mass%)

were studied using pure Al(99.95%).Annealing:

1-5 weeks at 560°C. These two crystal species

were reported to be ternary solid solutions

rather than ternary compounds. Reported to

form a part-section with Fe4Al13 and (Fe-Si).

[1931Fin] (Fe-Si)

(Fe-Si)

30.3

27.3

61.4

57.7

8.3

15.0

Alloys and heat treatments were same as

[1928Dix]. They assumed (Fe-Si) was a solid

solution of Si in Fe4Al13.

[1931Fus] Fe2Al6Si3 31.3 45.2 23.5 Fe2Al6Si3 formed by a peritectic reaction.

380


MSIT®

Al–Fe–Si

[1932Nis],

[1933Nis]

Fe2Al3Si2P

44.9

-

32.5

-

22.6

-

Fe2Al3Si2 was reported around the composition

Al-32Fe-30Si (mass%). The -phase was not

studied further.

[1935Bos] Fe2Al6Si3 - - -

[1936Jae] FeAl4Si2Hexagonal

Orthorhombic

Triclinic

27.2

-

-

-

47.6

-

-

-

25.2

-

-

-

XRD, goniometric and dilatometric

measurements were carried out in ternary alloys

up to 40%Fe and 30% Si (mass%). The

chemical compositions of the hexagonal

(a=836, c=1458 pm), orthorhombic (a=609,

b=996, c=374 pm) and triclinic (a=688, b=593,

c=432 pm, = 104.75°, =130.67°, =68.4°)

phases were not given. FeAl4Si2 has tetragonal

structure (a=615, c=947 pm).

[1937Ser] FeAlnSi

n = 4

n = 5

FeAl4Si2

29.1

25.6

25.4

56.3

61.6

49.1

14.6

12.8

25.5

Microscopic and XRD were carried out in

alloys up to 10%Fe and 25%Si (mass%). The

densities of FeAl5Si and FeAl4Si2 were

reported to be 3.35 and 3.30 g cm-3,

respectively. FeAl4Si2 was found to have cubic

crystal structure.

[1937Ura] -

-

-

-

-

-

According to these authors and are formed

by peritectic reaction, they have no definite

composition, and are solid solutions.

[1940Tak] K1:Fe3Al3Si2K2:Fe6Al12Si5K3:Fe5Al9Si5K4:FeAl3Si2K5:Fe6Al15Si5K6:FeAl4Si

55.0

41.9

42.2

28.9

38.1

29.1

26.6

40.5

36.7

41.9

46.0

56.3

18.4

17.6

21.1

29.2

15.9

14.6

These authors reported six ternary phases (K1 to

K6) formed by peritectic reactions.

[1943Phi] (Fe-Si)

(Fe-Si)

-

-

-

-

-

-

They investigated ternary alloys up to 12

mass% Fe and 6 mass% Si.

[1950Phr] c-FeAlSi

m-FeAlSi

t-FeAlSi

31.9

27.2-

27.8

-

62.5

59.3-

58.2

-

5.6

13.5-

14.0

-

Alloys up to 42%Fe and 30%Si(mass%) were

studied. c-FeAlSi has cubic (a=1254.83 pm),

m-FeAlSi has monoclinic (a=b=612.23,

c=4148.36 pm, =91°) and t-FeAlSi has

tetragonal (a=612.23, c=947.91 pm) structure.

[1951Pra2] (Fe-Si)

-(Fe-Si)

32.1-

32.7

26.7-

27.3

59.5-

57.0

59.5-

57.8

8.4-

10.3

13.8-

14.9

Chemical analysis and XRD were carried out on

extracted crystals. The crystal structure of

(Fe-Si) was reported to be the same as Fe4Al13

and (Fe-Si) represents a distinct ternary

compound.

[1951Now] (Fe-Si)

(Fe-Si)

(Fe-Si)

(Fe-Si)

30.6

27.2

28.9

-

59.1

59.1

41.9

-

10.3

13.7

29.2

-

150 ternary alloys up to 45%Fe and 30% Si

(mass%) were investigated by thermoanalytical,

microscopic and XRD methods. Homogeneity

ranges of these phases were reported to be

small. Approximate stoichiometries of (Fe-Si),

(Fe-Si), (Fe-Si) can be represented as

Fe1.5Al6Si, FeAl4.5Si, Fe0.5Al1.5Si,

respectively. The latter has tetragonal structure

(a = 495.0, c = 707.0 pm).


Fe Al Si

381


MSIT®

Al–Fe–Si

[1952Arm]

[1955Arm]1

2

3

27.3

29.2

35.3

65.7

59.5

51.9

7.0

11.3

12.8

Alloys up to 20%Fe and 50% Si (mass%) were

studied. Microscopic, XRD and density

measurements were performed to characterize

the phases in as-cast alloys. The crystal

structures of 1, 2 and 3 were reported to be

cubic (a = 1254.83 pm), hexagonal (a = 496,

c = 702.11 pm) or orthorhombic (a = 4360,

b = 4960, c = 7080 pm) and cubic (a = 1603.23

pm), respectively. The densities were 3.50, 3.58

and 3.65 g cm-3, respectively.

[1953Rob] -FeAlSi 32.5 58.8 8.7 Single crystals of -FeAlSi, prepared by

[1951Pra1] and [1951Pra2] were studied by

X-ray diffraction. The crystal structure and

density were reported to be hexagonal (with

P63/mmc symmetry and a = 1230, c = 2620 pm)

and 3.62±0.02 g cm-3 respectively.

[1954Spi] c-FeAlSi

t-FeAlSi

m-FeAlSi

-

-

-

-

-

-

-

-

-

The crystal structures of c-FeAlSi, t-FeAlSi and

m-FeAlSi were reported to be cubic

(a = 1254.23 pm), tetragonal (a = 612.23,

c = 948.94 pm) and monoclinic (a = b = 612.23,

c = 4148.36 pm, = 91°), respectively. They

correspond to (Fe-Si), (Fe-Si) of [1943Phi]

and of [1927Gwy], respectively.

[1955Bla] Fe2Al9Si2 27.2 59.1 13.7 XRD was carried out on the extracted crystals

of [1951Pra1]. The crystal structure and density

were reported to be tetragonal (with 4/m

symmetry and a = 618±6, c = 4250±50 pm) and

3.50±0.1 g cm-3, respectively.

[1955Obi] (Fe-Si)

(Fe-Si)

30.2-

32.8

23.4-

25.8

58.1-

60.0

57.6-

58.5

11.2-

7.2

19.0-

15.7

(Fe-Si) was obtained in Al-5Fe-(3 to 7)Si

(mass%) which were water quenched after

annealing at 615 to 620°C for 1 h, and (Fe-Si)

was obtained in Al-4Fe-(9 to 13)Si (mass%)

alloys which were f/c cooled after the same heat

treatment. These crystals were extracted from

alloys after subjecting to different heat

treatments and were studied by XRD. The

powder patterns obtained from these two phases

were almost the same as c-FeAlSi and

m-FeAlSi of [1950Phr]. The lattice parameters

of (Fe-Si) and (Fe-Si) were a=1254.8 pm;

and a = b = 612.2, c = 4148.4 pm, and = 91°,

respectively.

[1956Spe] (Mn, Fe)AlSi - - - Found in wrought commercial 2024 alloy.

[1964Lai] FeAl5Si - - - Formed in an Al-1.5 mass% Si alloy plated with

Fe and annealed at 500°C. The ternary phase

was identified by X-ray and electron diffraction

techniques.


Fe Al Si

382


MSIT®

Al–Fe–Si

[1967Coo] -FeAlSi 31.9 61.7 6.4 XRD study of these crystals yielded cubic

structure with a=1256 pm, 138 atoms/unit cell

and Im3 symmetry. The composition of the

crystals was close to Fe5Al20Si2 and the density

was ~3.59±0.06 g cm-3.

[1967Mun] -CrFeAlSi

-FeAlSi

-FeAlSi

-FeAlSi

-FeAlSi

-

-

-

33.0-

38.0

-

-

-

-

54.0-

43.5

-

-

-

-

13.0-

18.5

-

Alloys containing up to 22 mass% (Fe+Si) were

cooled at 0.75°C/min. The phases were

analyzed by X-ray and electron diffraction. The

crystal structures of -CrFeAlSi, -FeAlSi and

-FeAlSi were reported to be cubic (a=1250 to

1270 pm), hexagonal (a=1230, c=2620 pm) and

C-face-centered monoclinic (a=1780±10,

b=1025±5, c=890±5 pm, =132°), resp. The

"cubic" (a=1603 pm) pattern of 3 of

[1955Arm] was indexed on the basis of this

monoclinic cell. -FeAlSi was reported to be

the same as 2 of [1952Arm].

[1967Sun] 1(FeAlSi)

2(Fe2Al8Si)

3(FeAl3Si)

(FeAl5Si)

(FeAl4Si2)

31.1

30.0-

33.0

34.0-

35.2

25.5-

26.5

25.0-

26.0

60.8

62.6-

56.0

50.4-

47.7

62.4-

58.9

49,0-

47.0

8.1

7.4-

11.0

15.6-

17.1

12.1-

14.6

26.0-

27.0

50 different ternary and quaternary alloys were

analyzed by chemical and X-ray diffraction.

The 1 crystals were reported to contain 1.05

mass% Mn. The crystal structures of 1 and 2

were reported to be cubic (a = 1250±10 pm) and

hexagonal, respectively.

[1969Pan] FeAl3Si2 28.9 41.9 29.2 The alloy was annealed at 800°C for 14 h and

water quenched, and was analyzed by XRD.

The crystal structure was reported to be

tetragonal (a = 607, c = 950 pm) of PdGa5-type,

[1973Kow] Fe2Al9Si2 - - - Found in Al-11.17Si-0.4Fe-0.49Mg-9.8Si and

Al-0.1Fe-0.4Mg-7.5Si-0.1Ti (mass%) alloys.

The extracted crystals were analyzed by XRD

and microprobe analysis. The composition of

the precipitate as given by the authors does not

add up to 100.

[1974Mur],

[1981Zar]

A: Fe15Al57-47Si28-38

B: Fe22Al40Si38

C: Fe32Al38Si30

D: Fe36Al36Si28

E: Fe40Al40Si20

F: Fe25Al60Si15

G: Fe25Al50Si25

K: Fe22Al63-52Si15-36

L: Fe15Al70Si15

M: Fe17Al72Si11

26.5-

27.5

36.4

48.9

53.3

57.7

40.5

40.6

36.7-

36.6

26.6

29.7

40.0-

48.6

32.0

28.1

25.8

27.8

39.1

47.1

50.7-

41.7

60.0

60.7

33.5-

24.9

31.6

23.0

20.9

14.5

20.4

12.3

12.6-

21.7

13.4

9.6

The crystal structures of Fe25Al50Si25,

Fe25Al60Si15 and Fe22Al63-52Si15-36 were

reported to be orthorhombic (a = 768, b = 1530,

c = 1600 pm), hexagonal (a = 752.6, c = 763.2

pm) and monoclinic (a = 420, b = 760, c = 1533

pm, = 89°), respectively. The crystal

structures of other phases were not reported.

The A-phase has hexagonal crystal structure

with lattice parameters varying from

a = 630±0.5, c = 941±0.7 pm at Fe15Al57Si28 to

a = 612±0.5, c = 953±0.7 pm at Fe15Al47Si38.

In the as-cast samples, the F-phase has

hexagonal structure, but its structure is different

after annealing at 600°C.


Fe Al Si

383


MSIT®

Al–Fe–Si

[1975Bar] FeAl5Si

Fe2Al8Si

25.0

31.0

62.0

61.0

13.0

8.0

These two phases were found in

Al-Fe-Mn-Mg-Si alloys. The crystal structures

of FeAl5Si and Fe2Al8Si were reported to be

monoclinic (a = b = 612, c = 4150 pm, = 91°)

and hexagonal (with P63/mmc symmetry and

a = 1230, c = 2630 pm), respectively.

[1977Cor] -(FeAlSi) 32.5 58.8 8.7 The extracted crystal of [1951Pra2] were

analyzed by X-ray diffraction using Mo-K ,

Fe-K and Cu-K radiations. The crystal

structure was reported to be hexagonal

(a = 1240.4±0.1, c = 2623.4±0.2 pm) with 44.9

atoms of Fe, 167.8 atoms of Al and 23.9 atoms

of Si and the density was reported to be

3.665 g cm-3.

[1977Hoi] -FeAlSi

'-FeAlSi

-

-

-

-

-

-

Found in an Al-0.2 mass% Fe-0.55 mass%

Mg-0.6 mass% Si alloy. -FeAlSi was present

in as-cast alloy and it transforms to '-FeAlSi

upon annealing at 580°C for 1 h. The crystal

structures of -FeAlSi and '-FeAlSi were

reported to be monoclinic (a=b=618, c=2080

pm, =91°) and hexagonal (a=1230, c=2630

pm), respectively.

[1977Sim] '-Fe5Al20Si2-Fe2Al8Si

Unknown phase

-

-

34.1

-

-

65.5

-

-

<0.5

Found in strip cast Al-0.5 mass% Fe-0.2 mass%

Si alloy. The precipitates were characterized by

TEM with EDAX analyzer. The crystal

structures of '-Fe5Al20Si2, -Fe2Al8Si and the

unknown phases were cubic (a = 1260 pm),

hexagonal and monoclinic (a = 869±6, b =

635±2, c = 632±6 pm, = 93.4°±0.5°,

isomorphous with Al9Co2), respectively.

[1979Mor] 2-FeAlSi

-FeAlSi

30.0-

33.0

25.0-

30.0

64.0-

55.0

63.0-

55.0

6.0-1

2.0

12.0-

15.0

About 80 extracted particles from the

homogenized commercial 6063 aluminium

alloy were analyzed by EDAX. The size and

Fe/Si ratio in 2-FeAlSi were found to be 3 m

and 2.75 to 5.5, respectively. Similar figures for

the -FeAlSi were 8 m and 1.6 to 2.25.

[1982Wes] '-FeAlSi

"-FeAlSi

-

-

-

-

-

-

Found in direct-chilled cast commercial purity

Al-Fe-Si alloys. The precipitates were

characterized by TEM/STEM and EDAX

analyzer. The crystal structures of '-FeAlSi

and "-FeAlSi were found to be monoclinic

(a = 890, b = 490, c = 4160 pm, = 92°) and

tetragonal (a = 1260, c = 3720 pm),

respectively. The Fe/Si ratio in ' was almost

unity and that in " was between 7 and 9.


Fe Al Si

384


MSIT®

Al–Fe–Si

[1984Don] v-FeAlSi

(Fe3Al12.4-14.6Si1.0-2.1)

31.6-

27.0

63.1-

63.5

5.3-

9.5

Found in direct-chill cast as well as heat treated

(400 to 600°C) three industrial cast alloys.

Electrical resistivity and TEM/EDAX were

performed to characterize the phases. The

crystal structure was reported to be monoclinic

(a = 847, b = 635, c = 610 pm, = 93.4°).

[1985Don1] T-FeAlSi

(Fe3Al13Si1.0-1.5)

-FeAlSi

(Fe3Al13Si1.0-2.0)

30.6-

29.9

29.2-

30.7

64.2-

62.6

61.0-

64.2

5.2-

7.5

9.8-

5.1

Found in both strip cast and direct-chill cast of

10 commercial Al-alloys which were heat

treated between 400 to 600°C. The precipitates

were analyzed by TEM and the crystal

structures of T-FeAlSi and -FeAlSi reported

to be c-centered monoclinic (a = 2810, b =

3080, c = 2080 pm, = 97.74°) and bcc (a =

1250 pm).

[1985Don2] -FeAlSi

'-FeAlSi

-FeAlSi

v-FeAlSi

T-FeAlSi

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

Found in a number of strip cast alloys in the

range of Al-(0.21 to 2.98) mass% Fe-(0.06 to

1.16) mass% Si, and also after heat treatment at

450°C for 1 week.

[1985Gri] - 31.5 60.7 7.8 Found in as-cast and heat treated Al-(17 to 35)

mass% Fe (4 to 14) mass% Si alloy. The

precipitates were characterized by X-ray

diffraction and EDAX analysis.

[1985Liu],

[1986Liu1],

[1986Liu2],

[1987Liu],

[1988Liu1],

[1988Liu2]

-FeAlSi

1-FeAlSi

2-FeAlSi

25.0

25.8

27.8

69.7

70.5

68.8

5.3

3.7

3.4

Dilute Al-Fe-Si alloys with Fe/Si mass ratios of

2 and 4 were studied. Formation of the

precipitates was reported to be a function of

Fe/Si ratio, alloy purity, solidification rate and

alloy heat treatment. The composition and the

crystal structures of the phases were analyzed

by EDAX and STEM. The crystal structures of

-FeAlSi, 1-FeAlSi and 2-FeAlSi were found

to be bcc (a = 1256 pm), c-centered

orthorhombic (with Cmmm symmetry and a =

1270, b = 3620, c = 1270 pm) and monoclinic

(with Pm symmetry and a = 1250, b = 1230, c =

1930 pm, = 109°), respectively. In the

commercial alloy with Fe/Si ratio of 2,

1-FeAlSi transformed to 2-FeAlSi upon

annealing at 600°C. But in a high purity alloy

with Fe/Si ratio of 2, neither 1 nor 2-FeAlSi

formed, and -FeAlSi persisted even after

prolonged annealing at 600°C.

[1985Suz] -FeAlSi

-FeAlSi

32.0

27.0

60.0

59.0

8.0

14.0

The and crystals were extracted from Al-4

mass% Fe-5 mass% Si and Al-4 mass% Fe-10

mass% Si ingots, respectively, which were heat

treated at 590 to 640°C for 1 h. The precipitates

were characterized by EPMA, X-ray diffraction

and Mössbauer spectroscopy.


Fe Al Si

385


MSIT®

Al–Fe–Si

[1986Dun] -FeAlSi

-FeAlSi

-

-

-

-

-

-

The and phases were observed after

complete crystallization of an Fe14Al74Si12

amorphous alloy obtained by melt-spinning

(cooling rate: ~1.5 106 °C/s).

[1987Cha],

[1988Cha]

- 27.0-

19.0

73.0-

78.0

0.0-

3.0

Found in Al-6 mass% Fe alloy which was

atomized and extruded at 400°C. The crystal

structure of the metastable phase was reported

to be rhombohedral (with R3c or R3c symmetry,

a = 890 pm, = 111.8°) or hexagonal (a =

1470, c = 780 pm). The above phase was not

present after a heat treatment at 450°C for 54 h.

[1987Czi] -FeAlSi

‘-FeAlSi

-FeAlSi

-

-

-

-

-

-

-

-

-

Investigated microstructures of direct-chill cast

and heat treated alloys: Al-0.58 mass% Fe-0.28

mass% Si and Al-0.54 mass% Fe-0.95 mass%

Si. The as-cast microstructure of first alloy

contains - and '-AlFeSi precipitates having

hexagonal and cubic structure, respectively. The

as-cast microstructure of first alloy contains

-AlFeSi precipitates. Isothermal heat treatment

at 350, 400, 450, 530 and 600°C resulted in the

formation of Fe4Al13 and FeAl6 precipitates.

[1987Gri2] H-FeAlSi 33.5 58.5 8.0 Alloys close to the composition of Fe2Al8Si

were prepared and annealed at 600°C for 1

month. X-ray powder diffraction and EPMA

were used to characterize the phase. The

hexagonal structure (a = 1240.56±0.7, c =

2623.6±0.2 pm and P6c/mmc symmetry) was

confirmed. The details of the powder diffraction

data were also presented.

[1987Nag] C-FeAlSi

H-FeAlSi

-

-

-

-

-

-

A number of ternary alloys in direct-chill cast

state and heat treated (450 to 620°C) were

investigated by means of X-ray diffraction,

EPMA and Mössbauer spectroscopy.

C-FeAlSi was reported to be metastable and

decomposes into Fe4Al13 and Si, which in turn

react to form H-FeAlSi.

[1987Skj1] "-FeAlSi 30.9-

32.5

65.4-

63.3

3.7-

4.2

Found in direct-chill casting of Al-0.25 mass%

Fe-0.13 mass% Si alloy. The precipitates were

analyzed by EDAX, TEM and HREM. The

crystal structure was reported to be c-centered

orthorhombic (a=1300, b=3600, c=1260 pm).

[1987Ste] -FeAlSi

-FeAlSi

-FeAlSi

2-FeAlSi

28.0-

36.0

25.0-

28.0

31.0-

37.0

40.0-

42.0

66.0-

51.0

62.0-

56.0

60.0-

45.0

48.0-

42.0

6.0-

13.0

13.0-

16.0

9.0-

18.0

12.0-

16.0

Alloys up to 20 to 35 mass% Fe and 4 to 14

mass% Si were investigated. As-cast alloys

were reported to contain some non-equilibrium

phases. The compositions of the ternary phases

were found to depend on the heat treatment. The

precipitates were analyzed by means of X-ray

diffraction and electron probe microanalysis.


Fe Al Si

386


MSIT®

Al–Fe–Si

[1987Tur] -FeAlSi

C-FeAlSi

Hexagonal

Rhombohedral

-

-

-

-

-

-

-

-

-

-

-

-

-FeAlSi (having cubic structure) formed in an

Al-0.5 mass% Fe-1 mass% Si alloy, whereas

C-FeAlSi, hexagonal and rhombohedral

phases formed in an Al-0.5 mass% Fe-0.2

mass% Si alloy. The lattice parameters of latter

three phases were a = 1256 pm; a = 1776, c =

1088 pm; a = 2082 pm and = 95.2°,

respectively.

[1988Ben2] -FeAlSi

'-FeAlSi

''-FeAlSi

-

-

-

-

-

-

Decomposition of rapidly solidified Al-(10 to

14) mass% Fe-2 mass% Si alloys were

investigated by TEM. -FeAlSi forms from an

amorphous phase at 380°C and was reported to

be metastable and decomposes into '-FeAlSi

and "-FeAlSi superlattices above 430°C. The

crystal structures of -FeAlSi, '-FeAlSi and

"-FeAlSi were reported to be cubic (a = 1250

pm), rhombohedral (with R3 symmetry and a

= 2080, = 95.2°) or c-hexagonal (a = 2080, c

= 3260 pm) and trigonal (with P3 symmetry and

a = 1776, c = 1088 pm), respectively.

[1988Zak] -FeAl5Si

-FeAl4Si2

25.9-

26.6

25.9-

27.8

61.3-

60.1

48.8-

45.8

12.8-

13.3

25.3-

26.4

-FeAl5Si has monoclinic structure and

-Fe4Si2 has tetragonal structures and their

densities are 3.61 and 3.36 g cm-3, respectively.

[1993Car] -Fe3Al10Si2 - - - -Fe3Al10Si2 has B-face centered orthorhombic

structure with lattice parameters a = 618.4, b =

625, c = 2069 pm. The approximate

composition corresponds to the EDS data.

However, based on the density data of

[1950Phr] and measured unit cell volume, the

proposed formula is Fe2Al5Si

[1994Mur]

[1996Mur]

-FeAl5Si 19.5-

26.8

57.3-

67.9

12.5-

15.8

Observed in Al-7Si-0.3Mg-0.6Fe,

Al-7Si-0.3Mg-0.8Fe,

Al-7Si-0.3Mg-0.64Fe-0.27Be and

Al-7Si-0.3Mg-1Fe-0.26Be (mass%) alloys.

The density of -phase is 3.29 g cm-3.

[1996Mul] -Fe2Al8Si

-FeAl5Si

31.7

25.1

60.0

61.9

8.3

13.0

The and phases were observed in an Al-0.29

mass% Fe-0.58 mass% Si-0.58 mass% Mg

alloy. -Fe2Al8Si forms by L

(Al) + -Fe2Al8Si, and -FeAl5Si forms by

L+ -Fe2Al8Si (Al)+ -FeAl5Si. -Fe2Al8Si

is cubic with a = 1250 pm, and -FeAl5Si is

monoclinic with lattice parameters a = b = 612

pm, c = 4150 pm and = 91°.

[1999Cho] -FeAl4Si2 25.9- 61.3- Observed in Al-8 mass% Fe-20 mass% Si and

Al-5 mass% Fe-30 mass% Si alloys, cooled at

about 10°C/min. -FeAl4Si2 has tetragonal

structure, and it transforms to equilibrium

Fe2Al9Si2 phase at 500°C.


Fe Al Si

387


MSIT®

Al–Fe–Si


[2000Sri] -Fe2Al8Si

'-(Fe,Al,Si)

-FeAl5Si

-FeAl3Si

-FeAl9Si3FeAl4Si2

31.6

32.1

27.2

33.0-

38.0

15.0

25.4

60.6

52.9

59.3

44.0-

54.0

65.0

49.1

7.8

8.7

13.3

13.0-

18.0

20.0

25.5

Bulk intermetallics prepared from elemental

powders by self-propagating high temperature

synthesis. However, only -Fe2Al8Si and

FeAl4Si2 were single phase.

[2000Zhe] -(Fe-Al-Si) - - - Observed in Al-7Si-0.3Mg-0.6Fe (mass%) alloy

prepared by [1996Mur]. They found that

-FeAl5Si is actually a multiphase composite.

An A-centered orthorhombic phase (space

group Cmcm, #63) with a=618, b=620 and

c=2080 pm was observed.

[2001Hsu] C-FeAlSi - - - Observed in a model 6xxx alloy containing 0.3

mass% Fe, 0.6 mass% Si and 0.8 mass% Mg.

Cubic C-FeAlSi may form by L+Fe4Al13

(Al)+ C-FeAlSi and L (Al)+ C-FeAlSi. The

atomic ratio Al:Fe:Si in C-FeAlSi may vary

from 7:4:1 to 9:5:1.

[2001Kre] 1/ 9: Fe3(Al0.4Si0.6)5

2: Fe2(Al1-xSix)7

0.2 < x < 0.33

3: FeAl2.25Si0.75

4: FeAl3Si2

5: Fe2Al7.4Si

6: FeAl4.5Si

7: FeAl1.5Si1.5

8: FeAl0.67Si1.33

10: Fe5Al12Si3

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

-

All ternary phases exist at 550°C. Previously

reported 1 and 9 [1992Gho] are established as

one phase with large homogeneity range.

[2001Sha] -FeAlSi

-FeAlSi

-

-

-

-

-

-

Observed in a model 6xxx alloy containing 0.3

mass% Fe, 0.6 mass% Si and 0.8 mass% Mg.

-FeAlSi may be simple cubic with a = 1252

pm, or bcc with a = 1256 pm. -FeAlSi is

monoclinic. They may form by the following

reactions: L+Fe4Al13 (Al)+ -FeAlSi, L (Al)+

-FeAlSi, and L+ -FeAlSi (Al)+ -FeAlSi.

-FeAlSi is metastable.

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

(Al)

660.452

cF4

Fm3m

Cu

a = 404.88 pure Al at 24°C [V-C]

( Fe)

1538

cI2

Im3m

W

a = 286.65 pure Fe at 20°C [V-C]


Fe Al Si

388


MSIT®

Al–Fe–Si

(Si)

1414

cF8

Fm3m

C-diamond

a = 543.088

a = 542.86

at 20°C and 99.999 at.% purity [V-C]

at 20°C and 99.97 at.% purity [V-C]

1, Fe3Al

552.5

cF16

Fm3m

BiF3

a = 578.86 to 579.3 [2003Pis], solid solubility

ranges from 22.5 to 36.5 at.% Al

2, FeAl

1310

cP2

Pm3m

CsCl

a = 289.76 to 290.78 [2003Pis], at room temperature solid

solubility ranges


, Fe2Al31102-1232

cI16? a = 598.0 [2003Pis], solid solubility ranges


FeAl2 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

[2003Pis], at 66.9 at.% Al



, Fe2Al5 1169

oC24

Cmcm

a = 765.59

b = 641.54

c = 421.84

[2003Pis], at 71.5 at.% Al

solid solubility

ranges from 71.0 to 72.5 at.% Al.

Fe4Al13

1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

[2003Pis], 74.16 to 76.7 at. % Al



[2003Pis], at 76.0 at.% Al.

Also denoted FeAl3 or Fe2Al7

1, Fe3Si

1235

cF16

Fm3m

BiF3

a = 565.54 [V-C]; 11.0 to 30.5 at.% Si

[Mas]

2

1280

cP2

Pm3m

CsCl

- 10.0 to 23.5 at.% Si [Mas]

Fe2Si

1212-1040

hP6

P63/mmc

Fe2Si

a = 405.2

c = 508.55

[V-C]; 33.0 to 34.5 at.% Si

[Mas]

Fe5Si31060-825

hP16

P63/mmc

Mn5Si3

a = 675.52

c = 471.74

[V-C]

FeSi

1410

cP8

P213

FeSi

a = 448.91 [V-C]; 49.0 to 51.0 at.% Si

[Mas]

FeSi2(h)

1220-937

tP3

P4/mmm

FeSi2

a = 269.5

c = 509.0

[V-C]; 69.5 to 73.0 at.% Si

[Mas]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

389


MSIT®

Al–Fe–Si

FeSi2(r)

982

oC48

FeSi2

a = 986.3

b = 779.1

c = 783.3

[V-C]

* 1/ 9,

Fe3Al2Si3

-

aP16

P1

Fe3Al2Si3

-

a = 465.1

b = 632.6

c = 749.9

= 101.37°

= 105.92°

= 101.23°

a = 462.3

b = 637.4

c = 759.9

= 102.81°

= 105.6°

= 100.85°

a = 469.1

b = 632.5

c = 751.1

= 100.6°

= 105.5°

= 101.78°

a = 468.7

b = 633.1

c = 751.9

= 100.43°

= 105.44°

= 101.63°

[1940Tak], likely to correspond to the

E-phase of [1974Mur] and [1981Zar].

D-phase of [1981Zar] and 9 of

[1992Gho].

[1996Yan], Fe3Al2Si3 annealed at 600°C

[2001Kre], at Fe38.2Al29Si32.8

[2001Kre], at Fe38Al35Si27


* 2, -AlFeSi,

Fe2Al5Si2

-

c**

mC*

m**

-

a = 1603.23

a = 890.0

b = 1025.0

c = 1780.0

= 132.0°

a = 889.3

b = 1018.8

c = 1766.9

= 132.18°

a = 420.0

b = 760.0

c = 1533.0

= 89.0°

at Fe6Al12Si6 [1940Tak]

[1952Arm, 1955Arm], in an Al-35.3

mass% Fe-12.8 mass% Si alloy

[1967Mun],

Fe19.4-23Al59-61.4 Si27.6-15.6 and is likely

to correspond to the K-phase of

[1974Mur] and [1981Zar]


[1974Mur, 1981Zar]. K-phase at

Fe22Al63-52Si15-26.

Annealed at 600°C.

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

390


MSIT®

Al–Fe–Si

* 3,

Fe5Al9Si5,

FeAl2Si

-

oC128

Cmma

FeAl2Si

-

a = 768.0

b = 1530.0

c = 1600.0

a = 799.5

b = 1516.2

c = 1522.0

a = 726.2

b = 1551.2

c = 1550.6

a = 795.8

b = 1517.8

c = 1523.7

[1940Tak], likely to correspond to the

G-phase of [1974Mur] and [1981Zar]

[1974Mur, 1981Zar], G-phase at

FeAl2Si. Annealed at 600°C.

[1989Ger2] at 600°C,

Fe25Al50Si25



* 4, -AlFeSi,

FeAl3Si2 tI24

I4/mcm

PdGa5

a = 607.0

c = 950.0

a = 615.0

c = 947.0

a = 612.23

c = 947.91

a = 612.23

c = 948.91

a = 612.0

c = 953.0

a = 630.0

c = 941.0

a = 606.1

c = 952.5

a = 608.74

c = 951.36

[1940Tak], at FeAl3Si

[1969Pan], annealed at 800°C

for 14 h and water quenched.

[1936Jae], at FeAl4Si2. In an

Al-27.04Fe-25.01Si (mass%) alloy

[1950Phr], an Al-15 mass%

Fe-20 mass% Si alloy

[1954Spi]

[1974Mur, 1981Zar], A-phase

at FeAl2.76Si2.24. Annealed at 600°C.

[1974Mur, 1981Zar], A-phase at

FeAl3.35Si1.65. Annealed at 600°C.

[1995Gue1]

[2001Kre], at Fe16.9Al49.5Si33.3. Single

phase at 700°C.

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

391


MSIT®

Al–Fe–Si

* 5, -AlFeSi,

Fe2AL7.4Si

Fe46(Al0.875Si0.125)200-x

x 7

-

hP245

P63/mmc

Fe2Al7.4Si

-

a = 1240.4

c = 2623.4

a = 1240.56

c = 2623.6

a = 1239.4

c = 2621.0

a = 1239.2

c = 2619.3

a = 1241.0

c = 2626.4

a = 1230.0

c = 2630.0

a = 1230.0

c = 2630.0

a = 1230.0

c = 2620.0

a = 1230.0

c = 2630.0

a = 1240.06

c = 2622.41

a = 1238.9

c = 2625.5

a = 1239.86

c = 2621.9

[1940Tak], at Fe6Al15Si5[1977Cor], at Fe1.9Al7.1Si. Likely to

correspond to the M-phase of [1974Mur]

and [1981Zar].

[1987Gri2], at Fe2.1Al7.6Si.

Annealed at 600°C for a month.

[1987Gri2], 9.5 ± 5 mass% Si in 5.


[1987Gri2], 9.0 ± 5 mass% Si in 5.


[1987Gri2], 7.0 ± 4 mass% Si in 5.


[1975Bar], at Fe1.95Al7.93Si

[1953Rob]

[1967Mun]

[1977Hoi]

[1997Vyb], at Fe19.2Al71.2Si9.6



Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

392


MSIT®

Al–Fe–Si

* 6, -AlFeSi

Fe2Al9Si2

-

C2/c

mC52

Fe2Al9Si2

oC?

Cmcm

t**

-

-

a = 612.23

b = 612.23

c = 4148.36

= 91.0°

a = 612.23

b = 612.23

c = 4148.36

= 91.0°

a = 612.2

b = 612.2

c = 4148.4

= 91.0°

a = 612.0

b = 612.0

c = 4150.0

= 91.0°

a = 2081.3

b = 617.5

c = 616.1

= 90.42°

a = 612

b = 612

c = 4150

= 91°

a = 579.2

b = 1227.3

c = 431.3

= 98.9°

a = 615.59 to 620.89

b = 616.87 to 619.78

c = 2076.7 to 2081.2

= 90.1° to 90.6°

a = 2079.7

b = 616.9

c = 616.87

= 90.01°

a = 2082.7

b = 616.6

c = 616.71

= 90.01°

a = 618.4

b = 625.0

c = 2069.0

a = 618.0

b = 620.0

c = 2080.0

a = 618.0

c = 4250.0

[1940Tak], at FeAl4Si

[1950Phr], Fe2Al9Si2. Composition may

vary from 27.2 to 27.4 mass% Fe and

13.5 to 13.6 mass% Si. Likely to

correspond to the L-phase of [1974Mur]

and [1981Zar].

[1954Spi]

[1955Obi]

[1975Bar], at Fe2Al10.26Si2.06

[1994Rom]

[1996Mul], at Fe14Al71.6Si14.4

[1994Mur, 1996Mur]

[1997Vyb]

[2001Kre], at Fe15Al68.5Si16.5


[1993Car]

[2000Zhe]

[1955Bla], at Fe2Al8.98Si2

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

393


MSIT®

Al–Fe–Si

Table 3: Classification of Metastable Phases Based on the Crystal System

* 7,

Fe22Al40Si38

Fe(Al0.5Si0.5)3

P21/c

mP64

Fe2Al3Si3

-

a = 717.9

b = 835.4

c = 1445.5

= 93.8

a = 718.9

b = 831.7

c = 1454.2

= 93.48

[1974Mur, 1981Zar], B-phase.

Annelaed at 600°C.

[1995Gue2] at 800°C

[2001Kre] at Fe25.3Al45Si29.7

* 8,

Fe3Al2Si4,

Fe(Al0.33Si0.67)2

oC36

Cmcm

Fe3Al2Si4

-

a = 366.8

b = 1238.5

c = 1014.7

a = 366.7

b = 1236.2

c = 1014.0

[1974Mur, 1981Zar], C-phase.

Fe32Al38Si30 Annealed at 600°C.

[1996Yan], at Fe3Al2Si4 annealed at

500°C

[2001Kre]

* 10,

Fe5Al12Si3Fe(Al0.8Si0.2)3

hP26 or

hP28

P63/mmc

Mn3Al10 or

Co2Al5

a = 752.6

c = 763.2

a = 750.9

c = 759.4

a = 1551.8

c = 729.7

[1974Mur, 1981Zar], F-phase in the

as-cast sample. The crystal structure of

F-phase after annealing at 600°C is

different from that in the as-cast samples.

[1989Ger1], at Fe1.7Al4Si


Phase

Designation

Crystal

System

Composition (mass%) Lattice

Parameters [pm]

References

Fe Al Si

1 Cubic 25.4

31.9

27.3

-

30.2- 32.8

31.9

-

31.1

-

29.2-30.7

25.0

-

-

49.1

62.5

65.7

-

58.1- 60.0

61.7

-

60.8

-

61.0-64.2

69.7

-

-

25.5

5.6

7.0

-

11.7- 7.2

6.4

-

8.1

-

9.8- 5.1

5.3

-

-

-

a = 1254.83

a = 1254.83

a = 1254.53

a = 1254.8

a = 1256.0

a = 1250 to 1270

a = 1250±10

a = 1260.0

a = 1250

a = 1256.0

a = 1256.0

a = 1250

a = 1250

[1937Ser]

[1950Phr]

[1952Arm], [1955Arm]

[1954Spi]

[1955Obi]

[1967Coo]

[1967Mun]

[1967Sun]

[1977Sim]

[1985Don1]

[1986Liu1, 1986Liu2, 1987Liu]

[1987Tur]

[1988Ben2]

[1996Mul]

2 Tetra-

gonal

-

-

-

-

-

-

a = 495.0

c = 707.0

a = 1260.0

c = 3720.0

[1951Now]

[1982Wes]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

394


MSIT®

Al–Fe–Si

3 Ortho-

rhombic

-

29.2

25.8

30.9-32.5

-

59.5

70.5

65.4-63.3

-

11.3

3.7

3.7- 4.2

a = 609.0

b = 996.0

c = 374.0

a = 4360.0

b = 4960.0

c = 7080.0

a = 1270.0

b = 3620.0

c = 1270.0

a = 1300.0

b = 3600.0

c = 1260.0

[1936Jae]

[1952Arm], [1955Arm],

[1967Mun]

[1986Liu1], [1986Liu2],

[1987Liu]

[1987Skj1]

4 Rhombo-

hedral

27.0-19.0

-

-

73.0-78.0

-

-

0.0- 3.0

-

-

a = 890.0

= 111.8°

a = 2082.0

= 95.2°

a = 2080.0

= 95.2°

[1987Cha], [1988Cha]

[1987Tur]

[1988Ben2]

5 Hexagonal -

29.2

27.0-19.0

-

-

-

59.5

73.0-78.0

-

-

-

11.3

0.0-3.0

-

-

a = 836.0

c = 1458.0

a = 496.0

c = 702.1

a = 1470.0

c = 780.0

a = 1776.0

c = 1088.0

a = 1776.0

c = 1088.0

[1936Jae]

[1952Arm], [1955Arm],

[1967Mun]

[1987Cha], [1988Cha]

[1987Tur]

[1988Ben2]

Phase

Designation

Crystal

System


Parameters [pm]

References

Fe Al Si

395


MSIT®

Al–Fe–Si


6 Mono-

clinic

32.1-32.7

-

34.1

-

31.6-27.0

30.6-29.9

27.8

59.5-57.0

-

65.5

-

63.1-63.5

64.2-62.6

68.8

8.4-10.3

-

< 0.5

-

5.3- 9.5

5.2- 7.5

3.4

-

a = 618.0

b = 618.0

c = 2080.0

= 91.0°

a = 869.0 ± 6

b = 635.0 ± 2

c = 632.0 ± 6

= 93.4 ± 0.5°

a = 890.0

b = 490.0

c = 4160.0

= 90.0°

a = 847.0

b = 635.0

c = 610.0

= 93.4°

a = 2810.0

b = 3080.0

c = 2080.0

= 97.74°

a = 1250.0

b = 1230.0

c = 1930.0

= 109.0°

[1951Pra2]

[1977Hoi]

[1977Sim]

[1982Wes]

[1984Don]

[1985Don1]

[1986Liu1], [1986Liu2],

[1987Liu]

7 Triclinic - - - a = 688.0

b = 593.0

c = 432.0

= 104.75°

= 130.67°

= 68.4°

[1936Jae]

Reaction T [°C] Type Phase Composition (mass%)

Fe Al Si

L + Fe2Si 1 + FeSi 1180 U1 - - - -

L + 2 + Fe2Al5 1120 U2 L

, Fe2Al3

2

Fe2Al5

51.0

56.5

58.0

45.0

46.0

43.0

28.0

52.0

3.0

0.5

14.0

3.0

L + 1 + FeSi 1 1050 P1 L

1

FeSi

1

50.0

63.0

66.3

55.0

31.0

26.0

0.4

26.6

19.0

11.0

33.3

18.4

L + 2 Fe2Al5 + 1 1030 U3 L

2

Fe2Al5

1

48.5

65.0

45.0

55.0

37.5

25.0

52.5

26.6

14.0

10.0

2.5

18.4

Phase

Designation

Crystal

System


Parameters [pm]

References

Fe Al Si

396


MSIT®

Al–Fe–Si

L + Fe2Al5 Fe4Al13 + 1 1020 U4 L

Fe2Al5Fe4Al13

1

48.0

45.0

39.2

55.0

38.0

52.5

60.0

26.6

14.0

2.5

0.8

18.4

L + FeSi FeSi2(h) + 1 1000 U5 L

FeSi

FeSi2(h)

1

42.0

66.3

44.8

55.0

26.0

0.4

0.5

26.6

32.0

33.3

54.7

18.4

L + Fe4Al13 + 1 2 940 P2 L

Fe4Al13

1

2

40.0

39.2

55.0

41.9

41.0

60.0

26.6

40.5

19.0

0.8

18.4

17.6

L + 1 + 2 7 935 P3 L

1

2

7

39.0

55.0

41.9

42.2

39.0

26.6

40.5

36.7

22.0

18.4

17.6

21.1

L + 1 FeSi2(?) + 7 885 U6 L

1

FeSi2(?)

7

28.0

55.0

49.7

42.2

36.0

26.6

0.5

36.7

36.0

18.4

49.8

21.1

L + FeSi2(?) 7 + (Si) 880 U7 L

FeSi2(?)

7

(Si)

26.0

49.7

42.2

0.01

38.0

0.5

36.7

0.013

36.0

49.8

21.1

99.977

L + 7 + (Si) 4 865 P4 L

7

(Si)

4

23.0

42.2

0.01

28.9

45.0

36.7

0.013

41.9

32.0

21.1

99.977

29.2

L + Fe4Al13 + 2 5 855 P5 L

Fe4Al13

2

5

25.0

39.2

41.9

38.1

58.0

60.0

40.5

46.0

17.0

0.8

17.6

15.9

L + 7 2 + 4 835 U8 L

7

2

4

22.0

42.2

41.9

28.9

56.0

36.7

40.5

41.9

22.0

21.1

17.6

29.2

L + 2 4 + 5 790 U9 L

2

4

5

18.0

41.9

28.9

38.1

61.0

40.5

41.9

46.0

21.0

17.6

29.2

15.9

L + 4 + 5 6 700 P6 L

4

5

6

7.2

28.9

38.1

29.1

78.8

41.9

46.0

56.3

14.0

29.2

15.9

14.6

L + Fe4Al13 (Al) + 5 632 U10 L

Fe4Al13

(Al)

5

2.0

39.2

0.05

38.1

93.8

60.0

99.31

46.0

4.2

0.8

0.64

15.9


Fe Al Si

397


MSIT®

Al–Fe–Si

Table 5: Coordinates of the /( + ) and ( + )/ Phase Boundaries in the Al-Fe-Si System

L + 5 (Al) + 6 613 U11 L

5

(Al)

6

1.8

38.1

0.04

29.1

92.0

46.0

98.96

56.3

6.2

15.9

1.0

14.6

L + 4 6 + (Si) 600 U12 L

4

6

(Si)

1.5

28.9

29.1

0.01

84.2

41.9

56.3

0.012

14.3

29.2

14.6

99.978

L 6 + (Al) + (Si) 573 E1 L

6

(Al)

(Si)

0.5

29.1

0.01

0.01

87.8

56.3

98.34

0.01

11.7

14.6

1.65

99.98

Composition mass% Temperature [°C] of the

Al Si /( + ) boundary ( + )/ boundary

0.16

0.19

0.31

0.44

0.44

0.48

0.64

0.71

0.74

0.25

0.58

0.93

0.19

0.53

0.13

0.23

0.65

0.24

905

952

1014

935

976

948

1030

1048

1000

1385

1351

1300

1350

1326

1347

1275

1270

1303


Fe Al Si

20

40

60

80

20 40 60 80

20

40

60

80

Fe Al


Axes: at.%

τ1 [1940Tak]

τ2

τ3

τ4

τ5 [1940Tak]

τ6

τ7 [1974Mur, 1981Zar]

τ8 [1974Mur, 1981Zar]τ9 [1974Mur, 1981Zar]

τ5

[1974Mur, 1981Zar]

[1974Mur, 1981Zar]

[1974Mur, 1981Zar]

[1940Tak]

[1940Tak]

[1940Tak]

[1936Jae]

τ10 [1974Mur, 1981Za

[1985Gri2] [1975Bar][1977Cor]

[1967Mur][1955Obi][1950Phr]

[1950Phr]

[1955Bla]

[1975Baz]

τ5 [2001Kra]

τ10 [2001Kre]

τ3 [2001Kre]

τ1/τ9 [2001Kre]

τ8 [2001Kre]τ8 [1996Yan]

[2001Kre][1988Zak]

[2001Kre, 1988Za[1996Mul]

τ7 [2001Kre]

[1974Mur, 1981Zar]

Fig. 1: Al-Fe-Si.

Distribution of the

equilibrium ternary

phases, as reported by

different authors

398


MSIT®

Al–Fe–Si

10

20

30

40

60 70 80 90

10

20

30

40

Fe 50.00Al 50.00Si 0.00

Al

Fe 0.00Al 50.00Si 50.00 Data / Grid: at.%

Axes: at.%

[1986Lin1,1986Lin2, 1987Lin][1986Lin1, 1986Lin2, 1987Lin]

µ6µ3[1987Skj1][1977Sim]

µ1

[1952Arm][1985Don1]

[1985Don1][1984Don][1950Phr]

[1967Coo][1955Obi]

[1955Obi]

µ4 or µ5[1987Cha, 1988Cha]

[1951Bra2]

µ6

[1967Sun]µ6

[1984Don]

[1952Arm, 1967Mun], µ3 or µ4

µ1

[1968Don]

µ1, [1937Ser]

10 200

250

500

750

1000

1250

1500

Fe 75.00Al 25.00Si 0.00

Fe 75.00Al 0.00Si 25.00Si, at.%

Tem

pera

ture

, °C

(αFe)

1223°C

750°C

550°C

α2(B2)

α1(DO3)

640°C

460°C

(αFe)+α1+α2

(αFe)+α1

(αFe)+α2

Fig. 2: Al-Fe-Si.

Distribution of the

metastable ternary

phases, as reported by

different authors

Fig. 3: Al-Fe-Si.

The Fe3Al-Fe3Si

sections showing the

boundaries of 1

(D03), 2 (B2) and

( Fe) (disordered

bcc) phases

399


MSIT®

Al–Fe–Si

Fig

. 4a:

Al-

Fe-

Si.R

eact

ion

schem

e, p

art

1

Al-

Fe

Fe-

Si

A-B

-CA

l-F

e-S

iA

l-S

i

l + α

2ε

12

32

p1

L+

Fe 2

Si

α 1+

FeS

ica

.11

50

U1

l F

eSi+

FeS

i 2(h

)

12

12

e 1

l F

eSi 2

(h)+

(Si)

12

07

e 2

l F

eSi+

Fe 2

Si

12

03

e 3

lα 1

+ F

e 2S

i

12

00

e 4

lη

+ε

11

65

e 5

L +

α2

η+

τ 11

030

U3

L +

η F

e 4A

l 13

+τ 1

10

20

U4

Fe 2

Si+

FeS

i F

e 5S

i 3

10

60

p3

Fe 2

Si

Fe 5

Si 3

+F

e 3S

i

10

40

e 8

FeS

i+F

eSi 2

(h)

FeS

i 2(r

)

98

2p4

FeS

i 2(h

)F

eSi 2

(r)+

(Si)

93

7e 9

ε +

η F

eAl 2

11

56

p2

lη

+ F

e 4A

l 13

11

60

e 6

εα 2

+ F

eAl 2

11

02

e 7L

+ ε

α 2+

η1

120

U2

L +

α1

+ F

eSi

τ 11

050

P1

L +

FeS

i F

eSi 2

(h)

+ τ1

10

00

U5

L+

τ 1 +

τ2

τ 79

35

P3

L +

Fe 4

Al 13

+τ 1

τ 29

40

P2

L +

τ1

FeS

i 2(r

) +

τ7

88

5U6

L+

α 1+

FeS

iF

eSi+

α 1+

Fe 2

Si

L+

α 2+

ηε+

α 2+

η

α 1+

FeS

i+τ 1

L+

FeS

i+τ 1

FeS

i+F

eSi 2

(h)+

τ 1

L+

FeS

i 2(r

)+τ 7

τ 1+

FeS

i 2(r

)+τ 7

L+

τ 2+

τ 7

τ 7+τ

1+

τ 2

Fe 4

Al 13+L

+τ 2

Fe 4

Al 1

3+L

+τ 1

Fe 4

Al 13+η

+τ 1

α 2+η

+τ 1

η+L

+τ 1L

+α 1

+τ 1

L+

τ 1+

τ 2

L+

τ 1+

τ 7

L+

FeS

i 2(h

)+τ 1

Fe 4

Al 13+

τ 1+

τ 2

400


MSIT®

Al–Fe–Si

Fig

. 4b:

Al-

Fe-

Si.R

eact

ion s

chem

e, p

art

2

Al-

Fe

Fe-

Si

A-B

-CA

l-F

e-S

iA

l-S

i

L +

FeS

i 2(r

)τ 7

+ (

Si)

88

0U7

L +

τ7

+ (

Si)

τ 4

86

5P4

L +

τ7

τ 2+

τ 48

35

U8

L +

Fe 4

Al 13

+τ 2

τ 58

55

P5

L +

τ2

τ 4+

τ 57

90

U9

L +

τ4

+τ 5

τ 67

00

P6

l F

e 4A

l 13

+ (

Al)

65

5e 11

L +

Fe 4

Al 13

(A

l) +

τ5

63

2U10

L +

τ5

(A

l) +

τ6

61

3U11

L +

τ4

τ 6+

(S

i)6

00

U12

Lτ 6

+ (

Al)

+ (

Si)

57

3E1

l (

Al)

+ (

Si)

57

7e 12

Fe 5

Si 3

α 2+

FeS

i

82

5e 10

L+

(Al)

+τ 6

τ 5+

(Al)

+τ 6

τ 6+

(Al)

+(S

i)

τ 4+

τ 6+

(Si)

L+

τ 6+

(Si)

FeS

i 2(r

)+τ 7

+(S

i)L

+τ 7

+(S

i)

τ 7+

(Si)

+τ 4 τ 7

+τ 2

+τ 4

τ 2+

τ 4+

τ 5L

+τ 2

+τ 5

L+

τ 7+

τ 4

L+

(Si)

+τ 4

Fe 4

Al 13+

(Al)

+τ 5

L+

(Al)

+τ 5

L+

τ 4+

τ 6L

+τ 5

+τ 6

τ 4+

τ 5+

τ 6

Fe 4

Al 13+

τ 2+

τ 5L

+τ 2

+τ 5

L+

FeS

i 2(h

)+(S

i)L

+F

eSi 2

(r)+

τ 7

L+

τ 2+

τ 7

L+

τ 2+

Fe 4

Al 13

L+

Fe 4

Al 13+

τ 5L+

τ 2+

τ 4

401


MSIT®

Al–Fe–Si

Si, mass%

Fe,mass%

2

0

Al10

2

3

4

5

6

0

1

4 6 8 12 14 16

(Al)

650°C

660°C

670°C680°C

690°C

700°C

710°C720°C730°C740°C750°C760°C770°C780°C

640°C

620°C

620°C

610°C

610°C

600°C

590°C

580°C

630°C

(Si)

U11

P6

U12

E1

U10

Fe Al 13

4 �5

�2

�6

�4

20

40

60

80

20 40 60 80

20

40

60

80

Fe Al


Axes: at.%

1400

1350

1300

12501207°C,e2

FeSi2(h)

1212°C, e1

(Si)

1050

1000950

900P4

U7

τ1

U5

P1

U3

P2

U8τ7

U9P5τ2

U6

900

U4

τ5

τ6

(Al)U10

U11

P6 U12e12

700

750800

850

U2

Fe2 Al

5

Fe4 Al

13

τ4

655°C,e11

13501300 1250 1150

FeSi

Fe2Si U1

α2

1300

1350

1200

1100

1200°C, e4

1203°C, e3

1400

1500

1232°C, p1 1165°C, e5 1160°C, e6

(αFe)

α2

α1

ε

E1

P3

1200

Fig. 6: Al-Fe-Si.

Liquidus surface

Fig. 5: Al-Fe-Si.

Calculated liquidus

surface of Al-corner

[1999Liu]

402


MSIT®

Al–Fe–Si

10

90

10

Fe 20.00Al 80.00Si 0.00

Al


Axes: at.%

L+τ4

L+τ4+τ6

L+τ6

L+τ5+τ6

L+τ5

L

L+Fe4Al13+τ5

L+Fe4Al13

L+(Al)

L+(Al)+Fe4Al13(Al)

(Al)+Fe4Al13

20

40

60

80

20 40 60 80

20

40

60

80

Fe Al


Axes: at.%

FeSi2(h)+L+(Si)

L+(Si)

L

L+FeSi2(h)FeSi

2 (h)+L+τ1

FeSi2(h)

FeSi2 (h)+τ

1 +FeSi

L+τ1

τ1

τ1 +η+α

2

L+Fe4Al13

τ1+L+Fe4Al13

Fe4Al13

Fe4Al13+τ1+Fe2Al5

FeAl2 η

α2+η

α1+τ1

α2

α1+FeSi

α1+Fe5Si3+FeSiFeSi+τ

1 +α1

FeSi

Fe5Si3

α1+Fe5Si3

(γFe) (γFe)+(αFe)

(αFe)

α1

Fig. 7: Al-Fe-Si.

Isothermal section

at 1000°C

Fig. 8: Al-Fe-Si.


the Al-corner

at 640°C

403


MSIT®

Al–Fe–Si

20

40

60

80

20 40 60 80

20

40

60

80

Fe Al


Axes: at.%

Fe4Al13ηFeAl2(αFe)+α2

α2

α1+α2

FeSi

FeSi2

(Si)+FeSi2

(Si)

(Al)+(Si)

(Al)

(Al)+(Si)+τ

4

τ4 +τ

7 +(Si)

(Si)+FeSi2 +τ7

τ7+τ8+FeSi2τ8+FeSi2+FeSi

τ1/τ9+FeSi+α2

(αFe)+α1

(αFe)

α1

α2

α2+τ1/τ9+η

FeAl2+α2 (Al)+τ5+Fe4Al13

(Al)+τ6+τ4τ6

τ5

τ10

τ2

τ7

τ3

τ1/τ9

α1+FeSiτ4

τ8

τ1 /τ

9 +τ8 +τ

10

τ1 /τ

9 +FeSi+τ8

10

20

30

70 80 90

10

20

30

Fe 40.00Al 60.00Si 0.00

Al


Axes: at.%

τ2

τ5

Fe4Al13

(Al)+Fe4Al13+τ5

(Al)

(Al)+τ6+(Si)(Al)+τ5+τ6

τ6

Fig. 10: Al-Fe-Si.

Isothermal section

at 600°C

Fig. 9: Al-Fe-Si.


the Al-corner

at 570°/600°C, see

text

404


MSIT®

Al–Fe–Si

Fe 1.00Al 99.00Si 0.00

Al


Axes: at.%

(Al)+τ6+(Si)

(Al)+(Si)

(Al)

(Al)+τ5

(Al)+τ5+τ6

(Al)+τ6

(Al)+Fe4Al13

(Al)+τ5+Fe4Al13

20

40

60

80

20 40 60 80

20

40

60

80

Fe Al


Axes: at.%

(Al)+(Si)+τ

6

τ6α2

τ8

FeSi2

FeSi

ηFeAl2 Fe4Al13

τ4τ1/τ9 τ7

τ2

τ3τ10 τ5

FeSi+FeSi2+τ

8 (Si)+τ8+τ7

(Si)+τ7 +τ

4

(Si)

(Al)

FeSi

2+τ

8+(

Si)

Fig. 12: Al-Fe-Si.


the Al-corner

at 500°C

Fig. 11: Al-Fe-Si.

Partial isothermal

section at 550°C

405


MSIT®

Al–Fe–Si

70

80

90

10 20 30

10

20

30

Fe Fe 60.00Al 40.00Si 0.00


Axes: at.%

(αFe)

(αFe)+α1

α2 α1+α2

α1+α2

α1 α2

70

80

90

10 20 30

10

20

30

Fe Fe 60.00Al 40.00Si 0.00


Axes: at.%

(αFe)α2

α1

Fig. 14: Al-Fe-Si.


the Fe-corner

at 650°C

Fig. 13: Al-Fe-Si.


the Fe-corner

at 700°C

406


MSIT®

Al–Fe–Si

70

80

90

10 20 30

10

20

30

Fe Fe 60.00Al 40.00Si 0.00


Axes: at.%

α2

α1+α2

α1

(αFe)+α1

α1+α2

(αFe)

α2

Fig. 16: Al-Fe-Si.


the Fe-corner

at 450°C

70

80

90

10 20 30

10

20

30

Fe Fe 60.00Al 40.00Si 0.00


Axes: at.%

(αFe)

α1+α2

(αFe)+α1

α1 α2

α2

Fig. 15: Al-Fe-Si.


the Fe-corner

at 550°C

407


MSIT®

Al–Fe–Si

10400

500

600

700

800

Fe 1.97Al 98.03Si 0.00

Fe 1.98Al 83.22Si 14.80Si, at.%

Tem

pera

ture

, °C

(Al)+τ6+(Si)(Al)+Fe4Al13+τ5

(Al)+Fe4Al13

(Al) +τ5

(Al)+τ5+τ6

(Al)+τ6

(Al)+L+τ6 L+τ6+(Si)

L+τ4+τ6

L+τ4

L+τ6

L+τ5+τ6

L+τ5

L+Fe4Al13+τ5(Al)+L+Fe4Al13

(Al)+τ5+L

L+Fe4Al13

L

632°C

613°C

573°C

600°C

Fig. 18: Al-Fe-Si.

Polythermal section at

a constant Fe content

of 4.0 mass%

10500

600

700

Fe 0.30Al 99.70Si 0.00

Fe 0.30Al 80.30Si 19.40Si, at.%

Tem

pera

ture

, °C

Fe4Al13+(Al)

(Al)+Fe4Al13+τ5

(Al)+τ5

(Al)+τ5+τ6

τ6+(Al)

L+τ6+(Al)

(Al)+(Si)+τ6

L+(Si)+τ6

L+(Si)+τ4

L+(Si)

L+τ5+(Al)

L+(Al)

11.33 at.%573

613

L+(Al)+Fe4Al13655°C, e11

632

L

Fig. 17: Al-Fe-Si.

Polythermal section at

a constant Fe content

of 0.7 mass%

408


MSIT®

Al–Fe–Si

400

500

600

700

Fe 2.00Al 90.10Si 7.90

Fe 0.00Al 92.30Si 7.70Al, at.%

Tem

pera

ture

, °C

LL+τ5

L+τ5+τ6

L+τ5+Fe4Al13

L+Fe4Al13

L+τ6

(Al)+L+τ6 573°CL+(Al)

(Al)+τ6+(Si)

(Al)+(Si)

L+(Al)+(Si)

91 92

Si, mass%

Fe,mass%

10-3

�

0.2

0

Al

0.4 0.6 0.80 1.0 1.2 1.4 1.6 1.8

10

15

20

25

30

35

40

45

50

5

�6

�5

(Si)

Fe Al4 13

640°C

630°C

620°C

610°C

590°C

580°C570°C

560°C550°C530°C510°C490°C470

450

600°C

Fig. 19: Al-Fe-Si.

Polythermal section

at a constant Si

content of 8.0 mass%

Fig. 20: Al-Fe-Si.

(Al)-solidus (dash

lines) and -solvus

(solid lines) surfaces,

calculated using the

dataset of [1999Liu]

409


MSIT®

Al–Fe–Si

Fe, mass%

Si,mass%

1

0

Al2 3 4 5 60

2

4

6

12

10

8

e , 577°C12

e , 655°C11

secondary (Al)

650°C

640°C

630°C

sec. FeAl3

650°C

640°C

sec. �5

U10

sec.

� 6

U11

E1

sec.

(Si)

sec. (Si)

sec. �6

tern. (Si)

640°C

650°C

660°C

660°C

tern. �6

sec. �6

670°C

620°

C

sec.

� 5

620°C

600°C

590°C

600°C

580°C

590°C

sec. (Al)

sec. (Al)

tern. (Al)

630°C

secondary �5

ternary (Al)

615°C

615°C

620°C 630°C

Fig. 21: Al-Fe-Si.

Surface of secondary

crystalization of

Al-corner

410


MSIT®

Al–Fe–Sm

Aluminium – Iron – Samarium

Gabriele Cacciamani and Paola Riani

Literature Data

The Al-Fe-Sm system has been investigated only for low Sm content (0-33 at.%). Phase equilibria have

been studied by [1974Viv2] at 500°C and 0-33 at.% Sm by means of XRD and micrography.

Microstructural studies have also been performed by [1999Kub] on selected alloys homogenized at 1050°C

in the region close to the Sm2(Fe1–xAlx)17 phase.

The Sm2(Fe1–xAlx)17 phase has been widely studied. Structural and magnetic properties of this phase have

been investigated by [1976McN, 1991Wei, 1994Jia, 1995Che, 1995Yan, 1996Zar, 1998Ono, 1999Ren,

2000Kub, 2000Ren, 2001Ter]. The same properties for the R2(Fe1–xTx)17 phases with R = Rare Earth and

T = Al, Si, Ga have been recently reviewed by [2002Ram].

The structure of the binary and/or ternary Laves phases along the SmAl2-SmFe2 section has been

investigated by [1968Dwi, 1971Oes, 1973Zar, 1975Dwi].

Other phases have been investigated by [1974Viv1, 1976Bus, 1978Bus] ( 3 or Sm(Fe1–xAlx)12), [1992Hu]

( 2 or Sm6Fe11Al3), [1998Thi] ( 4 or SmFe2Al10), [2000Sam] (Sm(Fe1–xAlx)7, metastable).

Alloy samples were generally prepared by arc or induction melting the pure elements (typically 99.5% Sm

and 99.99% Fe and Al) under an inert atmosphere. Samples were then homogenized at appropriate

temperature (typically 500-1000°C) and quenched.

Amorphous alloys were also obtained by [2001Kon1, 2001Kon2] who studied also their magnetic

properties.

Binary Systems




The Al-Sm binary system is accepted from the assessment by [2003Bod], and Fe-Sm from [2000Oka]

(reporting a previous assessment by [1993Oka]). A thermodynamic assessment of the Fe-Sm system has

been recently produced by [2002Zin].

Solid Phases

Table 1 summarizes the crystal structure data relevant to all the Al-Fe-Sm solid phases. Four ternary phases

and several binary-based solid solutions have been identified in the system. Most of them show quite

extended line solubility due to the mutual substitution between Fe and Al (at constant Sm concentration).

The ternary Laves phase 1 shows the MgZn2 type structure [1968Dwi, 1973Zar, 1975Dwi] (not detected

by [1971Oes]), different from the binary solid solutions Sm(Al1–xFex)2 and Sm(Fe1–xAlx)2 belonging to the

MgCu2 type. The solubility ranges of the three phases have been investigated by [1974Viv2, 1975Dwi].

2 has been identified by [1992Hu] by powder XRD (Debye-Sherrer and Guinier-Huber methods) in

samples annealed at 800°C and quenched. No solid solubility has been reported.

The structure of 3 has been mainly studied at the SmFe4Al8 composition [1976Bus]. Its solubility range

has been determined by [1974Viv2].

4 has been identified by [1998Thi]. It does not show any solid solubility.

Structural properties of Sm2(Fe1–xAlx)17 have been studied, as a function of the Al concentration, by several

authors, generally at temperatures where the Th2Zn17 type structure is stable. Single crystal [1998Ono] and

Rietveld refinement [2001Ter] have been carried out. The ternary solubility of the high temperature form

(Ni2Th17 type), however has not been determined.

A metastable phase, Sm(Fe1–xAlx)7, has been obtained by [2000Sam]; its tetragonal structure is similar to

Sm2Fe14B with empty boron sites.

411


MSIT®

Al–Fe–Sm

Isothermal Sections

[1974Viv2] determined the Al-Fe-Sm isothermal section at 500°C in the 0-33 at.% Sm composition range.

It is presented in Fig. 1, slightly adapted in order to be consistent with the accepted binary systems (Sm3Al11

was not included in the original section). The 2 phase, identified by [1992Hu] in samples annealed at higher

temperature, is not reported in this section.


Magnetic properties such as coercive force, TC, magnetic anisotropy, etc. of Sm2(Fe1–xAlx)17 have been

investigated as a function of the Al concentration by several authors [1976McN, 1991Wei, 1994Jia,

1995Che, 1995Kat, 1996Kat, 1996Zar]. [1996Sab] calculated magnetic properties and site occupancies,

[1999Kub] investigated the influence of the Fe substitution by Al on the microstructure and the HDDR

(hydrogenation-disproportionation-desorption-recombination) process and [1998Lon] investigated the

Sm2(Fe1–xAlx)17 solid solution by Mössbauer spectroscopy: he confirmed that Al site occupancies are

independent on the R element, determined the Fe site magnetic moments and revealed an important covalent

contribution in the Al-Fe bonding. Magnetic properties of the metastable Sm(Fe1–xAlx)7 phase [2000Sam]

and of amorphous Al-Fe-Sm alloys [2000Fan, 2001Kon1, 2001Kon2] have been studied.

[1998Hag] studied the magnetic properties of the Sm(Fe1–xAlx)12, phase at the SmFe4Al8 composition and

[2003Kan] carried out an atomistic simulation of its lattice constants.

References



Experimental, 49)




[1968Dwi] Dwight, A.E., “The Crystal Chemistry of Some Scandium and Lanthanide Compounds”,

Proc.: 7th Rare Earth Res. Conf., Coronado, Calif., 1, 273-281 (1968) (Crys. Structure, 8)

[1971Bus] Buschow, K.H.J., “The Samarium-Iron System”, J. Less-Common Met., 25, 131-34 (1971)

quoted by H. Okamoto, (Equi. Diagram, Crys. Structure, Experimental)



[1973Zar] Zarechnyuk, O.S., Rykhal, R.M., Vivchar, O.I., “Laves Phases in Ternary Systems

Rare-Earth Metal - Transition Metal of the IV Period - Aluminium”, Sb. Nauchn. Rab. Inst.

Metallofiz., Akad. Nauk Ukr. SSR, 42, 92-94 (1973) (Crys. Structure, Experimental,

Review)

[1974Viv1] Vivchar, O.I., Zarechnyuk, O.S., “Compounds of the ThMn12-type Structure in R-Fe-Al

Systems” (in Russian), Tezisy Dokl.-Vses. Konf. Kristallokhim. Intermet. Soedin., Rykhal,

R.M. (Ed.), Vol. 2, Gos. Univ., Lvov, 41 (1974) (Crys. Structure, Experimental, 0)

[1974Viv2] Vivchar, O.I., Zarechnyuk, O.S; Ryabov, V.R., “The Ternary System Sm-Fe-Al in the

Range 0-33.3 at.% Sm” (in Russian), Dop. Akad. Nauk Ukrain. RSR, Ser. A, Fiz-Mat. Tekh.

Nauki, 4, 363-365 (1974) (Experimental, Crys. Structure, Equi. Diagram, *, 7)


Mössbauer Study of (Sc, Y, Ln)(Fe, Al)2 Intermetallic Compounds”, J. Less-Common Met.,





412


MSIT®

Al–Fe–Sm

[1976McN] McNeelly, D., Oesterreicher, H., “Structural and Low-Temperature Magnetic Studies on

Compounds Sm2Fe17 with Al Substitution for Fe”, J. Less-Common Met., 44, 183-193



Aluminium Compounds (RFe4Al8)”, J. Phys. F: Met. Phys., 8, 921-932 (1978) (Magn.





[1989Gle] Glebova, O.D., Domyshev, O.V., Basargin, O.V., Zakharov, A.I., “X-Ray Study of Phase

Composition and Thermal Expansion Coefficient of Sm2Fe17 Compound” (in Russian), Fiz.

Met. Metalloved., 68(3), 185-87 (1989), quoted by H. Okamoto, (Equi. Diagram, Crys.


[1991Wei] Weitzer, F., Hiebl, K., Rogl, P., “Samarium-Iron Based Magnet Materials with the

Th2Zn17-Type Structure”, J. Appl. Phys., 69(10), 7215-7218 (1991) (Crys. Structure,

Experimental, 20)


Mössbauer Spectra of Ternary RE6Fe11Al3 and RE6Fe13Ge Compounds”, J. Magn. Magn.



Alloys”, Okamoto, H. (Ed.), ASM International, Materials Park, Ohio 44073-0002, 12-28

(1993) (Review, 99)

[1993Oka] Okamoto, H., “Fe-Sm (Iron-Samarium)”, in “Phase Diagrams of Binary Iron Alloys”,

Okamoto, H. (Ed.), ASM International, Materials Park, Ohio 44073-0002, 382-84 (1993)

(Review, 17)



Crystallogr. Crys. Chem., 50B, 313-316 (1994) (Crys. Structure, Experimental, 9)




[1994Jia] Jianmin, W., Feng, L., Tai, L.C., “The Structure and Magnetic Properties of

Sm2(Fe1–xCox)17–yAly”, J. Magn. Magn. Mater., 134, 53-58 (1994) (Crys. Structure,


[1995Che] Cheng, Z., Shen, B., Liang, B., Zhang, J., Wang, F., Zhang, S., Gong, H., “The Change in

Magnetic Anisotropy in R2Fe17–xAlx Compounds (RSm or Tb)”, J. Phys.: Condensed

Matter, 7, 4707-4712 (1995) (Crys. Structure, Experimental, Magn. Prop., 16)

[1995Kat] Kato, H., Shiomi, J., Koide, T., Iriyama, T., Yamada, M., Nakagawa, Y., “High Field

Magnetization and Spin Reorientation in Sm2(Fe1–xAlx)17 Single Crystals”, J. Alloys

Compd., 222, 62-66 (1995) (Crys. Structure, Experimental, Magn. Prop., 14)

[1995Yan] Yang, F., Li, X., Tang, N., Wang, J., Lu, Z., Zhao, T., Li, Q., Liu, J.P., de Boer, F.R.,

“Magnetic Properties of Sm2Fe17Ny with Al Substituted for Fe”, J. Alloys Compd., 221,


[1996Kat] Kato, H., Knide, T., Yamada, M., Motokawa, M., Miyazaki, T., “High Field Magnetization

and Spin Reorientation in Sm2(Fe1–xAlx)17 and Nd2(Fe1–xAlx)17 Single Crystals”, Sci. Rep.

Res. Inst. Tohoku Univ. Ser. A, 42A(2), 283-288 (1996) (Experimental, Magn. Prop.)

[1996Sab] Sabirianov, R.F., Jaswal, S.S., “Electronic Structure and Magnetism in Sm2Fe17–xAx (A =

Al, Ga, Si)”, J. Appl. Phys., 79(82), 5942-44 (1996) (Crys. Structure, Experimental, Magn.

Prop.) as quoted in [C.A.] 124:358574R

[1996Zar] Zarek W., “Influence of Si, Al and C on the Crystal Structure and Magnetic Properties of

Sm2Fe17”, J. Magn. Magn. Mater., 157/158, 91-92 (1996) (Crys. Structure, Magn. Prop.,

Experimental, 8)

413


MSIT®

Al–Fe–Sm

[1997Kog] Kogachi, M., Haraguchi, T., “Quenched in Vacansies in B2-Structured Intermetallic

Compound FeAl”, Mater. Sci. Eng. A, 230A, 124-131 (1997) (Crys. Structure,

Experimental, 23)





RFe4Al8 Compounds Studied by Specific Heat Measurements”, J. Alloys Compd., 278,


[1998Lon] Long, G.J., Pringle, O.A., Ezekwenna, P.C., Mishra, S.R., Hautot, D., Grandjean, F., “A

Mössbauer Spectral Study of the Sm2Fe17–xAlx Solid Solutions”, J. Magn. Magn. Mater.,

186, L10-L20 (1998) (Crys. Structure, Experimental, Moessbauer, 22)

[1998Ono] Ono, Y., Shiomi, J., Kato, H., Iriyama, T., Kajitani, T., “X-Ray Diffraction Study of

Sm2(Fe1–xAlx)17 Single Crystals with x = 0.058, 0.081”, J. Magn. Magn. Mater., 187(1),


[1998Sac] Saccone, A., Cacciamani, G., Maccio, D., Borzone, G., Ferro, R., “Contribution to the Study

of the Alloys and Intermetallic Compounds of Aluminium with the Rare-Earth Metals”,

Intermetallics, 6, 201-215, (1998) (Experimental, Crys. Structure, Equi. Diagram, 62)






“Experimental Study of Thermal Expansion and Phase Transformations in Iron-rich Fe-Al


[1999Kub] Kubis, M., Gutfleisch, O., Gebel, B., Mueller, K-H., Harris, I.R., Schultz, L., “Influence of

M = Al, Ga and Si on Microstructure and HDDR-Processing of Sm2(Fe,M)17 and Magnetic

Properties of their Nitrides and Carbides”, J. Alloys Compd., 283, 296-303 (1999) (Equi.


[1999Ren] Ren, Z.Y., Lee, W.-Y., Qin, C.-D., Ng, D.H.L., Ma, X.-Y., “Structural and Magnetic

Properties of Sm2Fe17–xTxM (T = Co, Ti; M = Al, Si) Compounds”, J. Appl. Phys., 85(8),


[2000Fan] Fan, G.J., Loser, W., Roth, S., Eckert, J., “Glass-Forming Ability of RE-Al-TM Alloys (RE

= Sm, Y; TM = Fe, Co, Cu)”, Acta Mater., 48(15), 3823-3831(2000) (Magn. Prop.,

Experimental, 30)

[2000Kub] Kubis, M., Eckert, D., Gebel, B., Mueller, K.-H., Schultz, L., “Intrinsic Magnetic Properties

of Sm2Fe17–xMxNy/Cy (M = Al, Ga or Si)”, J. Magn. Magn. Mater., 217, 14-18 (2000)


[2000Oka] Okamoto, H., Desk Handbook Phase Diagrams for Binary Alloys, ASM International,

Materials Park, OH 44073-0002 (2000)

[2000Ren] Ren, Z.Y., Ng, D.H.L., Dai, S.Y., “Structural and Magnetic Properties of Sm2Fe16MAl2 (M

= Mn, Mo; Ni) and their Carbides”, IEEE Trans., Magn., 36, 3330-3332 (2000) (Crys.


[2000Sam] Samata, H., Kamonji, M., Sasaki, H., Yashiro, S., Kai, M., Uchida, T., Nagata, Y.,

“Magnetic Properties of Sm(Fe1–xAlx)7 Crystals”, J. Alloys Compd., 311, 130-136 (2000)



BCC Phases in the Fe-Rich Portion of the Fe-Al System”, Intermetallics, 9, 755-761 (2001)


[2001Kon1] Kong, H.Z., Li, Y., Ding, J., “Magnetic Hardening in Amorphous Alloy Sm60Fe30Al10”,

Scr. Mater., 44(5), 829-834 (2001) (Crys. Structure, Experimental, Magn. Prop., 16)

414


MSIT®

Al–Fe–Sm

[2001Kon2] Kong, H.Z., Ding, J., Wang, L., Li, Y., “Amorphous Magnetic RE-Fe-Al Alloys”, IEEE

Trans., Magn., 37(4), 2500-2502 (2001) (Experimental, Magn. Prop., 9)

[2001Ter] Teresiak, A., Kubis, M., Mattern, N., Mueller, K.-H., Wolf, B., “Crystal Structure of

Sm2Fe17–yMy Compounds with M = Al, Si, Ga”, J. Alloys Compd., 319, 168-173 (2001)


[2002Ram] Rama Rao, K. V. S., Ehrenberg, H., Markandeyulu, G., Varadaraju, U. V., Venkatesan, M.,

Suresh, K. G., Murthy, V. S., Schidt, P. C., Fuess, H., “On the Structural and Magnetic

Properties of R2Fe17–x(A,T)x (R = Rare Earth; A = Al, Si, Ga; T = Transition Metal)


Prop., Review, 51)

[2002Zin] Zinkevich, M, Mattern, N., Handstein, A., Gutfleisch, O., “Thermodynamics of Fe-Sm,

Fe-H and H-Sm Systems and its Application to the Hydrogen - Disproportionation -

Desorption - Recombination (HDDR) Process for the System Fe17Sm2-H2”, J. Alloys

Compd., 339, 118-139 (2002) (Thermodyn., Assessment, 101)

[2003Bod] Bodak, O., “Al-Sm (Aluminum-Samarium)”, MSIT Evaluation Program, in MSIT



[2003Kan] Kang, Y., Chen, N., Shen, J., “Atomistic Simulation of the Lattice Constants and Lattice

Vibrations in RT4Al8 (R = Nd, Sm; T = Cr, Mn, Cu, Fe)”, J. Alloys Compd., 352, 26-33

(2003) (Crys. Structure, 40)





Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


( Fe)

1538 - 1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

1394 - 912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2, 1993Kat]

Dissolves up to 1.2 at.% Al

( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12

Pure Fe at 25°C [Mas2]

Dissolves up to 45.0 at.% Al at 1310°C

0-18.8 at.% Al, HT [1958Tay]

0-19.0 at.% Al, HT [1961Lih]

0-18.7 at.% Al, 25°C [1999Dub]

( Sm)

1074 - 922

cI2

Im3m

W

a = 410 [Mas2], dissolves up to 12 at.% Al at

760°C [1998Sac]

415


MSIT®

Al–Fe–Sm

( Sm)

922 - 734

hP2

P63/mmc

Mg

a = 366.30

c = 584.48

[Mas2]

( Sm)

< 734

hR9

R3m

Sm

a = 362.90

c = 2620.7

at 25°C [Mas2]

Fe4Al13

< 1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7° to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16-76.70 at.% Al [1986Gri]


at 76.0 at.% Al [1994Gri]

Fe2Al5< 1169

oC24

Cmcm

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [1994Bur]

FeAl2< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [1993Kat]

1102 - 1232

cI16” a = 598.0 at 61 at.% Al [1993Kat]

FeAl

< 1310

cP8

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5-47.5 at.% Al [1961Lih]

36.2-50.0 at.% Al [1958Tay]

39.7-50.9 at.% Al [1997Kog] quenched

in water from 500°C

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

24- 37 at.% Al [2001Ike]

23.1-35.0 at.% Al [1958Tay]

24.7-31.7 at.% Al [1961Lih]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

Metastable

81.8 at.% Al [1993Kat]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

Metastable

85.7 at.% Al [1993Kat]

[1998Ali]

FeAl4+x t** a = 884

c = 2160


[1998Ali]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

416


MSIT®

Al–Fe–Sm

Sm3Al11

< 1380

tI10

I4/mmm

BaAl4

a = 428.4

c = 990

[1998Sac]

Sm3Al11

(metastable)

oI28

Immm

La3Al11

a = 433.3

b = 1281

c = 997

[V-C2]

SmAl3< 1130

hP8

P63/mmc

Ni3Sn

a = 638.2

c = 460.0

[1998Sac]

Sm(FexAl1–x)2

< 1480

SmAl2

cF24

Fd3m

MgCu2 a = 794.3

0 x 0.45 (0 to 30 at.% Fe) [1975Dwi]

[V-C2]

SmAl

< 960

oP16

Pbcm

DyAl

a = 590.1

b = 1160.2

c = 568.8

[1998Sac]

Sm2Al

< 860

oP12

Pnma

Co2Si

a = 666.2

b = 519.0

c = 962.5

[1998Sac]

Sm2Fe17

1280 - ~1200

hP38

P63/mcm

Ni17Th2

a = 849

c = 830

[1989Gle]

Sm2(Fe1–xAlx)17

Sm2Fe17

1200

hR57

R3m

Th2Zn17

a = 854 to 878.2

c = 1243 to 1275.6

a = 857.0

c = 1244.0

a = 855

c = 1244

a = 854.5 to 883.4

c = 1247.7 to 1283.1

a = 855.37 to 863.40

c = 1244.34 to 1255.29

a = 861.3

c = 1253

a = 859.1

c = 1249.4

a = 861.4

c = 1252.5

a = 859.1

c = 1248.8

a = 861.8

c = 1252.2

0 x 0.41 (annealed at 1000°C)

[1995Che]

[1971Bus]

[1989Gle]


[1976McN]


[1991Wei]

x = 0.12 (annealed at 1000°C) [1994Jia]

x = 0.058

x = 0.081 (single crystal, structure

refinement) [1998Ono]

x = 0.06

x = 0.12 (powders, Rietveld refinement)

[2001Ter]

SmFe3

< 1010

hR12

R3m

Ni3Pu

a = 518.7

c = 2491.0

[1971Bus]

Sm(Fe1–xAlx)2

< 900

SmFe2

cF24

Fd3m

MgCu2 a = 741.7

0 x 0.25 (0 to 17 at.% Al) [1975Dwi]

[1971Bus]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

417


MSIT®

Al–Fe–Sm

Sm(Fe1–xAlx)7 tP64

P42/mnm

a = 876

c = 1214

a = 878

c = 1215

a = 875

c = 1223

x = 0 (metastable phase) [2000Sam]

x = 0.047 [2000Sam]

x = 0.07 [2000Sam]

* 1, Sm(Fe1–xAlx)2

SmFeAl

hP12

P63/mmc

MgZn2 a = 547

c = 884

a = 536 to 540

c = 868 to 875

0.3 x 0.475 (20 to 32 at.%Al)

[1975Dwi]

at x = 0.5 [1968Dwi]

0.3 x 0.45 [1974Viv2]

* 2, Sm6Fe11Al3 tI80

I4/mcm

La6Co11Ga3

a = 811.43

c =2299.49

[1992Hu] (annealed at 800°C)

* 3, Sm(FexAl1–x)12

SmFe4Al8

tI26

I4/mmm

ThMn12

a = 881 to 871

c = 505 to 501

a = 877.3

c = 505.1

0.275 x 0.467 (25.4 - 43 at.% Fe)

[1974Viv2]

at x = 0.33 [1976Bus]

* 4, SmFe2Al10 oC52

Cmcm

YbFe2Al10

a = 898.9

b = 1018.6

c = 904.3

[1998Thi] (single crystal, structure

refinement)

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

References/Comments

20

40

60

80

20 40 60 80

20

40

60

80

Sm Fe


Axes: at.%

τ1

SmFe2 SmFe3αSm2Fe17

FeAl

FeAl2

Fe2Al5

Fe4Al13τ4

τ3

SmAl3

SmAl2

Sm3Al11

(Al)

(αFe)

Fe3Al

Sm(FexAl1-x)2

Sm(Fe1-xAlx)2

Fig. 1: Al-Fe-Sm.


500°C

418


MSIT®

Al–Fe–Tb

Aluminium – Iron – Terbium

Gabriele Cacciamani

Literature Data

The Al-Fe-Tb phase equilibria have not been systematically investigated: [1975Oes] analyzed several

samples quenched from the melt or annealed at 1000°C along sections at constant Tb content and [2001Yan]

studied the 500°C solubility ranges of the different phases at the Tb2(Fe,Al)17 ratio. Several authors studied

the structural and magnetic properties of the Al-Fe-Tb phases: particular attention was dedicated to the solid

solutions at the Tb2(Fe,Al)17 ratio [1973Oes1, 1976Bol, 1992Jac, 1995Che, 1996Mao, 1998Yel, 2001Yan]

and to the Tb(Fe1-xAlx)12 ternary phase [1974Viv, 1976Bus, 1980Fel, 1988Che, 1997Yan, 1998Sch,

1999Sch]. Binary and (or) ternary phases at the Tb(Fe,Al)2 atomic ratio have been mainly investigated by

[1971Oes, 1973Oes2, 1973Zar, 1974Dwi, 2000Shi]. The remaining phases have been studied by [1972Oes]

and [1998Thi].

Samples have been generally prepared by arc melting the pure elements (usually 99.9 mass% pure) under

an inert atmosphere. In a few cases cold crucible induction melting [1996Mao] or synthesis in Al2O3 at 400

to 800°C [1998Thi] was used. [1975Dwi] induction melted Al-Fe master alloys with appropriate amounts

of rare earth. Samples were generally annealed at appropriate temperatures (typically 600-800°C for one or

more weeks, according to the experimental needs) and then quenched.

Binary Systems

The binary systems Al-Fe and Al-Tb are accepted from [2003Pis] and [2003Gro], respectively. The Fe-Tb

phase equilibria are accepted from [1996Oka] which is mainly based on the thermodynamic assessment by

[1994Lan].

Solid Phases

Crystal structure data are reported in Table 1. Al-Fe binary compounds and phases are not reported to

dissolve Tb. Al-Tb and Fe-Tb phases generally show more or less extended solubility ranges due to

substitution between Al and Fe.

The binary Laves phases TbAl2 [1973Oes2] and TbFe2 [1973Oes2, 2000Shi] (isostructural, MgCu2 type)

dissolve more than 20 at.% of the third element. At intermediate compositions, however, a different Laves

phase ( 1, MgZn2 type) is formed: the solubility ranges have been determined by [1975Dwi] and crystal

structures have been studied by [1971Oes, 1973Oes2, 1973Zar, 1974Dwi, 2000Shi]. According to

[1974Dwi] the cubic MgCu2 cell of TbFe2 shows a rhombohedral distortion which decreases with

increasing Al content. [1972Oes] found the Tb6Fe23 phase to dissolve an appreciable amount of Al.

The 2 phase has been observed only by [1975Oes] and no isostructural phases have been found in other

systems with similar rare earths: its existence has then to be considered doubtful.

The solid solutions at the Tb2(Fe,Al)17 ratio have been studied by different authors, sometime with

contradictory results. The recent results by [2001Yan] (lattice parameters and solubility ranges at 500°C)

seem particularly accurate. However it has to be considered that the range of stability of the different

structures is probably appreciably dependent on temperature. According to [1996Mao] a TbFe7 metastable

phase with the TbCu7 type structure is present also in the Fe-Tb binary sub-system.

The 4 phase has been studied by several authors at the TbFe4Al8, [1974Viv], TbFe6Al6 [1980Fel,

1988Che, 1998Sch] and TbFe5Al7 [1997Yan] compositions. Also in this case the solubility range

appreciably varies with temperature.

Finally, with the same Tb(Fe,Al)12 ratio, a different ternary phase ( 5, at the composition TbFe2Al10) was

studied by [1998Thi].

419


MSIT®

Al–Fe–Tb

Isothermal Sections

Partial indications on isothermal phase equilibria at different temperatures have been reported in literature,

especially by [1975Oes] and [2001Yan]. However it is not possible to draw any reliable isothermal section

at a defined temperature. Data about the composition ranges of the solid solutions are reported in Table 1.


Structural and magnetic ordering in the Laves phases has been studied by [1975Dwi] by Mössbauer

measurements.

Magnetic properties have been studied for 4 at different compositions: TbFe4Al8 [1978Bus, 1988Sch,

1999Sch, 2000Duo, 2000Sik] (magnetic properties have been studied as a function of temperature and

magnetization direction; coercivities extremely large at low temperatures have been revealed), TbFe6Al6[1981Fel, 1988Che, 1998Sch] (ferrimagnetic ordering occurs at about 340 K), TbFe4.4Al7.6 [2001Duo,

2002Duo] (observation of a field-induced transformation from easy-plane antiferromagnetic to easy-axis

ferrimagnetic structure at 5 K and determination of the intersublattice-coupling constant), and for 5

[1998Thi, 2000Ree] (magnetic properties have been determined by a SQUID magnetometer in the 2-300 K

temperature range; antiferromagnetic order below 14 K was observed), 1, Tb(Fe1-xAlx)2 [1973Oes1,

2000Shi] (magnetostriction measured also in samples where Al was partially substituted by Mn) and the

phases at the Tb2(Fe,Al)17 ratio [1995Che, 1996Mis] (changes in magnetic anisotropy and Mössbauer

studies). Magnetic properties have been reviewed by [1994Liu, 2002Ram].

References



[1972Oes] Oesterreicher, H., Pitts, R., “The Th6Mn23 Structure at an Unusual Composition

Tb0.167Fe0.693Al0.20”, J. Less-Common Met., 29,100-103 (1972) (Crys. Structure,

Experimental, 9)

[1973Oes1] Oesterreicher, H., “X-Ray and Neutron Diffraction Study of Ordering on Crystallographic

Sites in Rare-Earth-Base Alloys Containing Al and Transition Metals”, J. Less-Common


[1973Oes2] Oesterreicher, H., “Structural, Magnetic and Neutron Diffraction Studies on TbFe2-TbAl2,

TbCo2-TbAl2 and HoCo2-HoAl2”, J. Phys. Chem. Solids, 34, 1267-1280 (1973) (Crys.


[1973Zar] Zarechnyuk, O.S., Rikhal, R.M., Vivchar, O.I., “Laves Phases in Ternary Systems of the


Metallofiz., 46, 92-94 (1973) (Crys. Structure, Experimental, 22)

[1974Dwi] Dwight, A.E., Kimball, C.W., “TbFe2, a Rhombohedral Laves Phase”, Acta Crystallogr,

Ser. B: Struct. Crystallogr. Crys. Chem., B30, 2791-2793 (1974) (Crys. Structure,

Experimental, 12)


Systems” (in Russian), Tezisy. Dokl. - Vses. Konf. Kristallokhim. Intermet. Soedin.,

Rykhal, R.M. (Ed.), Vol. 2, L'vov. Gos. Univ.: Lvov, USSR., 41 (1974) (Crys. Structure,

Experimental, 0)


Mössbauer Study of (Sc, Y, Ln)(Fe, Al)2 Intermetallic Compounds”, J. Less-Common Met.,

40, 285-291 (1975) (Crys. Structure, Moessbauer, Experimental, 8)

[1975Oes] Oesterreicher, H., “Structural Studies on Materials from TbFe3 to Tb2Fe17 with Al

Substitution for Fe”, J. Less-Common Met., 40(2), 207-219 (1975) (Crys. Structure,

Experimental, 29)

420


MSIT®

Al–Fe–Tb

[1976Bol] Boller, H., Oesterreicher, H., “Tb2(Fe0.832Al0.168)17: A Simple Crystal Structure Derived

by Disordered Substitution in the Th2Ni17 Type”, J. Less-Common Met., 45, 103-109


[1976Bus] Buschow, K.H.J., Van Der Vucht, J.H.N., Van Den Hoogenhof, W.W., “Note on the Crystal



[1978Bus] Buschow, K.H.J., Van der Kran, A.M., “Magnetic Ordering in Ternary Rare Earth Iron

Aluminium Compounds (RFe4Al8)”, J. Phys. F: Met. Phys., 8, 921-932 (1978)




10)


RFe6Al6 (R = Rare Earth)”, Phys. Chem. Solids, 42, 369-377 (1981) (Crys. Structure, Magn.









[1992Jac] Jacobs, T.H., Buscow, K.H.J., Zhou, G.F., Li, X., de Boer F.R., “Magnetic Interactions in

R2Fe17-xAlx Compounds (R = Ho, Y)”, J. Magn. Magn. Mater, 116(1-2), 220-230 (1992)

(Magn. Prop., Experimental, 15)

[1994Liu] Liu, J.P., Boer, F.R. de, Chatel, P.F. de, Coehoorn, R., Buschow, K.H.J., “On the 4f-3d



[1994Lan] Landin, S., Agren, J., “Thermodynamic Assessment of Fe-Tb and Fe-Dy Phase Diagrams

and Prediction of the Fe-Tb-Dy Phase Diagram”, J. Alloys Compd., 207/208, 449-453

(1994) (Equi. Diagram, Assessment)

[1995Che] Cheng, Z., Shen, B., Liang, B., Zhang, J., Wang, F., Zhang, S., Gong, H., “The Change in

Magnetic Anisotropy in R2Fe17-xAlx Compounds (R = Sm or Tb)”, J. Phys.: Condens.

Matter, 7, 4707-4712 (1995) (Crys. Structure, Experimental, Magn. Prop., 16)

[1996Mao] Mao, O., Yang, J., Altounian, Z., Stroem-Olsen, J.O., “Metastable RFe7 Compounds (R =

Rare Earths and Their Nitrides with TbCu7 Structure)”, J. Appl. Phys., 79(8), 4605-4607


[1996Mis] Mishra, S.R., Long, G.J., Pringle, O.A., Marasinghe, G.K., Middleton, D.P., Buschow,

K.H.J., Grandjean, F., “A Magnetic and Moessbauer Spectral Study of the Tb2Fe17-xAlxSolid Solutions”, J. Magn. Magn. Mater., 162, 167-176 (1996) (Crys. Structure,

Experimental, 30)

[1996Oka] Okamoto, H., “Fe-Tb (Iron – Terbium)”, J. Phase Equilib., 17, 165 (1996) (Equi. Diagram,

Assessment, 5)

[1997Yan] Yanson, T.I., Manyako, M.B., Bodak, O.I., Cerny, R., Pacheko, J.V., Yvon, K., “Crystal

Structure of Terbium Iron Aluminide, TbFexAl12-x (x = 4.28), Lutetium Iron Aluminide,

LuFexAl12-x (x = 4 and 6.1), and Lanthanum Iron Aluminide, LaFexAl12-x (x = 4)”, Z.

Kristallogr. NCS, 212, 505-507 (1997) (Crys. Structure, Experimental, 6)



Concentrations x = 6”, Mater. Sci. Forum, 278-281, 542-547 (1998) (Crys. Structure, Magn.


421


MSIT®

Al–Fe–Tb



the Iron-Containing Series”, J. Mater. Chem., 8(1), 125-130 (1998) (Crys. Structure, Magn.


[1998Yel] Yelon, W.B., Luo, H., Chen, M., Chang, W.C., Tsai, S.H., “A Neutron Diffraction

Structural Study of R2Fe17-xAlx(C) (R = Tb, Ho) Alloys”, J. Appl. Phys., 83(11), 6914-6916


[1999Sch] Schobinger-Papamantellos, P., Buschow, K.H.J., Hagmusa, I.H., de Boer, F.R., Ritter, C.,

Fauth, F., “Magnetic Ordering of TbFe4Al8 Studied by Neutron Diffraction. I”, J. Magn.

Magn. Mater., 202, 410-425 (1999) (Crys. Structure, Experimental, 25)

[2000Duo] Duong, N.P., Hagmusa, I.H., Brueck, E., de Boer, F.R., Buschow, K.H.J., “Magnetic

Properties of TbFe4Al8”, J. Alloys Compd., 313, 21-25 (2000) (Crys. Structure,


[2000Ree] Reehuis, M., Fehrmann, B., Wolff, M.W., Jetschko, W., Hofmann, M., “Antiferromagnetic

Order in TbFe2Al10 and DyFe2Al10”, Physica B, 276-278, 594-595 (2000) (Crys. Structure,


[2000Shi] Shin, J.-C., Hsu, S.-Y., Chao, L.-J., Chin, T.-S., “The Magnetostriction of

Tb(Fe0.9MnxAl0.1-x)2 Alloys”, J. Appl. Phys., 88(6), 3541-3544 (2000) (Crys. Structure,


[2000Sik] Sikora, W., Schobinger-Papamantellos, P., Buschow, K.H.J., “Symmetry Analysis of the

Magnetic Ordering in RFe4Al8 (R = La, Ce, Y, Lu and Tb) Compounds (II)”, J. Magn.

Magn. Mater., 213, 143-156 (2000) (Calculation, Crys. Structure, Magn. Prop., 8)



Er) Phases”, J. Alloys Compd., 320(1), 108-113 (2001) (Crys. Structure, Equi. Diagram,

Experimental, 9)

[2002Duo1] Duong, N.P., Brueck, E., de boer, F:R., Buschow, K.H.J., “Magnetic Properties of

GdFe5Al7 and TbFe4.45Al7.55”, J. Alloys Compd., 338, 213-217 (2002) (Crys. Structure,


[2002Duo2] Duong, N.P., Brueck, E., Brommer, P.E., de Visser, A., de Boer, F.R., Buschow, K.H.J.,

“Extraordinary Magnetization Behavior of SingleCrystalline TbFe4.4Al7.6”, Phys. Rev. B,

65(2), 020408-1 - 020408-4 (2002) (Experimental, Magn. Prop., 8)

[2002Ram] Rama Rao, K.V.S., Ehrenberg, H., Markandeyulu, G., Varadaraju, U.V., Venkatesan, M.,

Suresh, K.G., Murthy, V.S., Schidt, P.C., Fuess, H., “On the Structural and Magnetic

Properties of R2Fe(17-x)(A, T)x (R = Rare Earth, A = Al, Si, Ga, T = Transition Metal)


Prop., Review, 51)

[2003Grö] Gröbner, J., Matusch, D., Turkevich, V., “Al-Tb (Aluminum – Terbium)”, MSIT Binary







422


MSIT®

Al–Fe–Tb


Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments

( Al) hP2

P63/mmc

Mg

a = 269.3

c = 439.8

at 25°C, 20.5 GPa [Mas2]

( Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe) hP2

P63/mmc

Mg

a = 246.8

c = 396.0


( Fe)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)

1394-912

cF4

Fm3m

Cu

a = 364.67 at 915°C [V-C2, Mas2]


( Fe)

< 912

cI2

Im3m

W

a = 286.65

a = 286.64 to 289.59

a = 286.60 to 289.99

a = 286.60 to 290.12



0-18.8 at.%Al, HT [2003Pis]

0-19.0 at.% Al, HT [2003Pis]

0-18.7 at.% Al, 25°C [2003Pis]

( Tb) HP hR3

R3mW

a = 341

c = 2450


( Tb)

1356 - 1289

cI2

Im3m

W

a = 402 [Mas2]

( Tb)

1289 – (-53)

hP2

P63/mmc

Mg

a = 360.55

c = 569.66

at 25°C [Mas2]

( 'Tb)

< -53

oC4

Cmcm

'Dy

a = 360.55

c = 569.66

at 25°C [Mas2]

Fe4Al13

< 1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7° to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

74.16-76.70 at.% Al [2003Pis]

sometimes called FeAl3 in the

literature

at 76.0 at.% Al [2003Pis]

423


MSIT®

Al–Fe–Tb

Fe2Al

5< 1169

oC24

Cmcm

Fe2Al

5

a = 765.59

b = 641.54

c = 421.84

at 71.5 at.% Al [2003Pis]

FeAl2

< 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

at 66.9 at.% Al [2003Pis]

1102 - 1232

cI16?

-

-

a = 598.0 at 61 at.% Al [2003Pis]

FeAl

< 1310

cP8

Pm3m

CsCl

a = 289.48 to 290.5

a = 289.53 to 290.9

a = 289.81 to 291.01

a = 289.76 to 190.78

34.5 - 47.5 at.% Al [2003Pis]

36.2 - 50.0 at.% Al [2003Pis]

39.7 - 50.9 at.% Al [2003Pis] 500°C

quenched in water

room temperature

Fe3Al

< 547

cF16

Fm3m

BiF3

a = 579.30 to 578.86

a = 579.30 to 578.92

~24 - ~37 at.% Al [2003Pis]

23.1 - 35.0 at.% Al [2003Pis]

24.7 - 31.7 at.% Al [2003Pis]

Fe2Al9 mP22

P21/c

Co2Al9

a = 869

b = 635

c = 632

= 93.4°

metastable

81.8 at.% Al [2003Pis]

FeAl6 oC28

Cmc21

FeAl6

a = 744.0

b = 646.3

c = 877.0

a = 744

b = 649

c = 879

metastable

85.7 at.% Al [2003Pis]

[2003Pis]

FeAl4+x t** a = 884

c = 2160


[2003Pis]

TbAl3< 1108

hR12

R3m

BaPb3

a = 617.6

c = 2116.5

[Mas2]

TbAl3(HP) hR20

R3m

HoAl3

a = 609.5

c = 3596

high pressure phase [V-C2]

Tb(FexAl1-x)2

TbAl2 < 1514

cF24

Fd3m

MgCu2

a = 786.5 to 770.7

a = 785.9

0 x 0.41 [1975Dwi]

at x = 0 – 0.37 [1973Oes2]

[Mas2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments

424


MSIT®

Al–Fe–Tb

TbAl

< 1079

oP16

Pmma

ErAl

a = 583

b = 1137

c = 562

[V-C2]

Tb3Al2 tP20

P42/mnm

Zr3Al2

a = 825.5

c = 756.8

[V-C2]

Tb2Al oP12

Pnma

Co2Si

a = 659.2

b = 511.3

c = 944.0

[Mas2]

Tb3Al cP4

Pm3m

Cu3Au

a = 479.4 [V-C2]

Tb(Fe1-xAlx)2

TbFe2

< 1187

cF24

Fd3m

MgCu2

a = 735.1 to 748.1

a = 739.07

a = 734.38

0 x 0.33 [1975Dwi]

at x = 0 - 0.26 [1973Oes2]

at x = 0.1 [2000Shi]

at x = 0 [V-C2]

Tb(Fe1-xAlx)2

TbFe2

hR*

R3m

a = 518.9

c = 1282.1

0 x 0.25 [1974Dwi]

at x = 0 rhombohedral distortion of the

cubic MgCu2 structure (decreasing

with increasing Al content) [1974Dwi]

TbFe3

< 1217

hR36

R3m

PuNi3

a = 511

c = 2442

[V-C2]

Tb6(Fe1-xAlx)23

Tb6Fe23

< 1276

cF116

Fm3m

Th6Mn23

a = 1217.3

a = 1207

at x = 0.25 [1972Oes]

at x = 0.0 [V-C2]

Tb2-y(Fe1-xAlx)17

Tb2Fe17

< 1312

hP38

P63/mmc

Th2Ni17 a = 853.2

c = 834.9

a = 848.7 to 859.1

c = 832.4 to 836.2

a = 845.1

c = 829.8

0 x 0.22 at 500°C

0 y 0.2 at 500°C [2001Yan]

at x = 0.19 [1973Oes2]

at x = 0 - 0.20, T = 500°C [2001Yan]

at x = 0.0 [V-C2]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments

425


MSIT®

Al–Fe–Tb

Tb2+y(Fe1-xAlx)17

Tb2Fe17

hR19

R3m

Th2Zn17

a = 852 to 866

c = 1241 to 1261

a = 857.68 to 862.12

c = 1251.91 to 1258.72

a = 872.6 to 876.1

c = 1266.3 to 1268.6

a = 875.6 to 880.7

c = 1264.5 to 1274.4

a = 854

c = 1243

0 x 0.56 at 500°C [2001Yan]

0 y 0.19 at 500°C at 52-60 at.%

Al [2001Yan]

at x = 0 - 0.3, T = 1000°C [1995Che]

at x = 0.12 - 0.24, T = 1100°C, neutron

diffraction [1998Yel]

at x = 0.40 - 0.47, T = 900°C [1992Jac]

at x = 0.45 - 0.56, T = 500°C,

[2001Yan]

at x = 0 [V-C2]

* 1, Tb(Fe1-xAlx)2 hP12

P63/mmc

MgZn2

a = 532.4 to 539.9

c = 875.8 to 872.1

a = 539.9

c = 872.1

a = 532.4

c = 870.6

0.35 x 0.54 [1975Dwi]

at x = 0.33 - 0.51 [1973Oes2]

at x = 0.5 [1971Oes]

TbFeAl

at x = 0.338 [1973Oes2]


P63/mmc

CeNi3

a = 522.6

c = 1679.4

0.20 x 0.33 at 1000°C

at x = 0.25 [1975Oes]


P6/mmm

TbCu7

a = 496.0 to 497.0

c = 420.1 to 420.3

a = 490

c = 418

0.23 x 0.26 at 500°C [2001Yan]

at x = 0, from graph in [1996Mao]

(metastable in the binary)

'3, Tb2(Fe1-xAlx)17 h**

P622

a = 853.2

c = 417.5

at x = 0.17, T = 800°C, disordered

derivative of Th2Ni17 [1976Bol]

(possibly the Tb(Fe1-xAlx)7 phase?)

* 4, Tb(FexAl1-x)12 tI26

I4/mmm

ThMn12

a = 874.9

c = 504.3

a = 874.0

c = 501.8

a = 865.1

c = 502.9

a = 865.1

c = 502.9

a = 868.1

c = 504.6

a = 874.3

c = 505.6

0.33 x 0.50

at x = 0.33 [1976Bus]

TbFe4Al8at x = 0.33 [1974Viv]

TbFe4Al8at x = 0.5 [1980Fel]

TbFe6Al6at x = 0.5 [1988Che]

at x = 0.5, neutron diffraction

[1998Sch]

at x = 0.36 [1997Yan]

* 5, TbFe2Al10 oC52

Cmcm

YbFe2Al10

a = 896.3

b = 1014.9

c = 901.3

[1998Thi]

Phase/

Temperature Range

[°C]

Pearson Symbol/

Space Group/

Prototype

Lattice Parameters

[pm]

Comments

426


MSIT®

Al–Fe–Ti

Aluminium – Iron – Titanium

Gautam Ghosh

Literature Data

Certain alloy compositions of this system are of technological interest in many applications, such as

elevated-temperature structural alloys, surgical implants and hydrogen storage. As a result a large number

of experimental studies have been carried out to determine the phase equilibria. Earlier investigations are

due to [1940Nis, 1954Sto, 1958Bok, 1958Kor, 1963Luz, 1969Vol, 1970Vol, 1971Vol, 1973Mar] and

[1981Sei]. [1969Vol] used electrolytic Fe, “iodide” Ti and AV-000 grade Al. The alloys were annealed at

800°C (200-400 h), 700°C (300 h) and 500°-600°C (1000 h). After annealing they were water quenched.

Thermal analysis and phase analysis by X-ray diffraction and microstructural observation were performed.

Volkova et al. presented temperature-composition sections [1969Vol], isothermal sections at 1100, 800 and

550°C [1970Vol, 1971Vol]. [1981Sei] used electrolytic Fe, Ti sponge and 99.99% purity Al. First, the Fe-Ti

alloys were prepared by electron-beam melting and then the ternary alloys were made in an arc furnace

using an argon atmosphere. X-ray diffraction, metallographic analysis and microhardness tests were

conducted by [1981Sei] on about 80 ternary alloys. [1981Sei] presented a liquidus surface, a complete

isothermal section at 800°C, and a partial isothermal section at room temperature. A critical assessment of

these results along with several amendments of liquidus surface of [1981Sei] were presented by [1987Rag].

[1990Kum] presented a brief review of the phase equilibria.

[1987Men] studied order-disorder transitions involving ( Fe), B2 ( 2) and D03 ( 1)phases using five

ternary alloys of Fe-(17.3 to 25.2) at.% Al-(4.4 to 5.2) at.% Ti. They carried out the transmission electron

microscopic investigations to establish phase relations in the temperature range of 400 to 1000°C.

[1989Maz] produced 50 to 100 g ingots of nine ternary alloys in the composition range of Al-(16.6 to 34.1)

at.% Ti-(1.6 to 17.8) at.% Fe. The alloys were prepared by arc melting in vacuum. Some alloys were

annealed at 1200°C for 500 h in Ar-atmosphere, some were annealed subsequently at 800°C for 300 h. The

samples were chemically analyzed to determine their final composition and then examined by

metallography, X-ray diffraction and electron microprobe. It was reported that the O and N impurity levels

remained below 500 ppm by mass. [1991Nwo] determined the ( Ti)+( Ti) two-phase field at 700 and

800°C by annealing alloys for 10 h at 800°C and 30 h at 700°C. The alloys were prepared using elements

of following purity: Ti 99.5%, Al 99.99% and Fe 99.9%. The phases were detected by X-ray diffraction,

SEM and TEM and quantitatively analyzed by EDAX. These along with the earlier results were reviewed

by [1992Gho]. [1993Rag] presented an update of phase equilibria based on the published results between

1985 and 1992.

In a significant contribution, [1995Pal] determined two complete isothermal sections at 800 and 1000°C.

They prepared 59 ternary alloys in a crucible-free levitation furnace and cast into a copper mold. They used

elements of following purity: 99.99% Al, 99.97% Fe and 99.77% Ti. Prepared samples were encapsulated

in quartz ampoules and heat treated at 1000 and 800°C for 100 and 500 h, respectively, followed by

quenching in brine solution. In addition, they also performed six diffusion couple experiments at 1000°C.

The phase equilibria were studied by metallography, SEM, EPMA and XRD.

[1995Yan1] investigated the phase equilibria at 800°C using nine ternary alloys in the composition range

of Al-(0.5 to 8) at.% Fe-(25 to 35) at.% Ti. They used elements of purity of 99.999% Al, 99% Fe and 99%

Ti. The final heat treatment was at 800°C for 10 days. They employed SEM/EDX and TEM techniques to

identify the phases. [1998Ohn] studied the order-disorder transitions in Fe-rich alloys, and reported three

temperature-composition sections, and two isothermal sections of Fe-corner at 800 and 900°C. They

prepared 24 ternary alloys and several diffusion couples to study order-disorder transitions, and to

determine the phase equilibria using DSC/DTA, EPMA and TEM techniques. [1999Gor] investigated the

phase equilibria in ten ternary alloys that were heat treated at 1000°C for 96 h. Phase equilibria were

determined by metallography, EPMA and XRD. Supplementing the results of [1995Pal], [1999Gor]

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presented an updated isothermal section at 1000°C. [1999Li] studied the effect of 1 at.% Fe on the

Ti3Al-TiAl phase boundaries between 1000 and 1250°C.

The phase equilibria of Ti-rich alloys were investigated by [2000Kai1] and [2000Kai2]. [2000Kai1]

prepared alloys in the composition range of Ti-(35 to 47) at.% Al-(0.5 to 12) at.% Fe using 99.99% Al,

99.99% Fe and 99.7% Ti. The final heat treatments were at 1000°C for either 168 or 504 h, at 1200°C for

168 h, and at 1300°C for 24 h. They determined the tie-line compositions involving ( Ti), ( Ti) and TiAl

phases using EPMA. [2000Kai2] investigated the order-disorder transitions (A2 B2), and determined

tie-line compositions involving ( Ti), ( Ti) and FeTi phases in Ti-rich area at 1000°C. They used ternary

alloys in the composition range of Ti-(11 to 27) at.% Al-(3 to 25) at.% Fe. Furthermore, the tie-line

compositions were in diffusion couples equilibrated at 1000°C. [2000Mab] also investigated the phase

equilibria of Al-rich alloys in the composition range of Al-(2 to 14) at.% Fe-(25 to 40) at.% Ti. They

produced samples as sintered compacts and ingots. For sintered compacts the starting powders of 99.9% Al,

99.9% Fe and 99.5% Ti were used, and for ingots elements of purity of 99.99% Al, 99.9% Fe and 99.7% Ti

were used. The final heat treatments for the sintered compacts were at 1150°C for 24 h and at 1000°C for

48 h, while the ingots were heat treated at 1150°C for 48 h and at 1000°C for 144 h. The phase equilibria

were studied by SEM, EPMA, TEM and XRD. [2002Rag] presented a further update of phase equilibria

based on the published results between 1981 and 2000.

Very recently, [2001Pra] reported the phase compositions of eight as-cast ternary alloys. They found that

except for two alloys lying in the Fe2Ti+L21 field, the phase compositions agree with the previously

reported 800°C isothermal section due to Palm et al [1995Pal]. In a more recent significant work, Ducher

et al [2003Duc] re-investigated the liquidus surface using 38 alloys selected from those used by Palm et al

[1995Pal]. [2003Duc] used DTA, metallography, SEM/EDX and XRD to identify the reactions during

solidification. Based on their extensive results, a reaction scheme was proposed.

Binary Systems

The Al-Fe, Al-Ti and Fe-Ti binary phase diagrams are accepted from [2003Pis], [2003Sch] and [1982Kub],

respectively.

The Al-Fe phase diagram has undergone slight modification due to recently established congruent melting

behavior of the Fe4Al13 phase [1986Len]. The Al-Ti binary phase diagram is accepted from the recent

review of [2003Sch]. The system is characterized by the presence of five intermediate phases and eight

invariant reactions. [2003Sch] accepted the invariant temperatures based on a CALPHAD modeling of the

phase equilibria. However, in this assessment the temperature of the peritectoid reaction

TiAl+Ti2Al5 TiAl2 is taken as 1205°C [1991Mis] rather than 1199°C [2003Sch] for the reasons discussed

in “Invariant Equilibria”.

Solid Phases

The Fe3Al ( 1) phase dissolves a significant amount of Ti [1973Mar] and [1977Ath]. Addition of Ti in

Fe3Al increases both the D03 B2 and B2 A2 [1987Men, 1987For, 1994Sel, 1995Ant, 1996Pra, 1997Nis1,

1997Nis2, 1998Ohn, 1999Mek, 2003Ste] transition temperatures. For example, the increase in D03 B2

transition temperature of Fe3Al is about 60°C/at.% Ti [1995Ant]. Addition of Ti also increases the Curie

temperature [1994Sel] and lattice parameter of Fe3Al [1996Pra, 1997Nis2]. The details of substitution of

Fe by Ti have been studied using X-ray diffraction, transmission electron microscopy and Mössbauer

spectroscopy [1977Ath, 1995Mah]. The Mössbauer spectroscopic data show that Ti replaces Fe at a specific

lattice site with 8 nearest Fe atoms rather than a site with 4 Fe and 4 Al nearest atoms [1977Ath, 1995Mah].

This implies that TiFe2Al is a Heusler phase (L21) [1985Okp, 1995Mah] and not (Fe,Ti)3Al (D03).

The FeAl ( 2) phase also dissolves a significant amount of Ti [1995Pal, 1998Ohn, 1999Gor, 2002Aze]

leading to an increase in lattice parameter. For example, the lattice parameter of Fe0.7-xTixAl0.3 can be

expressed as [2002Aze]

a (in pm) = 291.0 + 9.2 x.

[1997And] determined the site occupancy of Ti in Fe50Al45Ti5 and Fe52Al45Ti3 ( 2) alloys by ALCHEMI

(Atom Location by CHanneling Enhanced MIcroanalysis) in TEM, and found that about 85% of the

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“Al-site” is occupied by Ti. The residual “Fe-site” occupancy is attributed to the kinetics of site-equilibrium

mechanism. The Fe4Al13, Fe2Al5 and FeAl2 phases can dissolve up to 6.5, 2.5 and 1.8 at.% Ti, respectively

[1995Pal]. At room temperature, Fe4Al13 can dissolve about 2.5 at.% Ti [1981Zhu].

The TiFe phase dissolves a substantial amount of Al [1980Dew, 1981Sei, 1995Pal, 1999Gor]. The

maximum solubilities at 800, 900 and 1000°C are 13, 24 and 33 at.% Al, respectively [1999Pal, 1999Gor].

The substitution of Al in TiFe causes a linear increase in lattice parameter [1980Dew, 1995Pal, 1999Lee].

For example, the lattice parameter (a) of Ti(Fe,Al) can be expressed as [1995Pal]

a (in pm) = 297.0 + 5.07 (50-xFe),

where xFe is the Fe-content in at.%. This is also in good accord with the lattice parameter reported by

[1980Dew].

The Laves phase TiFe2 also dissolves a substantial amount of Al [1967Mar, 1973Mar, 1974Dwi, 1980Dew,

1995Pal, 1999Gor]. The data of [1973Mar] show a linear increase of both a and c lattice contents as Al

replaces Fe in TiFe2. However, recent measurements by [1995Pal] show a linear increase of the a lattice

constant while a non-linear increase of the c lattice constant of Ti(Fe,Al)2 as

a (in pm) = 477.7 + 0.506 (70- xFe)

c (in pm) = 778.3 + 1.406 (70- xFe)-6.78532x10-3 (70- xFe)2

where xFe is the Fe-content in at.%.

Among the Al-Ti intermetallics, TiAl3, Ti2Al5, TiAl2, TiAl and Ti3Al can dissolve up to 1.2, 0.8, 2.5, 2.5

and 1.5 at.% Fe at 1000°C, respectively [1995Pal]. [2001Sun] obtained 1.92 at.% Fe in the TiAl phase in a

Ti52Fe2Al46 alloy that heat treated at 900°C for 8 h. [1985Pas] reported 0.5 at.% Fe in TiAl at 550 to 600°C.

All these results clearly demonstrate that the solubility of Fe in TiAl increases with temperature.

Furthermore, results of ALCHEMI experiments in TEM show that Fe atoms reside primarily on the Al-site

in TiAl structure [1999Hao, 2000Yan]. Due to low solubility, the site occupancy of Fe in Ti3Al could not

be determined conclusively [1999Hao].

The ternary phases accepted in this assessment are 2 (TiFeAl2) and 3 (Ti8Fe3Al22). The 2 phase was

discovered by [1967Mar], and subsequently confirmed by [1980Dew] and [1981Sei]. It forms by a

peritectic reaction at about 1225°C [2003Duc]. [1973Mar] reported that the homogeneity range of the 2

phase at 800°C is from 40 to 50 at.% Al at 24 at.% Fe, and that reported by [1981Sei] is from 53 to 55.5

at.% Al and 21 to 24 at.% Fe. [1980Dew] reported that the homogeneity range of the 2-phase at 1000°C is

from 28 to 52 at.% Al at 25 at.% Fe. Recent results of [1995Pal] show that 2 phase split into two islands at

1000°C, one with homogeneity range of 30 to 39 at.% Al, and the other with a homogeneity range of 44.5

to 54.5 at.% Al. Also, [1995Pal] reported that the ambient crystal symmetry of 2 changes from cubic, when

the Ti-content is in the range of 30.8 to 50.9 at.%, to tetragonal when the Ti-content is less than 24 at.%.

[1999Lev] also observed both cubic and tetragonal phases in a Al-49.6 at.% Ti-1.9 at.% Fe alloy that was

heat treated at 1400 and 1300°C for 40 min and 90 min, respectively, water quenching or furnace cooling.

The Ti-content in the tetragonal phase was less 16 at.%. [1999Lev] concluded that the tetragonal- 2 is a

metastable phase, and it forms from Ti(Fe,Al) by a massive transformation. Very recently, [2001Tok]

characterized the present in a Ti-1.9 at.% Fe-46.9 at.% Al alloy that was heat treated at 1200°C for 8 h

followed by water quenching or furnace cooling. They found the cubic- 2 (Ti38Fe23Al39) in furnace cooled

specimen while the tetragonal- 2’ (Ti52Fe10Al38) in water quenched specimen. A recent single crystal

X-ray study for the 2 phase revealed a slightly modified Th6Mn23 type structure by filling the octahedral

void of Th6Mn23 by Al/Ti-atoms [2003Gry].

The 3 phase was first reported by [1973Mar], and subsequently confirmed by [1980Dew], [1981Sei] and

[1991Nic]. [1981Sei] designated the composition of 3 as Ti24Fe9Al66, while [1989Maz] reported

Ti28Fe8Al64. All subsequent investigations also confirmed a homogeneity range [1992Dur1, 1992Win,

1993Nak, 1995Pal, 1995Yan1, 1999Yam, 2000Mab], which increases with temperature. For example, at

800°C the homogeneity range is about 5 at.% Fe [1995Pal, 1995Yan1], and at 1200°C it is about 7 at.% Fe

[1989Maz]. Notwithstanding this homogeneity range, both TiAl2 and TiAl3 phases have been observed in

3 compositions that are expected to be single phase. For example, [1991Wu] observed both TiAl2 and TiAl

in single crystals of Al66.8Fe5.8Ti27.4. [1992Mor] also observed TiAl2 in Al64Fe8Ti28 and Al63Fe8Ti29

alloys that were heat treated between 600 and 1150°C. [1994Yan] observed precipitation of TiAl2 phase in

a Ti28Fe8Al64 alloy which corresponds to the geometric centre of 3’s composition range. The alloy was

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prepared using 99.999% Al, 99% Fe and 99% Ti, and heat treated at 1200°C for 50 h. Furthermore,

[1994Yan] observed three types of TiAl2: TiAl2I (ZrGa2-type), TiAl2

II (HfGa2-type) and TiAl2III. The latter

is similar to the other two, but with different stacking sequence. It is believed to be stabilized by Fe, and has

never been observed in binary Al-Ti alloys.

Based on a geometric approach [1991Dur] and electron-concentration approach [1992Dur2], Durlu et al

argued that 3 should be considered as TiAl2-based rather than TiAl3-based L12 phase. Furthermore,

[1992Dur2] proposed that Fe should replace Ti in stabilizing L12 structure. On the other hand,

electronic-level ab initio calculations [1990Car, 1991Car] showed that replacement of Al by Fe in TiAl3indeed energetically favors the cubic L12 structure over the tetragonal D022 structure. Indeed, ALCHEMI

results [1992Ma] show that Fe atoms reside primarily on the Al-sublattice in Al62.5±xTi25±yFey alloys.

[1973Mar] also reported another compound Ti6Fe25Al69, but later at the same composition [1981Sei] found

a two-phase mixture of Fe2Al5 and 3. On the other hand, [1995Pal] reported that this composition

represents a ternary extension of the binary phase Fe4Al13. [1981Sei] reported the 1 (TiFe2Al) phase

having cubic structure with lattice parameter a = 414.0 pm; however, subsequent investigation failed to

confirm the existence of this phase [1995Pal]. A cubic phase at TiFe2Al (Heusler-type) also repotred by

[1983Bus], but with lattice parameter very different from [1981Sei].

The details of the crystal structures and lattice parameters of all the binary and ternary solid phases are listed

in Table 1.


Figure 1 shows the reaction scheme, mostly adopted from the very recent works of [2003Duc] and

[1995Pal]. No distinction is made between disordered ( Fe) and its ordered forms B2 and D03; similarly,

no distinction is made between disordered ( Ti) and ordered ( Ti); 2 is the Ti-rich variant and 2’ is the

Al-rich variant. The systematic study of [2003Duc] by DTA followed by careful characterization of

as-solidified microstructures have led to a number of changes in the reaction scheme compared to that first

proposed by [1981Sei]. The study of [1995Pal] has contributed significantly to our knowledge of solid-solid

phase equilibria. However, the reaction scheme proposed by [2003Duc] suffers from at least four

drawbacks, which have been rectified in this assessment.

First, [2003Duc] did not consider the primary crystallization of Ti2Al5. To account for this, we have

introduced two ternary invariant reactions, P1 (L+TiAl+Ti2Al5 3) and U1 (L+Ti2Al5 TiAl3+ 3),

tentatively occurring around 1380 and 1370°C, respectively. Second, [2003Duc] considered four binary

invariant reactions, labelled c1, pd1, pd2 and pd3, originating from Al-Ti system that are incompatible with

the presently accepted Al-Ti phase diagram. Accordingly, these and the associated ternary invariant

reactions are not considered in Fig. 1. Third, [2003Duc] proposed the invariant reaction U6 around 1150°C:

( Ti)+( Ti) Ti3Al+TiAl. However, this is inconsistent with the observation of the three-phase field

( Ti)+( Ti)+Ti3Al in 1100, 1000, 900 and 800°C isothermal sections [1995Pal, 1999Gor]. To overcome

this problem, we have rewritten the invariant reaction as ( Ti)+TiAl ( Ti) +Ti3Al. In addition, two more

corrections in the reaction scheme of [2003Duc] are made in this assessment. The monovariant and

invariant equilibria E3 and U10 of [2003Duc], respectively, are correctly written as L Fe4Al13+ 3 and

L+ 3 Fe4Al13+ 2’. Fourth, [2003Duc] proposed the invariant reaction U20 around 900°C: TiAl+Fe2Ti

2’+ 2. Once again, the consequences of this reaction contradict the experimental observations. For

example, the 2 phase splits into two islands, 2 and 2’ above 1000°C [1995Pal]. A further serious

drawback is that none of the experimental isothermal sections at 1000, 900 and 800°C shows 2’+ 2+Fe2Ti

and/or 2’+ 2+TiAl phase fields. Therefore, this invariant reaction is not considered in Fig. 1.

[2002Rag] proposed a reaction scheme in which the invariant reaction L+Ti2Al5 TiAl+TiAl3 (U2 in

[2002Rag]) takes place around 1340°C, and this gives rise to the three phase field Ti2Al5+TiAl+TiAl3 that

persists until about 1200°C. However, in the presence of ternary phase 3, in the vicinity of TiAl2 and TiAl3,

the existence of Ti2Al5+TiAl+TiAl3 phase field is very unlikely. Ducher et al [2003Duc] have discussed

other major differences between their reaction scheme and that proposed by [2002Rag].

[1989Maz] observed TiAl2 phase in ternary alloys heat treated at 1200°C. Accordingly, three-phase fields

such as TiAl3+TiAl2+ 3, TiAl2+TiAl+ 3 are expected at this temperature as they have been observed at

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Al–Fe–Ti

1150°C [2000Mab]. To account for these three-phase fields at 1200°C, the binary invariant reaction

TiAl+Ti2Al5 TiAl2 is considered to take place at 1205°C [1991Mis] instead of 1199°C [2003Sch]. The

proposed reaction scheme in Fig. 1 is consistent with the observed phase fields in 1300 [2000Kai1], 1200

[2000Kai1], 1150 [2000Mab], 1100 [1970Vol], 1000 [1995Pal, 2000Mab], 900 [1999Gor] and 800°C

[1970Vol, 1973Mar, 1995Pal] isothermal sections, and also the vertical sections reported by other

investigators [1969Vol, 1973Vol, 1987Men, 1998Ohn].

Liquidus Surface

[1940Nis] and [1958Bok] reported the liquidus surface of Al-corner only. A comprehensive report of the

liquidus surface was first given by [1981Sei], and subsequently modified by [2003Duc]. Figure 2 shows the

liquidus surface and the melting grooves separating 13 different areas of primary crystallization. To

incorporate the primary crystallization of Ti2Al5, a slight modification has been made. The doubtful regions

of the liquidus surface are shown by dotted lines. Using the melting temperature data of [2003Duc],

approximate isotherms at 100°C intervals from 1600°C to 1000°C are also shown in Fig. 2.

Isothermal Sections

The early works of [1940Nis, 1954Sto] and [1958Bok] were restricted to the Al corner. [1958Bok] reported

two isotherms at 640 and 600°C with up to 2.2 at.% Fe and 1.1 at.% Ti. [1958Kor] reported the isothermal

sections at 1100, 1000, 800 and 550°C with up to 30 mass% (Fe+Al). Recent significant results are the

complete isothermal sections at 1000, 900 and 800°C [1995Pal, 1999Gor], isothermal sections of Al-corner

at 1150 [2000Mab], 1000 [2000Mab] and 800°C [1995Yan1], isothermal sections of Fe-corner at 900 and

800°C [1998Ohn], and isothermal sections of Ti-corner at 1300 and 1200°C [2000Kai1].

Figures 3 and 4 show the isothermal sections of Ti-corner depicting phase equilibria involving ( Ti), ( Ti)

and TiAl. The phase equilibria of the Al-corner at 1200 [1989Maz], and 1150°C [2000Mab] are shown in

Figs. 5 and 6, respectively. The original phase diagram reported by [2000Mab] had to be modified to comply

with the Al-Fe and Al-Ti binary phase diagrams. In particular, the liquid phase should be present in the

Al-rich side at 1150°C, but this was not considered by [2000Mab]. The phase boundaries involving the

liquid phase are shown dotted as their exact locations are not known.

Figure 7 shows a partial isothermal section in the region Ti-TiAl-TiFe at 1100°C, based on the work of

[1970Vol]. Figures 8, 9 and 10 show complete isothermal sections at 1000, 900 and 800°C adopted from

the works of [1995Pal], [1999Gor] and [2000Kai2]. Since ( Ti) in Al-Ti system undergoes a second-order

transition to form B2 structure [2000Ohn], a similar behavior is expected in ternary alloys as well. In fact,

[2000Kai2] established the phase boundaries at 1000°C associated with the second-order transition in

Ti-rich alloys. Accordingly, the ( Ti) field in Fig. 8 is divided into A2 and B2 regions by a second-order

line. Figure 11 shows the isothermal section at 550°C after [1970Vol] in the region of Ti-TiAl-TiFe. Below

550°C, the phase fields remain unchanged down to room temperature as has been confirmed by [1981Sei].

Minor adjustments have been made in the isothermal sections to comply with the binary phase diagrams

accepted here.


[1969Vol] determined three vertical sections at constant Al/Fe mass ratios 3:1, 1:1 and 1:3 and (Al+Fe) was

varied from 0 to 30 mass%. [1973Vol] determined four vertical sections of the Ti-rich alloys at 5, 10, 12

and 16 mass% Al. [1969Vol] reported three vertical sections in the Ti corner at constant Al/Fe ratios of 3:1,

1:1, and 1:3 with a (Al+Fe) content up to 30 mass%, and [1991Nwo] gave the transus and solubility for

sections with 2 and 4 mass% Al up to 16 mass% Fe.

Figures 12 and 13 show the vertical sections at constant Al-content of 25 and 23 at.%, respectively

[1998Ohn]. In addition to ( Fe)+ 2 phase field as in the case of Al-Fe system, the presence of 1+ 2 phase

field in the ternary system may be seen in Figs. 12 and 13. As discussed by [1998Ohn], the topology of the

phase boundaries involving ordered ( 1, 2) and disordered phases ( Fe) are consistent with the general

features of phase diagrams associated with multicritical points [1982All].

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Al–Fe–Ti

Addition of about 5 at.% Ti is reported to shift the ( Fe)+ 1 phase field to higher temperature and to lower

Al contents compared to Al-Fe alloys [1987Men]. [1998Ohn] also re-investigated the vertical of Fe-5 at.%

Ti-xAl, and found good agreement with the results of [1987Men]. Their results are summarized in Fig. 14.

The effects of substitution of Fe by Ti in Fe3Al ( 1) and the substitution of Al by Ti in FeAl ( 2) on the

order-disorder transitions are summarized in Fig. 15. This conjoined vertical section was originally

published by [1998Ohn], but the Fe3Al-side has been significantly modified to make it consistent with the

Figs. 12 and 14. It is seen that Fe2TiAl (L21) undergoes a second-order phase transition to B2 at about

1220°C. However, the ideal transition temperature is predicted to be about 500°C higher [2002Ish]. The

addition of Co and Ni in Fe2TiAl should increase the critical temperature [2002Ish]. In Figs. 12, 13 and 15,

minor adjustments have been made to comply with the accepted Al-Fe phase diagram.

Thermodynamics

[1979Dew, 1979Kau1] and [1979Kau2] calculated the isothermal section at 1000°C. However, they did not

consider the ternary phases, because the Gibbs energies of formation of these phases are not known. The

calculated ternary ( Fe)/( Fe)+( Fe) and ( Fe)+( Fe)/( Fe) phase boundaries have also been reported

[1986Gho, 1988Kum].

[1987Kal] performed theoretical studies of the effect of Fe on the D019-type ordering of Ti3Al. They found

that Fe increases the ordering temperature.

[1990Car] studied the effect of Fe on the relative stability of cubic L12 and tetragonal D022 structures of

TiAl3 phase using ab initio (augmented-spherical-wave method) electronic band structure calculations.

They found that 4.5 at.% Fe is sufficient to stabilize the L12 structure which is in reasonable agreement with

the experimental homogeneity range of 3.

[1998Ohn] carried out theoretical studies of order-disorder phase transitions and the BCC phase equilibria,

in the composition range Fe-FeAl-FeTi, employing cluster variation method using the irregular tetrahedron

method. They considered first- and second-nearest neighbor as well as tetrahedron interactions. They found

an excellent agreement between the calculated and experimental results.

[2000Kai2] employed Bragg-Williams-Gorsky approximation to model A2/B2 transition in Ti-rich ternary

alloys. Extrapolating the ternary results to Al-Ti system, they predicted that a Ti-23.5 at.% Al alloy

undergoes metastable A2/B2 transition at 1000°C.


[1983Bus] reported the magneto-optical Kerr rotation effect of the Heusler phase TiFe2Al. [1994Sel]

studied the magnetic and electrical properties of Fe0.73Al0.27-xTix (0 x < 0.16) alloys. [1979Sup] studied the

magnetic susceptibility of the 2 phase.

Addition of Ti in Fe73Al27 increases its hardness, and also its deformation mode [1996Pra]. The hardness,

density, temperature dependence of Young’s modulus and yield stress, and creep properties of

Ti33.1Fe33.9Al33 were reported by [1996Mac]. [2000Sha] demonstrated superplastic deformation of Fe-28

at.% Al-2 at.% Ti and Fe-28 at.% Al-4 at.% Ti alloys in the temperature range of 600 to 750°C. The

compressive creep behavior, in the temperature range of 600 to 800°C, of Fe-rich two- and three-phase

alloys is reported to exhibit power-law behavior with the exponent varying from 3 to 6, and the activation

energy varying from 400 to 600 kJ/mol [2001Pra]. The order-disorder transitions in Al-Fe and Al-Fe-Ti

alloys lead to non-monotonic behavior of temperature-dependent mechanical properties, which have been

discussed in detail by [1997Nis2] and [2003Ste].

The mechanical properties of the ternary phase 3 have been studied extensively. [1991Nic] reported the

hardness and Young’s modulus of 3 at Al22Fe3Ti8. [1991Wu] reported the deformation behavior of single

crystal Al66.8Fe5.8Ti27.4 ( 3) as a function orientation and temperature dependence of yield stress of up to

1200°C. The compressive yield stress as a function of temperature has been reported by [1991Ino] for 3 at

Al67.5Ti25Fe7.5 and by [1991Kum] for 3 at Al22Ti8Fe3. The hardness and cracking load of Al64Fe8Ti28 and

Al63Fe8Ti29 alloys were reported by [1992Mor]. The ambient yield and fracture properties of Ti30Fe4Al66

and Ti26Fe8Al66 were reported by [2002Bra].

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A Ti-5 mass% Al-2.5 mass% Fe is reported to be biocompatible, thus, a candidate implant material for hip

prosthesis [1986Zwi]. This alloy, with ( Ti)+( Ti) microstructure, exhibits superplasticity at 850°C.

Furthermore, powder metallurgy processing of this alloy reduces the Young’s modulus from about 111 GPa

to 10 GPa which is very close to that of bone (5 to 9 GPa) [1986Zwi]. The stress-induced –>

transformation and associated superplasticity in the temperature range of 777 to 927°C in a Ti-5.5 mass%

Al-1 mass% Fe alloy has been discussed by [2000Koi].

[1999Lee] studied the hydrogen absorption-desorption behavior of TiFe1-xAlx alloys at 50°C. Addition of

Al causes a increase in lattice parameter of TiFe, and also inhibits the formation of -hydride. The latter

was attibuted to different sizes of octahedral sites, and preferential site occupation of hydrogen atoms.

[2001Ish] also studied hydrogen absorption-desorption of Ti75-xAl25Fex (0 x 25) alloys. At x=15, the

desorption temperature is about 510°C which is about the same as binary Ti3Al; however, the hydrogen

absortion is significantly reduced.

Miscellaneous

The transus temperature increases with increasing Al content [1991Nwo]. [1973Kol] investigated the

solubility of Ti in liquid (Al) in the temperature range of 700° to 850°C for Al - 0.7 mass% Ti and Al - 0.46

mass% Fe - 0.7 mass% Ti alloys. They found that the presence of Fe up to 0.5 mass% does not affect the

solubility of Ti in (Al) in the above temperature range.

[1998Akd] proposed that the value of activity coefficient of Al in -(Fe,Al,Ti) alloys has a strong influence

on the formation and growth kinetics of interfacial diffusion layer.

[1998Leo] synthesized nanocrystalline single-phase alloys of different structures in Al50Fe50-xTix(10 x 40) by mechanical alloying. Along the quasibinary section Ti50Al50-Ti50Fe50, they observed a

number of phase transformations during mechanical alloying in the sequence A3 (hcp) C14 (hcp) D8a

(fcc) B2(bcc) A2(bcc). During continuous heating, they also found that the nanocrystalline state is

preserved until about 500°C.

[2000Izu] studied the sulfidation of TiAl-2 at.% Fe alloy at 900°C using a gas mixture of H2-H2S. The

multilayer sulfide-scale was reported to consist of Ti- and Al-sulfides. They discussed the results in terms

of diffusion paths.

References

[1940Nis] Nishimura, H., Matsumoto, E., “The Equilibrium Diagram of the Al-Fe-Ti System and the

Segregation of Fe and Ti” (in Japanese), Nippon Kinzoku Gakkaishi, 10, 339-343 (1940)


[1954Sto] Stone, L., Margolin, H., “The Ti-V-Fe and Ti-Al-Fe Systems”, U.S. Atomic Energy

Commission Publication, AD-43730, 1-72 (1954) (Equi. Diagram, Experimental, #, *)

[1958Bok] Bok, Y.V., Mal`tsev, M.V., “Investigation of the Equilibrium Diagram of the Al-Fe-Ti

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433


MSIT®

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[1971Vol] Volkova, M.A., Kornilov, I.I., “Phase Equilibriums and Some Mechanical Properties the

Ti-Al-Fe and Ti-Al-V Alloys” (in Russian), Izv. Akad. Nauk SSSR, Met., 1, 200-205 (1971)


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434


MSIT®

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435


MSIT®

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[1991Nwo] Nwobu, A., Maeda, T., Flower, H.M., West, D.R.F., “The Constitution of Ti Rich Alloys of

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Structure of Fe4Ti0.93Al12.07, a Substitutional Variant of the Fe4Al13 Structure Type”,

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436


MSIT®

Al–Fe–Ti

[1997Nis1] Nishino, Y., Kumada, C., Asano, S., “Phase Stability of Fe3Al with Addition of 3d

Transition Elements”, Scripta Mater., 36, 461-466 (1997) (Crys. Structure, Equi. Diagram,

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with Addition of Transition Elemnets”, Mater. Sci. Eng. A, A234-236, 271-274 (1997)



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Separation in the b.c.c. Phase of the Fe-Al-Ti System”, Acta Mater., 46(6), 2983-2094

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[1999Gor] Gorzel, A., Palm, M., Sauthoff, G., “Constitution-based Alloy Selection for the Screening

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[1999Li] Li, J., Zong, Y., Hao, S.H., “Effects of Alloy Elements (C, B, Fe, Si) on the Ti-Al Binary

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[1999Yam] Yamamoto, Y., Hashimoto, K., Kimura, T., Nobuki, M., Kohno, N., “L12 Single Phase

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and (L1o) Phases in Ti-Al Base Ternary Alloys”, Intermetallics, 8, 855-867 (2000) (Crys.

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[2000Kai2] Kainuma, R., Ohnuma, I., Ishukawa, K., Ishida, K., “Stability of B2 Ordered Phase in the

Ti-Rich Portion of Ti-Al-Cr and Ti-Al-Fe Ternary Systems”, Intermetallics, 8, 869-875


[2000Koi] Koike, J., Shimoyama, Y., Ohnuma, I., Okamura, T., Kainuma, R., Ishida, K., Maruyama,

K., “Stress-Induced Phase Transformation During Superplastic Deformation in Two-Phase

Ti-Al-Fe”, Acta Mater., 48, 2059-2069 (2000) (Calculation, Crys. Structure, Equi. Diagram,


[2000Mab] Mabuchi, H., Nagayama, H., Tsuda, H., Matsui, T., Mori, K., “Formation of Ternary L12

Intermetallic Compound and Phase Relation in the Al-Ti-Fe System”, Mater. Trans. , JIM,

41(6), 733-738 (2000) (Crys. Structure, Equi. Diagram, Experimental, #, *, 50)

[2000Ohn] Ohnuma, I., Fujita, Y., Mitsui, H., Ishikawa, K., Kainuma, R., Ishida, K., “Phase Equilibria

in the Ti-Al Binary System”, Acta Mater., 48, 3113-3123 (2000) (Calculation, Equi.

Diagram, Experimental, Thermodyn., #, *, 37)

[2000Sha] Shan, A., Lin, D., “Low Temperature Superplasticity in Fe3Al Alloy”, Key Engineering

Materials, 171-174, 349-354 (2000) (Experimental, Mechan. Prop., 11)

437


MSIT®

Al–Fe–Ti

[2000Yan] Yang, R., Hao, Y., Song, Y., Guo, Z.X., “Site Occupancy of Alloying Additions in Titanium

Aluminides and its Application to Phase Equilibrium Evaluation”, Z. Metallkd., 91(4),

296-301 (2000) (Crys. Structure, Equi. Diagram, Review, 38)

[2001Ish] Ishikawa, K., Hashi, K., Suzuki, K., Aoki, K., “Effect of Substitutional Elements on the

Hydrogen Absorption-Desorption Properties of Ti3Al Compounds”, J. Alloys Compd., 314,


[2000Izu] Izumi, T., Yoshioka, T., Hayashi, S., Narita, T., “Sulfidation Properties of TiAl-2 at.% X

(X=V, Fe, Co, Cu, Nb, Mo, Ag and W) Alloys at 1173 K and 1.3 Pa Sulfur Pressure in an

H2S-H2 Gas Mixture”, Intermetallics, 8, 891-901 (2000) (Crys. Structure, Experimental,

42)

[2001Pra] Prakash, U., Sauthoff, G., “Structure and Properties of Fe-Al-Ti Intermetallics Alloys”,

Intermetallics, 9, 107-112 (2001) (Crys. Structure, Equi. Diagram, Experimental, Mechan.

Prop., 7)

[2001Sun] Sun, F.-S., Cao, C.-X., Kim, S.-E., Lee, Y.-T., Yan, M.-G., “Alloying Mechanism of Beta

Stabilizers in a TiAl Alloy”, Metall. Mater. Trans. A, 32A, 1573-1589 (2001) (Crys.

Structure, Equi. Diagram, Experimental, Mechan. Prop., 37)

[2001Tok] Tokar, A., Berner, A., Levin, L, “The Origin of a New Phase Observed During Quenching

of a TiAl-2Fe Alloy”, Mater. Sci. Eng. A, 308, 13-18 (2001) (Crys. Structure, Equi.


[2002Aze] Azez, K.A., AlL-Omari, I.A., Shobaki, J., Hasan, M.K., Al-Zoubi, G.M., Hamdeh, H.H.,

“Moessbauer Spectroscopic and Crystal Structure Investigation of the Fe0.7-xTixAl0.3 Alloy

System”, Physica B, 321(1-4), 178-182 (2002) (Crys. Structure, Experimental, Moessbauer,

16)

[2002Bra] Brandt, C., Inal, O.T., “Mechanical Properties of Cr, Mn, Fe, Co, and Ni Modified Titanium

Trialuminides”, J. Mater. Sci., 37(20), 4399-4403 (2002) (Crys. Structure, Experimental,

Mechan. Prop., 17)

[2002Ish] Ishikawa, K., Kainuma, R., Ohnuma, I., Aoki, K., Ishida, K., “Phase Stability of the X2AlTi

(X:Fe, Co, Ni and Cu) Heusler and B2-Type Intermetallic Compounds”, Acta Mater., 50,

2233-2243 (2002) (Calculation, Equi. Diagram, Experimental, Thermodyn., 12)

[2002Rag] Raghavan, V., “Al-Fe-Ti (Alimunum-Iron-Titanium)”, J. Phase Equilib., 23(4), 367-374

(2002) (Equi. Diagram, Review, *, 20).

[2003Duc] Ducher, R., Stein, F., Viguier, B., Palm, M., Lacaze, J., “A Re-examination of the Liquidus

Surface of the Al-Fe-Ti System”, Z. Metallkd., 94(4), 396-410 (2003) (Equi. Diagram,


[2003Gry] Grytsiv, A., Ding, J.J., Rogl, P., Weill, F., Chevalier, B., Etourneau, J. , Andre, G., Bouree,

F., Noel, H., Hundegger, P., Wiesinger, G., “Crystal Chemistry of the G-phases in the

Systems Ti-{Fe,Co,Ni}-Al with a novel filled variant of the Th6Mn23-type”, Intermetallics,

11, 351-359 (2003) (Experimental, Crys. Structure, 26)




[2003Sch] Schmid-Fetzer, R., “Al-Ti (Aluminium-Titanium)”, MSIT Evaluation Program, in MSIT


Stuttgart, to be published, (2002) (Equi. Diagram, Assessment, 86)

[2003Ste] Stein, F., Schneider, A., Frommeyer, G., “Flow Stress Anomaly and Order-Disorder

Transition in Fe3Al-Based Fe-Al-Ti-X Allos with X = V, Cr, Nb, or Mo”, Intermetallics,

11(1), 71-82 (2003) (Crys. Structure, Experimental, Mechan. Prop., 53)

438


MSIT®

Al–Fe–Ti


Phase/

Temperature Range

[°C]

Pearson Symbol/

Group Space/

Prototype

Lattice Parameters

[pm]

Comments

(Al)

< 660.452

cF4

Fm3m

Cu

a = 404.96 at 25°C [Mas2]

( Fe)(h2)

1538-1394

cI2

Im3m

W

a = 293.15 [Mas2]

( Fe)(h1)

1994-912

cF4

Fm3m

Cu

a = 364.67 [Mas2]

( Fe)(r)

< 912 °C

cI2

Im3m

W

a = 286.65 pure Fe at 20°C [V-C]

( Ti)(h)

1670-882

cI2

Im3m

W

a = 330.65 [Mas2]

( Ti)(r)

< 882

hP2

P63/mmc

Mg

a = 295.06

c = 468.25

pure Ti at 25°C [Mas2]

TiAl3 1393

tI8

I4/mmm

TiAl3

a = 384.9

c = 860.9

a = 384.8

c = 859.6

a = 384.7

c = 860.2

[2003Sch]

[2000Mab], at Al-25 at.% Ti

[1995Pal], contains 1.2 at.% Fe

Ti2Al51416-990

tP28

P4/mmm

Ti2Al5

a = 390.53

c = 2919.63

a = 387.5

c = 3348.4

a = 392.0

c = 2919.4

[2003Sch]

[1995Pal]

[2000Mab], Al-28.5 at.% Ti.

Heat treated at 1150°C for 24 h followed

by water quench

TiAl2 1205

tI24

I41/amd

HfGa2

a = 397.0

c = 2497.0

a = 397.1

c = 2432.0

[2003Sch]

[2000Mab], at Al-35 at.% Ti.


by water quench. Single phase alloy.

439


MSIT®

Al–Fe–Ti

TiAl

1463

tP4

P4/mmm

AuCu

a = 400.0

c = 407.5

a = 398.4

c = 406.0

a = 399.5

c = 408.0

a = 399.6

c = 407.7

a = 400.7

c = 404.9

a = 400.5

c = 404.7

[2003Sch], at 50 at.% Ti.

Solid solubility ranges

from 33.5 to 53.3 at.% Ti [2003Sch].

[2003Sch], at 38 at.% Ti.

[2000Mab], at Al-47 at.% Ti.


by water quench.

[1999Gor], at Al47.9Fe1.71Ti50.4

[1999Gor], at Al46Fe2.2Ti51.8

[1999Gor], at Al45.6Fe1.31Ti53.1

Ti3Al

1164

hP8

P63/mmc

Ni3Sn

a = 580.6

c = 465.5

a = 574.6

c = 462.4

a = 576.1

c = 462.4

[2003Sch], at 78 at.% Ti.

Solid solubility ranges

from 61.8 to 80 at.% Ti [2003Sch].

[2003Sch], at 62 at.% Ti.

[1999Gor], at Al36.3Fe0.93Ti62.8

1, Fe3Al

552.5

cF16

Fm3m

BiF3

a = 578.86 to 579.3 [2003Pis], solid solubility ranges

from 22.5 to 36.5 at.% Al.

Labelled as D03 (L21) in isothermal

sections.

2, FeAl

1310

cP2

Pm3m

CsCl

a = 289.76 to 290.78

a = 318.5

a = 318.5

[2003Pis], at room temperature

solid solubility ranges from 22.0 to

54.5 at.% Al.

Labelled as B2 in isothermal sections.

[1999Gor], at Al33.5Fe5.6Ti60.9

[1999Gor], at Al33.1Fe9.5Ti57.4

, Fe2Al31102-1232

cI16? a = 598.0 [2003Pis], solid solubility

ranges from 54.5 to 62.5 at.% Al

FeAl2 1156

aP18

P1

FeAl2

a = 487.8

b = 646.1

c = 880.0

= 91.75°

= 73.27°

= 96.89°

a = 487.2

b = 645.9

c = 879.4

= 91.76°

= 73.35°

= 96.89°

[2003Pis], at 66.9 at.% Al



[1995Pal], contains ablout 1.8 at.% Ti

Phase/

Temperature Range

[°C]

Pearson Symbol/

Group Space/

Prototype

Lattice Parameters

[pm]

Comments

440


MSIT®

Al–Fe–Ti

, Fe2Al5 1169

oC24

Cmcm

Fe2Al5

a = 765.59

b = 641.54

c = 421.84

a = 766.5

b = 640.9

c = 422.1

a = 765.6

b = 646.3

c = 422.9

[2003Pis], at 71.5 at.% Al


from 71.0 to 72.5 at.% Al.

[1995Pal], contains 1.5 at.% Ti

[1995Pal], contains 2.5 at.% Ti

Fe4Al13

1160

mC102

C2/m

Fe4Al13

a = 1552.7 to 1548.7

b = 803.5 to 808.4

c = 1244.9 to 1248.8

= 107.7 to 107.99°

a = 1549.2

b = 807.8

c = 1247.1

= 107.69°

a = 1548.9

b = 808.3

c = 1247.6

= 107.72°

a = 1565.3

b = 805.2

c = 1243.0

= 107.58°

[2003Pis], 74.16 to 76.7 at. % Al



[2003Pis], at 76.0 at.% Al

[1995Pal], contains about 6.5 at.% Ti

with Al being replaced

[1995Yan2], at Fe4Al12.07Ti0.93

TiFe2

1427

hP12

P63/mmc

MgZn2

a = 478.7

c = 781.5

a = 495.6

c = 803.2


from 24.0 to 36.0 at.% Ti [V-C]

[1996Mac], at Ti33.1Fe33.9Al33

TiFe

1317

cP2

Pm3m

CsCl

a = 297.6 solid solubility ranges

from 49.8 to 51.8 at.% Ti [V-C]

* 1, TiFe2Al cF16

Fm3m

AlCu2Mn

a = 414.0

a = 587.9

[1981Sei]

[1983Bus]

* 2’, Ti52Fe10Al38 t? a = 1150.0

c = 1380.0

[2001Tok], in a Ti-1.9 at.% Fe-49.6 at.%

Al alloy heat treated at 1200°C for 8 h

followed by water quench.

Phase/

Temperature Range

[°C]

Pearson Symbol/

Group Space/

Prototype

Lattice Parameters

[pm]

Comments

441


MSIT®

Al–Fe–Ti

* 2, TiFeAl2 cF116

Fm3m

Th6Mn23

filled Th6Mn23

filled Th6Mn23

tetragonal

a = 1199.0

a = 1182.0

a = 1211.0

a = 1203.8

a = 1207.6

a = 1209.9

a = 1189.0

a = 1209.2

a = 1211.0

a = 1197.3

c = 1276.83

a = 1195.9

c = 1274.59

a = 1197.0

c = 1276.0

[1967Mar, 2000Mab]

[1981Sei]

[1995Pal], at Al24.6Fe24.5Ti50.9

[1995Pal], at Al47.8Fe21.4Ti30.8

[1999Gor], at Al38.6Fe23Ti38.4

[1999Gor], at Al34.7Fe23.1Ti42.2

[2003Gry] at Al56Fe23.7Ti20.3

[2003Gry] at Al34.7Fe23.3Ti42

[1999Lev]

[1995Pal], at Al49Fe27Ti24

[1995Pal], at Al53.6Fe25.1Ti21.3

[1999Lev]

* 3,

Ti8Fe3Al22

cP4

Pm3m

AuCu3

a = 394.3

a = 394.3

a = 394.44

a = 393.5

[1991Nic], at Al22Fe3Ti8[1995Pal], at Al63.9Fe7.5Ti28.6

[1995Pal], at Al66.6Fe7.6Ti25.8

[2000Mab], at Al64Fe8Ti28

Phase/

Temperature Range

[°C]

Pearson Symbol/

Group Space/

Prototype

Lattice Parameters

[pm]

Comments

442


MSIT®

Al–Fe–Ti

Fig

. 1a:

R

eact

ion s

chem

e of

the

Al-

Fe-

Ti

syst

em

Al-

Fe

Fe-

Ti

A-B

-C

L (

αFe)

+T

iFe 2

13

05

e 1l

+ T

iFe 2

TiF

e

13

17

p5

L T

iFe 2

+ τ3

12

75

e 3

Al-

Fe-

Ti

L+

TiA

l+T

i 2A

l 5τ 3

ca.1

380

P1

Al-

Ti

l +

(βT

i) (

αTi)

14

90

p1

l+(α

Ti)

TiA

l

14

63

p2

l +

TiA

l T

i 2A

l 5

14

16

p3

l +

Ti 2

Al 5

TiA

l 3

13

93

p4

l (

αFe)

+ T

iFe 2

12

93

e 2

L+

Ti 2

Al 5

TiA

l 3+

τ 3ca

.13

70

U1

L+

(αT

i) (

βTi)

+T

iAl

>1300

U2

L +

τ3

TiA

l +

TiF

e 21

270

U3

L +

TiA

l (

βTi)

+T

iFe 2

12

35

U4

L+

(αF

e)+

TiF

e 2

(αT

i)+

(βT

i)+

TiA

l

L+

TiA

l 3+

τ 3

L+

(αF

e)+

TiF

e 2

p5

L+

TiF

e 2+

τ 3

L+

TiF

e 2+

τ 3L

+(β

Ti)

+T

iFe 2

(βT

i)+

TiF

e 2+

TiA

l

L+

(βT

i)+

TiA

l

L+

TiA

l+τ 3

TiA

l 3+

Ti 2

Al 5

+τ 3

TiA

l+T

i 2A

l 5+

τ 3

P1

L+

Ti 2

Al 5

+τ 3

TiA

l+T

iFe 2

+τ 3

L+

TiA

l+T

iFe2

U1

e 1

U2

U3

U1

443


MSIT®

Al–Fe–Ti

Fig

. 1b

:

Rea

ctio

n s

chem

e of

the

Al-

Fe-

Ti

syst

em

Al-

Fe

Fe-

Ti

A-B

-C

l +

(αF

e)ε

12

32

p6

(αT

i) T

i 3A

l +

TiA

l

11

18

e 6

ε (

αFe)

+ F

eAl 2

11

02

e 7

Al-

Fe-

Ti

L+

TiF

e 2+

τ 3τ 2

'1

225

P2

Al-

Ti

TiA

l+T

i 2A

l 5T

iAl 2

12

05

p7

Lε

+ F

e 2A

l 5

11

65

e 4

L F

e 2A

l 5+

Fe 4

Al 13

ca.1

160

e 5

ε +

Fe 2

Al 5

FeA

l 2

11

56

p8

L +

TiF

e 2 (

βTi)

+ T

iFe

ca.1

220

U5

TiA

l +

Ti 2

Al 5

τ 3 +

TiA

l 2ca

.12

00

U6

L +

TiF

e 2 (

αFe)

+ τ2'

11

40

U7

L +

(αF

e)τ 2

' + ε

ca.1

120

U8

(αT

i)+

TiA

l(β

Ti)

+ T

i 3A

lca

.11

10

U9

TiF

e 2+

(βT

i)T

iFe+

TiA

lca

.11

00

U10

p5

TiA

l+T

i 2A

l 5+

τ 3

U1

L+

TiF

e 2+

τ 3U3

(βT

i)+

TiF

e 2+

TiA

l

TiF

e 2+

τ 2'+

τ 3L

+τ 2

'+τ 3

L+

TiF

e 2+

τ 2'

e 1

(βT

i)+

TiF

e+T

iFe 2

Ti 2

Al 5

+T

iAl 2

+τ 3

L+

(βT

i)+

TiF

e

TiA

l+T

iAl 2

+τ 3

L+

(αF

e)+

τ 2'

U9

TiF

e 2+

TiF

e+T

iAl

(αT

i)+

(βT

i)+

Ti 3

Al

L+

ε+τ 2

'

U2

(αF

e)+

TiF

e 2+

τ 2'

(αF

e)+

ε+τ 2

'

U1

U8U9

(βT

i)+

TiF

e+T

iAl

U10

U6

P2

U1

U8

U6

U3

U1

U5 P2

e 3U4

L+

(βT

i)+

TiF

e 2

U4

(βT

i)+

TiA

l+T

i 3A

l

444


MSIT®

Al–Fe–Ti

Fig

. 1c:

Rea

ctio

n s

chem

e of

the

Al-

Fe-

Ti

syst

em

Al-

Fe

Fe-

Ti

A-B

-C

l (

βTi)

+ T

iFe

10

85

e 9

Lτ 3

+ F

e 4A

l 13

ca.1

100

e 8

Al-

Fe-

Ti

L+

τ 3τ 2

'+ F

e 4A

l 13

10

95

U11

Al-

Ti

L+

τ 3 T

iAl 3

+F

e 4A

l 13

10

92

U12

L+

ε τ 2

'+F

e 2A

l 51

088

U13

L F

e 4A

l 13+

τ 2'+

Fe 2

Al 5

10

85

E1

TiA

l+T

iFe+

TiF

e 2τ 2

10

75

P3

TiA

l+τ 3

TiF

e 2+

TiA

l 2ca

.10

70

U14

ε+F

e 2A

l 5τ 2

'+F

eAl 2

ca.1

070

U15

(βT

i)+

TiA

lT

iFe+

Ti 3

Al

ca.1

050

U16

ε (

αFe)

+F

eAl 2

+τ 2

'1

041

E2

L+

τ 2'+

Fe 4

Al 13

L+

TiA

l 3+

τ 3

ε+τ 2'+

Fe 2

Al 5

e 4 p8

L+

Fe 2

Al 5

+τ 2'

Fe 4

Al 13+

τ 2'+

Fe 2

Al 5

TiA

l+T

iFe+

τ 2T

iAl+

TiF

e 2+

τ 2T

iFe+

TiF

e 2+

τ 2

e 5

TiA

l+T

iFe 2

+T

iAl 2

TiF

e 2+

TiA

i 2+

τ 3

FeA

l 2+

ε+τ 2

'

(βT

i)+

TiF

e+T

iAl

U9

(βT

i)+

TiF

e+T

i 3A

lT

iAl+

TiF

e+T

i 3A

le 7

U8

P2

U5

L+

TiA

l 3+

Fe 4

Al 13

Fe 4

Al 13+

τ 2'+

τ 3

TiA

l 3+

Fe 4

Al 14+

τ 3

Fe 2

Al 5

+F

eAl 2

+τ 2

'

(αF

e)+

FeA

l 2+

τ 2'

L+

τ 2'+

τ 3

TiA

l+T

iAl 2

+τ 3

U6

U3

U1

U10

U9

U8

U6

U1

P2

U12

U9

P3'

U16

U14

P3

U10 T

iFe 2

+T

iFe+

TiA

l

445


MSIT®

Al–Fe–Ti

Fig

. 1d

:

Rea

ctio

n s

chem

e of

the

Al-

Fe-

Ti

syst

em

Al-

Fe

Fe-

Ti

A-B

-C

l(A

l)+

Fe 4

Al 13

65

5e 11

(βT

i) (

αTi)

+ T

iFe

58

3e 12

l +

TiA

l 3 (

Al)

66

4p9

Al-

Fe-

Ti

τ 3+

Ti 2

Al 5

TiA

l 2+

TiA

l 3ca

.99

5U17

Al-

Ti

Ti 2

Al 5

TiA

l 3+

TiA

l 2

99

0e 10

τ 3+

TiF

e 2τ 2

'+T

iAl 2

ca.9

70

U18

TiA

l 2+

TiF

e 2τ 2

'+T

iAl

ca.9

40

U20

TiA

l+T

iFe

τ 2+

Ti 3

Al

ca.9

50

U19

L+

TiA

l 3 (

Al)

+F

e 4A

l 13

65

8U21

(βT

i)(α

Ti)

+T

iFe+

Ti 3

Al

ca.5

80

E3

TiA

l 3+

Ti 2

Al 5

+τ 3

Ti 2

Al 5

+T

iAl 2

+τ 3

TiA

l 2+

TiA

l 3+

τ 3

TiF

e 2+

τ 2'+

τ 3

TiF

e 2+

TiA

l 2+

τ 3

TiA

l 2+

τ 2'+

τ 3 TiF

e+T

iAl 2

+τ 2

'

Ti 3

Al+

TiF

e+τ 2

TiA

l+T

i 3A

l+τ 2

TiA

l+F

eTi+

Ti 3

Al

TiA

l+T

iFe+

τ 2

TiA

l+T

iFe 2

+T

iAl 2

TiA

l+T

iAl 2

+τ 2

'

C1(<

94

0)

TiA

l+T

iFe 2

+τ 2

'

L+

TiA

l 3+

Fe 4

Al 13

(Al)

+F

eAl+

TiA

l 3

(βT

i)+

TiF

e+T

i 3A

l

(αT

i)+

TiF

e+T

i 3A

l

U16

U12P3

U14

U16 U14

U1

U6

P3'U9

(αT

i)+

(βT

i)+

Ti 3

Al

446


MSIT®

Al–Fe–Ti

20

40

60

80

20 40 60 80

20

40

60

80

Ti Fe


Axes: at.%

TiFe2

(αFe)

1600

1500

1400

1300 12

0012

00

FeTi

(βTi)

U7

(αTi)

Ti2Al5

Fe4Al13

Fe2Al5

U8

U13

τ

E1

U11

U12

1200

11001000

U2

e5

e4

p6

e11

p1

p2

TiAl3

U5

U4

U3

τ3

1300

1400

1400

1400

1500

1300

1300

p9

ε

U21

e8

e3

p3

p4

(Al)

TiAl

P1

U1

P2

e1

e2p5e9

Fig. 2: Al-Fe-Ti.

The liquidus surface

50

60

70

10 20

30

40

50

Ti 75.00Fe 0.00Al 25.00

Ti 45.00Fe 30.00Al 25.00

Ti 45.00Fe 0.00Al 55.00 Data / Grid: at.%

Axes: at.%

(αTi)

(αTi)+TiAl

(βTi)

(αTi)+(βTi)+TiAl

(αTi)+(βTi)

TiAl

Fig. 3: Al-Fe-Ti.

Partial isothermal

section at 1300°C

447


MSIT®

Al–Fe–Ti

50

60

70

10 20

30

40

50

Ti 75.00Fe 0.00Al 25.00

Ti 45.00Fe 30.00Al 25.00


Axes: at.%

TiAl

(βT

i)+T

iAl

(αTi)+(βTi)+TiAl

(αTi)+(βTi)

(αTi)+TiAl

(αTi)

(βTi)

10

20

30

40

10 20 30 40

60

70

80

90

Ti 50.00Fe 0.00Al 50.00

Ti 0.00Fe 50.00Al 50.00


Axes: at.%

τ3

L+τ3

TiAl

TiAl2

TiAl3

L+τ3+TiAl3

L+TiAl3

TiAl+τ3+TiFe

L

TiAl+TiAl2+τ3

TiAl2+Ti2Al5+τ3

Ti2Al5+TiAl3+τ3

Ti2Al5

Fig. 4: Al-Fe-Ti.

Partial isothermal

section at 1200°C

Fig. 5: Al-Fe-Ti.

Partial isothermal

section at 1200°C

448


MSIT®

Al–Fe–Ti

60

70

80

90

10 20 30 40

10

20

30

40

Ti Ti 50.00Fe 50.00Al 0.00


Axes: at.%

L+TiFe

L+(βTi)+TiFe

L+(βTi)

L

(βTi)

(αTi)

(βTi)+Ti3Al

TiFe+(βTi)

(βTi)+TiFe+TiAl

TiAl

Ti3Al

TiFe

10

20

30

40

50

10 20 30 40 50

50

60

70

80

90

Ti 60.00Fe 0.00Al 40.00

Ti 0.00Fe 60.00Al 40.00


Axes: at.%

τ2´TiFe2

L+τ2+τ3τ3

TiAl

L+τ 3

+TiA

l 3

TiAl3

L+TiAl3

Ti2Al5

L

TiAl2

L+τ3

Fig. 7: Al-Fe-Ti.

Partial isothermal

section at 1100°C

Fig. 6: Al-Fe-Ti.

Partial isothermal

section at 1150°C

449


MSIT®

Al–Fe–Ti

20

40

60

80

20 40 60 80

20

40

60

80

Ti Fe


Axes: at.%

L

Fe4Al13

Fe2Al5

FeAl2

B2

A2(αFe)

TiAl3

Ti2Al5

TiAl2

TiAl

Ti3Al

(αTi)

A2

B2

(βTi)

τ3

τ2´

τ2

TiFe

TiFe2B2+Ti3Al

A2+Ti3Al

A2+TiFe

B2+TiFeD03+B2

τ2´+B2τ2 ´+D03(L21)

B2+TiFe2

A2+TiFe2 (γFe)

D03(L21)

20

40

60

80

20 40 60 80

20

40

60

80

Ti Fe


Axes: at.%

(αFe)A2

Fe4Al13

L

Fe2Al5

FeAl2

B2

TiFe TiFe2

(βTi)

(αTi)

Ti3Al

TiAl

TiAl2

TiAl3

τ3

τ2´

τ2

B2+τ2 ´D0

3 (L21 )

D03(L21)

B2+TiFe2

B2+D03(L21)

Fig. 8: Al-Fe-Ti.


1000°C

Fig. 9: Al-Fe-Ti.


900°C

450


MSIT®

Al–Fe–Ti

20

40

60

80

20 40 60 80

20

40

60

80

Ti Fe


Axes: at.%L

Fe4Al13

Fe2Al5

FeAl2

B2+τ2 ´

B2

(αFe)

TiFe2

TiFe(βTi)

(αTi)

Ti3Al

TiAl

TiAl2

TiAl3τ3

B2+D03(L21)D03(L21)

D03 (L2

1 )+τ2 'τ2

τ2´

60

70

80

90

10 20 30 40

10

20

30

40

Ti Ti 50.00Fe 50.00Al 0.00


Axes: at.%

(αTi)+TiFe

Ti3Al+(αTi)+TiFe

TiFe+Ti3Al

TiFe+TiAl+Ti3Al

TiAl+Ti3Al

Ti3Al

(αTi)+Ti3Al

(αTi) TiFe

TiAl

Fig. 10: Al-Fe-Ti.


800°C

Fig. 11: Al-Fe-Ti.

Partial isothermal

section at 550°C

451


MSIT®

Al–Fe–Ti

10 20

500

750

1000

1250

Ti 0.00Fe 75.00Al 25.00

Ti 25.00Fe 50.00Al 25.00Ti, at.%

Tem

pera

ture

, °C

L

α2

(αFe)

α1

α1+α2

(αFe)+α1+α2

(αFe)+α1

(αFe)+α2

10 20

500

750

1000

1250

Ti 0.00Fe 77.00Al 23.00

Ti 25.00Fe 52.00Al 23.00Ti, at.%

Tem

pera

ture

, °C

α1+α2

(αFe)

α2

(αFe)+α2(αFe)+α1+α2

α1

(αFe)+α1

L

Fig. 12: Al-Fe-Ti.

Vertical section at a

constant Al-content of

25 at.%

Fig. 13: Al-Fe-Ti.


constant Al-content of

23 at.%

452


MSIT®

Al–Fe–Ti

20 30

500

750

1000

Ti 5.00Fe 79.00Al 16.00

Ti 5.00Fe 61.00Al 34.00Al, at.%

Tem

pera

ture

, °C

α2

(αFe)

(αFe)+α1

α1+α2

α1

1400

1200

1000

800

600

400

5 10 15 20 5101520

Fe Al3 Fe AlTi

2FeAl

L21

L L( Fe)�

�2

�1�1

��1+��

�� Fe)+ �1+

��Fe)+�1

�2

��Fe)+��

Temperature,°C

at.% Ti at.% Ti

Fig. 14: Al-Fe-Ti.


constant Ti-content of

5 at.%

Fig. 15: Al-Fe-Ti.

Conjoined vertical

sections along

Fe3Al-Fe2TiAl and

Fe2TiAl-FeAl

light metal systems. part 2: selected systems from al-cu-fe to al-fe-ti

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