modelling of phases in mg-db - computherm llc · computherm llc thermodynamic databases 8 1.3...

Thermodynamic Database

User’s Guide

Copyright © 2000-2014 CompuTherm LLC

CompuTherm LLC Thermodynamic Databases

i

Contents

1. PanAluminum .................................................................................... 6

1.1 Components .................................................................................... 7

1.2 Suggested Composition Range ......................................................... 7

1.3 Phases ............................................................................................. 8

1.4 Key Elements and Subsystems......................................................... 9

1.5 Database Validation ....................................................................... 10

1.6 References ..................................................................................... 14

2. PanCobalt ......................................................................................... 15

2.1 Components .................................................................................. 16

2.2 Suggested Composition Range ....................................................... 16

2.3 Phases ........................................................................................... 17

2.4 Key Elements and Subsystems....................................................... 18


2.6 References ..................................................................................... 22

3. PanIron ............................................................................................ 23

3.1 Components .................................................................................. 24


3.3 Phases ........................................................................................... 25


ii



3.6 References ..................................................................................... 35

4. PanMagnesium ................................................................................. 36

4.1 Components .................................................................................. 37


4.3 What's new in PanMg2014 ............................................................. 38

4.4 Phases ........................................................................................... 38



4.7 References ..................................................................................... 54

5. PanMolybdenum ............................................................................... 58

5.1 Components .................................................................................. 59


5.3 Phases ........................................................................................... 59



5.6 Reference ....................................................................................... 68

6. PanNiobium ...................................................................................... 69

6.1 Components .................................................................................. 70


iii


6.3 Phases ........................................................................................... 70



6.6 References ..................................................................................... 81

7. PanNickel ......................................................................................... 82

7.1 Components .................................................................................. 83


7.3 Phases ........................................................................................... 83



7.6 References ..................................................................................... 94

8. PanNoble .......................................................................................... 95

8.1 Components .................................................................................. 96


8.3 Phases ........................................................................................... 96



8.6 References ................................................................................... 102

9. PanSolution .................................................................................... 103


iv

9.1 General Information ..................................................................... 104

10. PanTitanium ................................................................................... 106

10.1 Components ............................................................................. 107

10.2 Suggested Composition Range ................................................... 107

10.3 Phases ...................................................................................... 107

10.4 Sub-System Information ........................................................... 108

10.5 Database Validation .................................................................. 110

10.6 References ................................................................................ 118

11. PanBMG ......................................................................................... 120

11.1 Components ............................................................................. 121


11.3 Phases ...................................................................................... 121



11.6 References ................................................................................ 129

12. ADAMIS .......................................................................................... 130

12.1 Components ............................................................................. 131


12.3 Phases ...................................................................................... 131



v


12.6 Applications .............................................................................. 137

12.7 References ................................................................................ 137

13. MDT Copper ................................................................................... 138

13.1 Components ............................................................................. 139


13.3 Phases ...................................................................................... 139

13.4 Key Elements and Subsystems .................................................. 141


13.6 References ................................................................................ 144


6

1. PanAluminum

Thermodynamic database for multi-component

Aluminum-rich casting and wrought alloys

Copyright © CompuTherm LLC

Al

Ag B C

Cr

Cu

Fe

Gd

Ge

Hf

Li Mg Mn Ni

Sc

Si

Sn

Sr

Ti

V

Y

Zn Zr


7

1.1 Components

Total of 23 components are included in the database as listed here:

Major alloying elements: Al, Cu, Fe, Mg, Mn, Si and Zn

Minor alloying elements: Ag, B, C, Cr, Gd, Ge, Hf, Li, Ni, Sc, Sn, Sr, Ti, V,

Y, and Zr

1.2 Suggested Composition Range

The suggested composition range for each element is listed in Table 1.1.

It should be noted that this given composition range is rather

conservative. It is derived from the chemistries of the multicomponent

commercial alloys that have been used to validate the current database.

In the subsystems, many of these elements can be applied to a much

wider composition range. In fact, some subsystems are valid in the entire

composition range as given in section 1.4.

Table 1.1: Suggested composition range

Element Composition Range (wt.%)

Al 80 ~ 100

Cu 0 ~ 5.5

Fe 0 ~ 1.0

Mg 0 ~ 7.6

Mn 0 ~ 1.2

Si 0 ~ 17.5

Zn 0 ~ 8.1

other 0 ~ 0.5


8

1.3 Phases

Total of 252 phases are included in the current database. The names and

thermodynamic models of the major phases are given in Table 1.2.

Information on all the other phases may be displayed in the TDB Viewer

of Pandat or can be found at www.computherm.com.

Table 1.2: Phase name and related information

Name Lattice Size Constituent

Al15_FeMn3Si2 (16)(4)(1)(2) (Al)(Fe,Mn)(Si)(Al,Si)

Al6_FeMn (6)(1) (Al)(Fe,Mn)

Al7Cu2Fe (7)(2)(1) (Al)(Cu)(Fe)

Al8FeMg3Si6 (8)(3)(1)(6) (Al)(Mg)(Fe)(Si)

Al8FeMnSi2 (16)(2)(2)(3) (Al)(Fe)(Mn)(Si)

AlMgMn_T (18)(3)(2) (Al)(Mg)(Mn)

AlMgZn_Tau (26)(6)(48)(1) (Mg)(Al,Mg)(Al,Mg,Zn)(Al)

Alpha_AlFeSi (0.66)(0.19)(0.05)(0.1) (Al)(Fe)(Si)(Al,Si)

Beta_AlFeSi (0.598)(0.152)(0.1)(0.15) (Al)(Fe,Mn)(Si)(Al,Si)

Cu16Mg6Si7 (0.551724)(0.206897) (0.241379)

(Cu)(Mg)(Si)

Fcc (1)(1) (Ag,Al,Cu,Fe,Gd,Ge,Li,Mg,Mn,Sc,Si,Sn,Zn,Cr,Ni,Ti,V,Zr,Hf,Sr,Y)(B,C,Va)

LiZn2 (1)(2) (Li)(Zn)

Liquid (1) (Ag,Al,B,C,Cr,Cu,Fe,Gd,Ge,Hf,Li,Mg,Mn,Ni,Sc,Si,Sn,Sr,Ti,V,Y,Zn,Zr)

Mg2Si (2)(1) (Mg)(Ge,Si)

Q (0.4375)(0.375)(0.1875) (Al)(Mg)(Cu)

http://www.computherm.com/


9

S (0.5)(0.25)(0.25) (Al)(Mg)(Cu)

T (26)(6)(48)(1) (Mg)(Al,Mg)(Al,Cu,Mg,Zn)(Al)

V (0.38461)(0.15385) (0.46154)

(Al)(Mg)(Cu)

1.4 Key Elements and Subsystems

Key elements of the system are listed as: Al-Cu-Fe-Mg-Mn-Si-Zn. The

modeling status for the constituent binaries and ternaries of these key

elements are given in Tables 1.3-1.4. The color represents the following

meaning:

: Full description

: Full description for major phases

: Extrapolation

Table 1.3: Modeling status of key constituent binary systems

Cu Fe Mg Mn Si Zn

Al Al-Cu Al-Fe Al-Mg Al-Mn Al-Si Al-Zn

Cu Cu-Fe Cu-Mg Cu-Mn Cu-Si Cu-Zn

Fe Fe-Mg Fe-Mn Fe-Si Fe-Zn

Mg Mg-Mn Mg-Si Mg-Zn

Mn Mn-Si Mn-Zn

Si Si-Zn

Table 1.4: Modeling status of key constituent ternary systems

Fe Mg Mn Si Zn

Al-Cu Al-Cu-Fe Al-Cu-Mg Al-Cu-Mn Al-Cu-Si Al-Cu-Zn

Al-Fe Al-Fe-Mg Al-Fe-Mn Al-Fe-Si Al-Fe-Zn

Al-Mg Al-Mg-Mn Al-Mg-Si Al-Mg-Zn

Al-Mn Al-Mn-Si Al-Mn-Zn

Al-Si Al-Si-Zn


10

1.5 Database Validation

The PanAl database is validated by a large amount of phase equilibrium

data. Two examples are shown here. Figure 1.1 shows the calculated

isotherm of Al-Cu-Mg-Si at 500ºC with Si content of 1.8wt%. The

experimental data of D.P. Smith [1962Smi] are plotted on it for

comparison. Figure 1.2 shows the calculated isopleth of Al-Fe-Mg-Si at

4wt.%Mg and 0.5wt.%Fe with experimental data from Phillips [1961Phi].

Figure 1.1: Comparison of a calculated isothermal section of Al-Cu-Mg-Si at 1.8wt%Si

and at T=500C with the experimental data [1962Smi]


11

Figure 1.2: Comparison of a calculated isopleth of Al-Fe-Mg-Si at 4wt.%Mg and

0.5wt.%Fe with the experimental data [1961Phi]

In addition to the validation of phase equilibria, the current database has

also been subjected to extensive validation by the solidification data of

commercial aluminum alloys. Figure 1.3 presents the Scheil model

predicted solidification paths of Al-5Cu-0.5Mg-0.5Ag (wt%) and Al-5Cu-

0.5Mg-0.5Ag-1.2Li (wt%) alloys. It is seen that 1.2 wt% of Li has

significant effect on this Al alloy.

0 2 4 6 8 10 12 14

400

450

500

550

600

650 Calculation of this work

DTA measurements

T(o

C)

wt.% (Si)


12

Figure 1.3: Scheil-model predicted solidification sequence for two aluminum alloys:

Al-Cu-Mg-Ag vs. Al-Cu-Mg-Ag-Li

This database can also supply important parameters for processing

simulation. One of these parameters is partition coefficient. The

calculated partition coefficients have also been extensively validated.

Examples for two Al-Cu-Mg-Zn quaternary alloys are given below.

Figures 1.4 and 1.5 show comparisons between calculated and measured

partition coefficient for Al-4Cu-0.9Mg-2.6Zn (wt%) and Al-2.5Cu-1.3Mg-

2.63Zn (wt%), respectively. The good agreement between the

experimental and calculated results, as shown in these figures, indicates

the reliability of the current PanAl thermodynamic database in providing

thermodynamic input for processing simulation.

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

460

480

500

520

540

560

580

600

620

640

660 Al-5Cu-0.5Mg-0.5Ag (wt.%)

Al-5Cu-0.5Mg-0.5Ag-1.2Li (wt.%)

L=(Al)+Al7CuLi+Al

2CuLi+S+AlMgAg

L=(Al)+Al7CuLi+Al

2CuLi+S

L=(Al)+Al7CuLi+Al

2CuLi

L=(Al)+AlCu_S+AlMgAg

L=(Al)+AlCu_S

T(o

C)

fs

L=(Al) L=(Al)+AlCu_

L=(Al)+Al7CuLi


13

Figure 1.4: Comparison between the calculated and experimentally determined

[1998Lia] partition coefficients of alloy Al-4wt%Cu-0.9wt%Mg-2.6wt%Zn

Figure 1.5: Comparison between the calculated and experimentally determined

[1998Lia] partition coefficients of alloy Al-2.5wt%Cu-1.3wt%Mg-2.63wt%Zn

Pa

rtitio

n C

oe

ffic

ien

t

Temperature Celsius

0.0

0.4

0.8

1.2

1.6

520 540 560 580 600 620

Temperature_Celsius

Pa

rtitio

n C

oeffic

ien

t

AlZnMgCu Liang

Partition coefficient of Al-4wt%Cu-0.9wt%Mg-2.6wt%Zn

520 540 560 580 600 6200

0.4

0.8

1.2

1.6

Pa

rtitio

n c

oe

ffic

ien

t

Temperature celsius

0.0

0.4

0.8

1.2

1.6

540 560 580 600 620

Temperature_celsius

Pa

rtitio

n c

oe

ffic

ien

t

ALCuMgZn Liang

Partition coefficient of Al-2.5wt%Cu-1.3wt%Mg-2.63wt%Zn

540 560 580 600 6200

0.4

0.8

1.2

1.6


14

The molar volume parameters for the major phases in the PanAl

database are also modeled. Figure 1.6 shows the calculated density of

the Al-6Mg-2Zn-2Cu-0.1Zr (wt.%) alloy from 650oC to room temperature.

Figure 1.6: Calculated density of the Al-6Mg-2Zn-2Cu-0.1Zr (wt.%) alloy using the

molar volume parameters in the PanAl database

1.6 References

[1962Smi] D.P. Smith, Metallurgia, 1, 1962, pp: 223.

[1961Phi] Phillips H.W.L., “Equilibrium diagrams of aluminum alloy systems,” The aluminum development association,

Information bul, London, Dec. 25, 1961, pp: 105-108

[1998Lia] 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).


15

2. PanCobalt

Thermodynamic Database for Cobalt-Based

Superalloys


Co

Al B

C

Cr

Cu

Fe

Mn

Mo Nb

Ni

Pt

Re

Si

Ta

Ti

W


16

2.1 Components


Al-B-C-Co-Cr-Cu-Fe-Mn-Mo-Nb-Ni-Pt-Re-Si-Ta-Ti-W










Element Composition range (wt%)

Co 50-100

Al 0-50

B,C,Cu,Mn,Pt,Si 0-0.5

Cr 0-30

Mo 0-20

Nb 0-10

Ni 0-50

Fe 0-20

Re 0-20

Ta 0-20

Ti 0-10

W 0-20


17

2.3 Phases







B2 (1)(1) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W) (Co,Cr,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W,Va)

Bcc (1)(3) (Al,Co,Cr,Cu,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W) (B,C,Va)

Chi (24)(10)(24) (Cr,Fe,Mo,Ni,Re)(Cr,Mo,Nb,Re,Ta,W) (Cr,Fe,Nb,Ni,Re,Ta,W)

Disorder (1) (Al,Co,Cr,Fe,Mo,Ni,Pt,Re,Ta,T,W)

Fcc (1)(1) (Al,Co,Cr,Cu,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W) (B,C,Va)

Hcp (1)(0.5) (Al,Co,Cr,Cu,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W) (B,C,Va)

L12 (0.75)(0.25)(1) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W) (Va)

Laves_C14 (2)(1) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ta,Ti) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ta,Ti,W)

Laves_C15 (2)(1) (Al,Co,Cr,Fe,Nb,Ni,Ta,Ti) (Al,Co,Cr,Fe,Mo,Nb,Ta,Ti,W)

Laves_C36 (2)(1) (Al,Co,Cr,Fe,Ni,Ta,Ti) (Al,Co,Cr,Fe,Mo,Nb,Ta,Ti)

Liquid (1) (Al,B,C,Co,Cr,Cu,Fe,Mn,Mo,Nb,Ni,Pt,Re,Si,Ta,Ti,W)

Mu (7)(2)(4) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ta,W) (Mo,Nb,Ta,Ti,W)



18

(Co,Cr,Fe,Mo,Nb,Ni,Ta,Ti,W)

Sigma (8)(4)(18) (Al,Co,Cr,Fe,Mn,Ni,Pt,Re,Ta,W) (Cr,Fe,Mo,Nb,Re,Ta,Ti,W) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Pt,Re,Ta,Ti,W)


Key elements of the system are listed as: Co-Al-Cr-Fe-Mo-Nb-Ni-Re-Ta-

Ti-W. The current modeling status for the constituent binaries and

ternaries are given in Tables 2.3-2.4. The color represents the following

meaning:

: Full description


: Extrapolation

Table 2.3: Key binaries of the Co-Al-Cr-Fe-Mo-Nb-Ni-Re-Ta-Ti-W system

Co Cr Fe Mo Nb Ni Re Ta Ti W

Al Al-Co Al-Cr Al-Fe Al-Mo Al-Nb Al-Ni Al-Re Al-Ta Al-Ti Al-W

Co Co-Cr Co-Fe Co-Mo Co-Nb Co-Ni Co-Re Co-Ta Co-Ti Co-W

Cr Cr-Fe Cr-Mo Cr-Nb Cr-Ni Cr-Re Cr-Ta Cr-Ti Cr-W

Fe Fe-Mo Fe-Nb Fe-Ni Fe-Re Fe-Ta Fe-Ti Fe-W

Mo Mo-Nb Mo-Ni Mo-Re Mo-Ta Mo-Ti Mo-W

Nb Nb-Ni Nb-Re Nb-Ta Nb-Ti Nb-W

Ni Ni-Re Ni-Ta Ni-Ti Ni-W

Re Re-Ta Re-Ti Re-W

Ta Ta-Ti Ta-W

Ti Ti-W

Table 2.4: Key ternaries of the Co-Al-Cr-Fe-Mo-Nb-Ni-Re-Ta-Ti-W system

Cr Fe Mo Nb Ni Ta Ti W

Co-Al Co-Al-Cr Co-Al-Fe Co-Al-Mo Co-Al-Nb Co-Al-Ni Co-Al-Ta Co-Al-Ti Co-Al-W

Co-Cr Co-Cr-Fe Co-Cr-Mo Co-Cr-Nb Co-Cr-Ni Co-Cr-Ta Co-Cr-Ti Co-Cr-W

Co-Fe Co-Fe-Mo Co-Fe-Nb Co-Fe-Ni Co-Fe-Ta Co-Fe-Ti Co-Fe-W

Co-Ni Co-Mo-Ni Co-Nb-Ni Co-Ni-Ta Co-Ni-Ti Co-Ni-W


19


The current thermodynamic database for cobalt alloys has been

extensively tested and validated using the published experimental data

[2008Ish, 2008Shi]. Some sub-quaternary systems of this database: Co-

Al-Ni-W, Co-Al-Cr-Ni, have been critically assessed, but have not been

published yet.

Figure 2.1 and Figure 2.2 show two calculated isoplethal sections in the

Co-Al-Ni-W quaternary system. Figure 2.1 is a vertical section at 10 at%

of Al and 7.5 at% of W and Figure 2.2 is at 10 at.% of Al and 10 at.% of

W. The measured solidus and ˊ solvus temperatures [2008Ish, 2008Shi]

are plotted on the figures for comparison. In both figures, the calculated

phase boundaries are in good agreement with the experimental data.

Figure 2.3 and 2.4 show two calculated isothermal sections with Ni

content at 60 at% at 1100oC and 1000oC, respectively. The calculated

results agree well with the experimental observations from anneal alloy

samples [2006Bur]. Figure 2.5 shows the comparison between the

calculated liquidus, solidus and ˊ solvus temperatures and the

experimentally measured ones.


20

Figure 2.1: Calculated Co-xNi-10Al-7.5W isopleth with measured solidus and ˊ solvus

temperatures [2008Ish, 2008Shi]

Figure 2.2: Calculated Co-xNi-10Al-10W isopleth with measured solidus and ˊ solvus

temperatures [2008Ish, 2008Shi]


21

Figure 2.3: Comparison of the calculated 1100oC isothermal section of the Ni-Al-Cr-Co

system with 60 at.% of Ni with experimental observations

Figure 2.4: Comparison of the calculated 1000oC isothermal section of the Ni-Al-Cr-Co

system with 60 at.% of Ni with experimental observations


22

900 1000 1100 1200 1300 1400 1500 1600

900

1000

1100

1200

1300

1400

1500

1600

Calc

ula

ted

Tem

pera

ture

(oC

)

Experimental Temperature (oC)

Liquidus

solidus

' solvus

Figure 2.5: Comparison between calculated results and experimental data for Liquidus,

solidus and ˊ solvus temperatures.

2.6 References

[2006Bur] J. Bursik, P. Broz, J. Popovic, "Microstructure and phase equilibria in Ni-Al-Cr-Co alloys", Intermetallics, 2006, 14, 1257-1261.

[2008Ish] K. Ishida, "Intermetallic Compounds in Co-base alloys - Phase Stability and Application to Superalloys", MRS

proceedings, 2008, vol. 1128.

[2008Shi] K. Shinagawa et al., "Phase Equilibria and Microstructure on g' Phase in Co-Ni-Al-W System", Materials Transactions,

2008, 49(6), 1474-1479.


23

3. PanIron


Fe-rich alloys


Fe

Al As B

C

Ca

Co

Cr

Cu

Mg

Mn

Mo N Nb

Ni

P

Pb

S

Si

Sn

Ti

V

W Zr


24

3.1 Components


Major alloy elements: Co, Cr, Fe, Mo, Ni, V and W.

Minor alloy elements: Al, As, B, C, Ca, Cu, Mg, Mn, N, Nb, P, Pb, S, Si,

Sn, Ti and Zr.










Elements Composition Range (wt.%)

Fe 50 ~ 100

Ni 0 ~ 31

Cr 0 ~ 27

Co, Mo 0 ~ 10

Pb, V, W 0 ~ 7

B, C, Cu, Mn, Nb, Si, Ti 0 ~ 4

Al, As, Ca, Mg, N 0 ~ 0.5

P, S, Sn, Zr 0 ~ 0.05


25

3.3 Phases

Total of 363 phases are included in the database. The names and






Bcc (ferrite)

(1)(3) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,P,S,Si,Sn,Ti, V,W,Zr)(B,C,N,Va)

Cementite (3)(1) (Co,Cr,Fe,Mn,Mo,Nb,Ni,V,W)(B,C,N)

Fcc (austenite)

(1)(1) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,P,S,Si,Sn,Ti, V,W,Zr)(B,C,N,Va)

Fcc_MC (1)(1) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,P,S,Si,Sn,Ti, V,W,Zr)(B,C,N,Va)

Graphite (1) (B,C)

Hcp (1)(0.5) (Al,B,Co,Cr,Cu,Fe,Mg,Mn,Mo,Nb,Ni,Si,Sn,Ti,V, W,Zr)(B,C,N,Va)

Laves_C14 (2)(1) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ti,W,Zr) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Ti,W,Zr)

Liquid (1) (Al,B,C,Co,Cr,Cu,Fe,Fe1Si1,Mg,Mn,Mn1Si1,Mo, N,Nb,Ni,P,S,Si,Sn,Ti,V,W,Zr)

M23C6 (20)(3)(6) (Co,Cr,Fe,Mn,Ni,V)(Co,Cr,Fe,Mn,Mo,Ni,V,W) (B,C)

M3C2 (3)(2) (Cr,Mo,V,W)(C)

M5C2 (5)(2) (Fe,Mn,V)(C)

M5Si3 (0.625)(0.375) (Cr,Fe,Mn,Mo,W)(Si)

M6C (2)(2)(2)(1) (Co,Fe,Ni)(Mo,Nb,W)(Co,Cr,Fe,Mo,Nb,Ni,V,W)



26

(C)

M7C3 (7)(3) (Co,Cr,Fe,Mn,Mo,Ni,V,W)(C)

Mu_PHASE (7)(2)(4) (Al,Co,Cr,Fe,Mo,Mn,Nb,Ni)(Mo,Nb,W)(Al,Co,Cr, Fe,Mo,Nb,Ni,W)

P_PHASE (24)(20)(12) (Cr,Fe,Ni)(Cr,Fe,Mo,Ni)(Mo)

R_PHASE (27)(14)(12) (Co,Cr,Fe,Mn,Ni)(Mo,W)(Co,Cr,Fe,Mn,Mo,Ni,W)

Sigma (8)(4)(18) (Al,Co,Fe,Mn,Ni,Si)(Cr,Mo,Nb,V,W)(Al,Co,Cr,Fe, Mn,Mo,Nb,Ni,Si,V,W)


Key elements of the system are listed as: Co-Cr-Fe-Mo-Ni-V-W. The



meaning:

: Full description


: Extrapolation

Table 3.3: Key binary systems for the Co-Cr-Fe-Mo-Ni-V-W

Cr Fe Mo Ni V W

Co Co-Cr Co-Fe Co-Mo Co-Ni Co-V Co-W

Cr Cr-Fe Cr-Mo Cr-Ni Cr-V Cr-W

Fe Fe-Mo Fe-Ni Fe-V Fe-W

Mo Mo-Ni Mo-V Mo-W

Ni Ni-V Ni-W

V V-W


27

Table 3.4: Key ternary systems for the major components


The current thermodynamic database for iron-based alloy systems has

been extensively tested and validated using the published experimental

data. This database can be used to calculate phase equilibria for multi-

component iron alloys, such as the equilibrium between Bcc (ferrite) and

Fcc (austenite). It can be used to predict phase transformation

temperatures, such as liquidus, solidus, and so on. The fraction of each

phase as a function of temperature, partitioning of components in

different phases can also be calculated. In addition to equilibrium

calculations, Scheil simulations can also be carried out using this

database. Some validation results are presented in Figures 3.1 to 3.4.

Figure 3.1 shows comparison between the calculated and experimentally

measured liquidus and solidus temperatures for variety of steels. Figure

3.2 shows comparison between the calculated and experimentally

observed amounts of austenite in duplex stainless steels. Figure 3.3 is a

comparison between the calculated and experimentally measured

partitioning of Fe, Cr, Mo, and Ni in ferrite and austenite.

Co Cr Mo Ni W

Fe-B Fe-B-Co Fe-B-Cr Fe-B-Mo Fe-B-Ni Fe-B-W

Fe-C Fe-C-Co Fe-C-Cr Fe-C-Mo Fe-C-Ni Fe-C-W

Fe-Co Fe-Co-Cr Fe-Co-Mo Fe-Co-Ni Fe-Co-W

Fe-Cr Fe-Cr-Mo Fe-Cr-Ni Fe-Cr-W

Fe-Mo Fe-Mo-Ni Fe-Mo-W

Fe-Ni Fe-Ni-W


28

Figure 3.1: Comparison between the calculated and experimentally measured liquidus

and solidus temperatures for iron-based alloys with experimental data from [1977Jer]

Figure 3.2: Comparison between the calculated and experimentally measured amounts

of austenite in duplex stainless steels of austenite (Fcc)

1200

1300

1400

1500

1600

1200 1300 1400 1500 1600

Measured (oC)

Calc

ula

ted

(oC

)

liquidus

solidus

Diagonal

0

20

40

60

80

100

0 20 40 60 80 100

Measured %

Calc

ula

ted

%

83Mae

85Hay

85Tho

91Lon

94Lon

94Bon

94Nys

Diagonal


29

Figure 3.3: Comparison between the calculated and experimentally measured

partitioning of Fe, Cr, Mo and Ni in ferrite and austenite

Figures 3.4a to 3.4e are comparisons between the calculated and

experimentally observed equilibrium compositions for Fe, C, Cr, Mo, Si, V

and W in austenite, ferrite and M6C, respectively. These figures show

reasonable agreement between the calculated values using the current

PanFe database and the experimental determined ones.

0

0.4

0.8

1.2

1.6

2

0 0.4 0.8 1.2 1.6 2

Measured

Ca

lcu

late

d

85Hay

91Cor

90Hay

91Mer

94Ham

Diagonal


30

Figure 3.4(a): Comparison between the calculated and measured equilibrium

composition of Fe in the Fcc (austenite) phase

Figure 3.4(b): Comparison between the calculated and measured equilibrium

compositions of C, Cr, and Mo in the Fcc (austenite) phase

88

89

90

91

92

93

94

88 89 90 91 92 93 94

Measured

Calc

ula

ted

diagonal

Fe

0

1

2

3

4

5

6

0 1 2 3 4 5 6Measured

Calc

ula

ted

diagonal

C

Cr

Mo


31

Figure 3.4(c): Comparison between the calculated and measured equilibrium

compositions of Si, V and W in the Fcc (austenite) phase

Figure 3.4(d): Comparison between the calculated and measured equilibrium

compositions of Cr, Mo, Si, V and W in the Bcc (ferrite) phase

0

0.5

1

1.5

2

0 0.5 1 1.5 2Measured

Calc

ula

ted

diagonal

Si

V

W

0

1

2

3

4

5

6

0 1 2 3 4 5 6Measured

Calc

ula

ted

diagonal

Cr

Mo

Si

V

W


32

Figure 3.4(e): Comparison between the calculated and measured equilibrium

compositions of Cr, Mo, Fe, V and W in the M6C phase

The molar volume data are modeled for all the elements of the Bcc and

Fcc phases in the PanFe database. Figure 3.1 shows one example which

compares the calculated molar volume of pure iron (in both ferrite and

austenite states) as a function of temperature with experimental data

[1957Gol, 1995Bas].

0

10

20

30

40

50

60

0 10 20 30 40 50 60

Measured

Calc

ula

ted

diagonal

Cr

V

W

Fe

Mo


33

Figure 3.5: Comparison between the calculated and experimental measured molar

volume of pure iron vs. temperature

The molar volumes of Bcc and Fcc phases in the Fe-X binaries can also

be calculated. Figure 3.6 shows the calculated molar volume of both Bcc

and Fcc phases in the Fe-Ni binary system at several temperatures.

Comparisons between calculated and experimental data [1972Mas,

1973Gup and 2005Mis] show good agreement.

One of the most important applications of the molar volume database is

to calculate the relative length change of iron-based alloys during casing

and/or heat-treatment processing. The comparison between the

calculated and experimentally measured relative length change of

SAE5120 alloy is shown in figures 3.7 and good agreements are

obtained.

7.0e-06

7.1e-06

7.2e-06

7.3e-06

7.4e-06

0 200 400 600 800 1000 1200

Temperature [oC]

Vm

[m

3

/mole

_ato

m

s]

austenite

ferrite

Calculated Vm for pure Fe of this workExperimental data [55Bas,57Gol]

Transformation temperature is 910oC

0 200 400 600 800 1000 12007.05e-006

7.15e-006

7.25e-006

7.35e-006

7.45e-006


34

Figure 3.6: Comparison between the calculated and experimental measured molar

volume of both BCC and Fcc phases of the Fe-Al binary system vs. Temperature

Figure 3.7: Comparison between the calculated and experimentally measured relative

length change of SAE5120 alloy

6.3e-06

6.4e-06

6.5e-06

6.6e-06

6.7e-06

6.8e-06

6.9e-06

7.0e-06

7.1e-06

7.2e-06

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

fcc-Fe

This work at 873KThis work at 673KThis work at 473KThis work at 298K1972Mas1972Mas1972Mas2005Mis

Fe NiMol. Fracn. Ni

Vm

[m

3

/mole

_ato

m

s]

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 16.3e-006

6.4e-006

6.5e-006

6.6e-006

6.7e-006

6.8e-006

6.9e-006

7e-006

7.1e-006

7.2e-006

6.6e-06

6.7e-06

6.8e-06

6.9e-06

7.0e-06

7.1e-06

7.2e-06

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

bcc-Fe

This work at 298KThis work at 673K2005Mis1973Gup

Fe NiMol. Fracn. Ni

Vm

[m

3

/mole

_ato

m

s]

0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 16.6e-006

6.7e-006

6.8e-006

6.9e-006

7e-006

7.1e-006

7.2e-006

0.000

0.002

0.004

0.006

0.008

0.010

0.012

0.014

0.016

100 200 300 400 500 600 700 800 900 1000 1100

Temperature [oC]

L/L

Calculation of this workSAE 5120 heating dilatation curve

100 200 300 400 500 600 700 800 900 1000 11000

0.002

0.004

0.006

0.008

0.01

0.012

0.014

0.016


35

3.6 References

[1957Gol] H.J. Goldschmidt, JISI, 186 (1957), 68-78

[1973Gup] A. Sen Gupta, Technology, 9(4) (1973), pp: 280

[1977Jer] Jernkontoret, A Guide to the Solidification of Steels. Jernkontoret, Stockholm, (1977).

[1983Mae] Y. Maehara, Y. Ohmori, J. murayama, N. Fujino and T. Kunitake, Metal Science, 17 (1983), 541-547.

[1984Tho] T. Thorvaldsson, H. Eriksson, J. Kutka and A. Salwen, in

Proceedings of the Conference for Stainless Steels, Goteborg, Sweden, (1984) 101-105.

[1985Hay] F. H. Hayes, J. Less Common Metals, 14 (1985) 89-96.

[1991Cor] M. B. Cortie and J. H. Potgieter, Met. Trans., 22A (1991)

2173-2179.

[1991Lon] R. D. Longbottom and F. H. Hayes, in User Aspects of Phase Diagram, The Institute of Metals, London, (1991) 32-39.

[1991Wis] H. Wisell, Met. Trans., 22A (1991) 1391-1405.

[1994Nys] M. Nystrom and B. Karlsson, in Proceedings of the Conference for Duplex Stainless Steels’94, Welding Institute, Cambridge, (1994) 104.

[1995Bas] Z.S. Basinski et al., Proc. Roy. Soc. A229, (1995), pp: 459-467

[2005Mis] Y. Mishin, M.J. Mehl, D.A. Papaconstantopoulos, Acta Materialia, 53(2005), pp: 4029


36

4. PanMagnesium


magnesium-rich casting and wrought alloys


Mg

Ag Al C

Ca

Ce

Cu

Dy

Fe

Gd

La

Li Mn Nd

Ni

Pr

Sc

Se

Si

Sn

Sr

Y

Zn Zr


37

4.1 Components


Major components: Mg, Al, Ca, Ce, Cu, Gd, La, Li, Mn, Nd, Si, Sn, Sr, Y,

and Zn

Minor components: Ag, Dy, Fe, Ni, Pr, Sc, and Zr

Trace component: C, Se










Element Type Composition Range

(wt%)

Mg Base 75~100

Al, Ca, Ce, Cu, Gd, La, Li, Mn, Nd, Si, Sn, Sr, Y, Zn

Major 0~10

Ag, Dy, Fe, Ni, Pr, Sc, Zr Minor 0~2

C, Se Trace 0~0.5

The components Ag, Fe, Ni, Sc, and Zr, are classified as "Minor" even

though their coverage in binary systems is similar to most "Major"

components. However, they are covered less extensively in ternary and


38

quaternary systems as detailed in section 4.5. More restrictions apply to

components C, Dy, Pr, and Se.

4.3 What's new in PanMg2014

Improvements in PanMg2014 compared to the previous version

PanMg2013 focused on extended modeling depth in descriptions

concerning mutual interactions of components in multicomponent alloys

and the addition of three new components.

Key improvements include:

Dy, Pr, and Se are added as new components

Seven new binary system descriptions

Five substantially improved binary system descriptions

One substantially improved ternary system description

More solid solution phases with ternary and higher composition

are unified from separate phase descriptions to a unique phase

description comprising phases with the same crystal structure.

That enables more realistic calculations involving multicomponent

alloy systems.

4.4 Phases

Total of 446 phases are included in the database. The phase names are

selected according to the following strict rules in Table 4.2 for consistent

and intuitive phase identification in different categories. In the category

of solid solution phases, indicated in the TDB Viewer of Pandat as

CEF(SLN), we distinguish


39

SE = Solution phase extending to at least one stable phase of an

elemental component, disordered.

SI = Solution intermetallic phase usually described by a model with more

than one sublattice.

In the category of stoichiometric phases (fixed composition) the TDB

Viewer of Pandat displays CEF(ST*), where * indicates the number of

components:

ST1 = Unary stoichiometric phase (C_graph and Se_A8)

ST2 = Binary stoichiometric phase

ST3 = Ternary stoichiometric phase

ST4 = Quaternary stoichiometric phase.

Table 4.2: Rules for phase names in PanMg

Category Rule for phase name

SE solution

CEF(SLN)

Structure names:

Bcc, Bct_A5, Cbcc, Cub, Dhcp, Fcc, Gas, Hcp, Liquid,

Si_diam

SI solution

Name = Selected approximate chemical stoichiometric

formula.


40

CEF(SLN) Name is selected close to an important/dominant binary

or ternary intermetallic phase with approximate

stoichiometry:

Al12Mg17, R5Mg41, ....

Name always starts with first element. Elements

alphabetical (AlFe, not FeAl). Exceptions: rare earth –

metal – non-metal.

Wild card "elements" R, M, X are used for extended

solution ranges:

R = Rare earth element (La, Ce,..., Lu)*, M = metal, X = non-

metal (C, N, O, F, P, S, Cl, As, Se, Br, Sb, Te, I)**.

Examples: RAl, RCu6, RMg, RMg12, GdM2, Mg2M

Phases may be distinguished/marked by affix for crystal

structure:

MgZn2_C14, MgZn2_C36, ..., AlCaMg_C36,

RMg12Zn_14H

Phase name may be crystal prototype name, such as

CaCu5;

that phase is stable as binary CaCu5, CeCu5, Cu5Gd,

LaCu5, Cu5Nd, CaNi5,

CeNi5, LaNi5, GdNi5, and NdNi5.


41

Temperature polymorphs may be distinguished by affix

_T1, _T2, _T3, ...:

R3Al11_T1 (low temperature), R3Al11_T2 (high

temperature).

Well established phase names might be given as affix,

upper case:

MgYZn3_W, YZn5_H, ...

or with first three letters of the established Greek

symbol, lower case:

AlMgZn_phi, AlMgZn_tau, AlCu_eps, AlCu_gam1,

AlCu_gam2

Stoichiometric

CEF(ST1),

CEF(ST2),

CEF(ST3),

CEF(ST4)

Name = Chemical stoichiometric formula.

Name always starts with first element. Elements

alphabetical;

Exceptions: rare earth element (La, Ce, Pr, Nd, Sm, Eu, Gd,

Tb, Dy, ... Lu) FIRST;

non-metal (C, N, O, F, P, S, Cl, As, Se, Br, Sb, Te, I) LAST.

Examples: AgCa, CeAg, MgSc, SiC, Si3N4, Al4SiC4,

Y2O3

Temperature polymorphs of same stoichiometry are


42

distinguished by affix ..._T*

Zn3Zr_T1 (low temperature), Zn3Zr_T2 (high

temperature)

Well established phase names might be given as affix,

upper case:

Mg10YZn_18R

*) Rare earth elements do not include Sc and Y; Lanthanides only R = (La, Ce, Pr,

Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er,Tm, Yb, Lu).

**) Non-metals are from "Pettifor-string", chemical order from 88 to 102, (Sb, As, P,

Te, Se, S, C, I, Br, Cl, N, O, F), and listed according to the periodic table.

The total 446 phases assessed in PanMg2014 comprise the 171 solution

phases (gas phase, liquid, plus 169 solid solution phases) and 275

stoichiometric phases. These 275 comprise two unary, 203 binary, 68

ternary, and two quaternary assessed stoichiometric phases.

As an illustration of the names and models assigned to the various

solution and stoichiometric phases a small representative selection is

listed in Table 4.3. For all 446 phases assessed in PanMg2014 this

information may be displayed in the TDB Viewer of Pandat or be found at

www.computherm.com.



43

Table 4.3: Example of phase names and related information

Name Model Lattice

Size Constituent

Gas *) GAS (1)

(Ag,Al,Al2,C,C2,C3,C4,C5,Ca,Ce,Cu,Cu2,Dy,Fe,Gd,Li,Li2,Mg,

Mg2,Mn,Nd,Ni,Pr,Sc,Sc2,Se,Se2,Se3,Se4,Se5,Se6,Se7,Se8,Si,Si2,Si3,Si4,Sn,Sr,Y,Zn,Zr,AlC,CSi,CSi2,C2Si)

Liquid CEF (SLN)

(1) (Ag,Al,C,Ca,Ca2Sn,Ce,Cu,Dy,Fe,Gd,La,Li,Mg,Mg2Sn,Mn,Nd,Ni,Pr,Sc,Se,Si,Sn,Sr,Y,Zn,Zr)

Hcp CEF (SLN)

(1) (Ag,Al,Ca,Ce,Cu,Dy,Fe,Gd,La,Li,Mg,Mn,Nd,Ni,Pr,Sc,Se,Si,Sn,Sr,Y,Zn,Zr)

Al12Mg17 CEF (SLN)

(10)(24)(24) (Mg)(Al,Ca,Cu,Li,Mg,Zn)(Al,Cu,Mg,Zn)

Al11Mn4_T1 CEF (SLN)

(11)(4) (Al)(Fe,Mn)

Al11Mn4_T2 CEF (SLN)

(29)(10) (Al,Mn)(Mn)

Al2Ca_C15 CEF (SLN)

(0.666667)(0.333333)

(Al,Mg)(Ca,Sr)

CaCu5 CEF (SLN)

(0.166667)(0.833333)

(Ca,Ce,La,Gd,Nd,Y)(Al,Cu,Ni)

GdM2_C15 CEF (SLN)

(0.333333) (0.666667)

(Gd,Y)(Li,Mg,Zn)

R5Mg41 CEF (SLN)

(5)(41) (Ca,Ce,La,Nd,Y)(Mg,Zn)

Si_diam CEF (SLN)

(1) (Al,C,Si,Sn,Zn)

Se_A8 CEF (ST1)

(1) (Se)

Ag2Ca CEF (ST2)

(0.666667) (0.333333)

(Ag)(Ca)

Al2CaSi2 CEF

(ST3) (0.4)(0.2)(0.4) (Al)(Ca)(Si)

Al17Cu9Mg45Si29

CEF (ST4)

(0.17)(0.09) (0.45)(0.29)

(Al)(Cu)(Mg)(Si)

*) For liquidus projection calculations it is usually recommended to suspend the gas phase


44


The modeling status for the constituent binaries, ternaries and

quaternaries is given in Tables 4.4-4.7. All binary systems for the 20

component-subset, excluding more restricted components, are listed in

Table 4.4. Modeled binary systems formed among the more restricted

components C, Dy, Pr, and Se are given in Table 4.5. Thermodynamic

descriptions for ternary systems are indicated in Table 4.6.

Thermodynamic descriptions validated or extended for quaternary

systems are indicated in Table 4.7.

The color represents the following meaning:

: Full description


: Extrapolation

Table 4.4: Modeling quality status of binary systems formed from

combinations of most major and minor components. Binary systems

formed with remaining components are given in Table 4.5.

Al Ca Ce Cu Fe Gd La Li Mg Mn Nd Ni Sc Si Sn Sr Y Zn Zr

Ag Ag-Al Ag-Ca Ag-Ce Ag-Cu Ag-Fe Ag-Gd Ag-La Ag-Li Ag-Mg Ag-Mn Ag-Nd Ag-Ni Ag-Sc Ag-Si Ag-Sn Ag-Sr Ag-Y Ag-Zn Ag-Zr

Al Al-Ca Al-Ce Al-Cu Al-Fe Al-Gd Al-La Al-Li Al-Mg Al-Mn Al-Nd Al-Ni Al-Sc Al-Si Al-Sn Al-Sr Al-Y Al-Zn Al-Zr

Ca Ca-Ce Ca-Cu Ca-Fe Ca-Gd Ca-La Ca-Li Ca-Mg Ca-Mn Ca-Nd Ca-Ni Ca-Sc Ca-Si Ca-Sn Ca-Sr Ca-Y Ca-Zn Ca-Zr

Ce Ce-Cu Ce-Fe Ce-Gd Ce-La Ce-Li Ce-Mg Ce-Mn Ce-Nd Ce-Ni Ce-Sc Ce-Si Ce-Sn Ce-Sr Ce-Y Ce-Zn Ce-Zr

Cu Cu-Fe Cu-Gd Cu-La Cu-Li Cu-Mg Cu-Mn Cu-Nd Cu-Ni Cu-Sc Cu-Si Cu-Sn Cu-Sr Cu-Y Cu-Zn Cu-Zr

Fe Fe-Gd Fe-La Fe-Li Fe-Mg Fe-Mn Fe-Nd Fe-Ni Fe-Sc Fe-Si Fe-Sn Fe-Sr Fe-Y Fe-Zn Fe-Zr

Gd Gd-La Gd-Li Gd-Mg Gd-Mn Gd-Nd Gd-Ni Gd-Sc Gd-Si Gd-Sn Gd-Sr Gd-Y Gd-Zn Gd-Zr

La La-Li La-Mg La-Mn La-Nd La-Ni La-Sc La-Si La-Sn La-Sr La-Y La-Zn La-Zr

Li Li-Mg Li-Mn Li-Nd Li-Ni Li-Sc Li-Si Li-Sn Li-Sr Li-Y Li-Zn Li-Zr

Mg Mg Mg-Mn Mg-Nd Mg-Ni Mg-Sc Mg-Si Mg-Sn Mg-Sr Mg-Y Mg-Zn Mg-Zr

Mn Mn-Nd Mn-Ni Mn-Sc Mn-Si Mn-Sn Mn-Sr Mn-Y Mn-Zn Mn-Zr

Nd Nd-Ni Nd-Sc Nd-Si Nd-Sn Nd-Sr Nd-Y Nd-Zn Nd-Zr

Ni Ni-Sc Ni-Si Ni-Sn Ni-Sr Ni-Y Ni-Zn Ni-Zr


45

Sc Sc-Si Sc-Sn Sc-Sr Sc-Y Sc-Zn Sc-Zr

Si Si-Sn Si-Sr Si-Y Si-Zn Si-Zr

Sn Sn-Sr Sn-Y Sn-Zn Sn-Zr

Sr Sr-Y Sr-Zn Sr-Zr

Y Y-Zn Y-Zr

Zn Zn-Zr

Table 4.5 Modeled binary systems formed with remaining components C,

Dy, Pr, and Se.

Al-C C-Ca C-Mg Dy-Mg Mg-Pr

Mg-Se C-Si

Total of 155 binary systems are modeled (marked green or yellow).

The same color code is used to indicate the quality of modeled ternary

and quaternary systems in Tables 4.6—4.7. Total of 98 ternary systems

and 16 quaternary systems are modeled.

Table 4.6: Modeled Ternary Systems

Ag-Al-Cu Al-Cu-Si Al-Mg-Zn Ce-Mg-Sn La-Mg-Zn

Ag-Cu-Mg Al-Cu-Sn Al-Mn-Sc Ce-Mg-Y Li-Mg-Mn

Al-C-Si Al-Cu-Zn Al-Mn-Si Ce-Mg-Zn Li-Mg-Si

Al-Ca-Ce Al-Fe-Mn Al-Nd-Y Cu-Fe-Si Li-Mg-Zn

Al-Ca-Fe Al-Fe-Si Al-Si-Y Cu-La-Ni Mg-Mn-Sc

Al-Ca-Li Al-Gd-La Al-Si-Zn Cu-Li-Mg Mg-Mn-Si

Al-Ca-Mg Al-Gd-Mg Al-Sn-Zn Cu-Mg-Ni Mg-Mn-Y

Al-Ca-Si Al-Gd-Nd Ca-Ce-Mg Cu-Mg-Si Mg-Mn-Zn

Al-Ca-Sr Al-Gd-Y Ca-Fe-Si Cu-Mg-Y Mg-Mn-Zr

Al-Ce-Gd Al-La-Nd Ca-Li-Mg Cu-Mg-Zn Mg-Nd-Y

Al-Ce-La Al-La-Y Ca-Li-Si Cu-Ni-Si Mg-Nd-Zn

Al-Ce-Mg Al-Li-Mg Ca-Mg-Si Cu-Sn-Zn Mg-Ni-Si

Al-Ce-Nd Al-Li-Mn Ca-Mg-Sn Fe-Mg-Si Mg-Si-Sn

Al-Ce-Si Al-Li-Si Ca-Mg-Sr Fe-Mn-Si Mg-Si-Zn

Al-Ce-Y Al-Mg-Mn Ca-Mg-Zn Gd-Li-Mg Mg-Y-Zn

Al-Cu-Gd Al-Mg-Sc Ca-Sr-Zn Gd-Mg-Mn Mg-Y-Zr

Al-Cu-Li Al-Mg-Si Ce-La-Mg Gd-Mg-Y Mn-Y-Zr

Al-Cu-Mg Al-Mg-Sn Ce-Li-Mn Gd-Mg-Zn

Al-Cu-Mn Al-Mg-Sr Ce-Mg-Mn La-Mg-Nd

Al-Cu-Nd Al-Mg-Y Ce-Mg-Nd La-Mg-Si


46

Table 4.7: Modeled Quaternary Systems

Ag-Al-Cu-Mg Al-Ce-Li-Mg Al-Fe-Mn-Si Ca-Ce-Mg-Sn Ce-Mg-Mn-Sc

Al-Ca-Ce-Mg Al-Cu-Mg-Si Al-Li-Mg-Si Ca-Mg-Si-Sn Gd-Mg-Mn-Sc

Al-Ca-Li-Mg Al-Cu-Mg-Zn Al-Mg-Mn-Zn Ce-Gd-Mg-Y Mg-Mn-Sc-Y

Mg-Mn-Y-Zr


The early development of the Mg-database, starting in 1995, is described

in [2001Sch] and aspects of quality assurance were first given by

[2005Sch].

Progress in systematic development of the current thermodynamic

database for Mg alloys is reported in [2012Sch]. Models for

multicomponent alloys are built in a methodical approach from

quantitative descriptions of unary, binary and ternary subsystems. For a

large number of ternary—and some higher—alloy systems, an evaluation

of the modeling depth is made with concise reference to experimental

work validating these thermodynamic descriptions. A special focus is on

ternary intermetallic phase compositions. These comprise solutions of

the third component in a binary compound as well as truly ternary solid

solution phases, in addition to the simple ternary stoichiometric phases.

Concise information on the stability ranges is given. That evaluation is

extended to selected quaternary and even higher alloy systems.

Thermodynamic descriptions of intermetallic solution phases guided by

their crystal structure are also elaborated and the diversity of such

unified phases is emphasized [2012Sch].

Key issues in this large thermodynamic Mg alloy database are

consistency, coherency and quality assurance. These issues and the

basic concept are elaborated in [2013Gro]. The structurally supported


47

modeling, especially of pertinent solid phases, requires proper

consideration of multicomponent solid solutions of intermetallic phases

which are abundant in magnesium alloys. Moreover, evidence on the

database application by predicting phase formation during solidification

or heat treatment in advanced multicomponent magnesium alloys from

thermodynamic calculations is given in detail in [2013Gro]. Highlights of

the most recent progress are given in [2015Sch].

The growing modeling depth of the PanMagnesium database enhances

predictive type calculations of phase formation during solidification, heat

treatment or other processing steps of Mg alloys. Evidence is given by

comparing the results of such calculations with the phase formation

reported in studies of advanced magnesium alloys, such as Mg—Zn--

Y/Zr/Gd/Ce/Nd, Mg—Al—Ca/Mn/Sr/Sn, Mg—Sn—Ca and higher order

Mg—Al—Sn—Ca/Sr and Mg—Sn—Ca--Ce/Gd/Zr alloys [2013Gro].

Reference is made to the extensive material provided in that most current

publication which is not repeated here.

The current thermodynamic database for magnesium alloys has also

been extensively tested and validated using published experimental data

[1998Lia, 1999Gro, 2001Gro4, 2001Gro6, 2001Kev1, 2001Kev2,

2001Kev3, 2002Gro1, 2002Gro2, 2003Gro1, 2003Gro2, 2004Bru,

2004Kev, 2004Gro, 2006Ohn4]. Some sub-quaternary systems of this

database have been critically assessed: Mg-Al-Ca-Ce, Mg-Al-Ca-Li, Mg-

Al-Ce-Li, Mg-Al-Cu-Zn, Mg-Mn-Y-Zr. The quaternary systems Mg-Al-Li-Si

[2001Kev4] and Mg-Ce-Mn-Sc, Mg-Gd-Mn-Sc, Mg-Mn-Sc-Y [2000Pis2,

2001Gro2] were thermodynamically modeled and used for technical

applications.


48

Figure 4.1: Invariant temperatures for various ternary alloys included in

PanMagnesium: Comparison between calculated and experimental data.

For the reliability of the calculated phase diagrams the fitting of the

invariant temperatures are of paramount importance. Since the

measured temperatures of the invariant reactions are not affected by

super-cooling related problems, these nonvariant data are perfect criteria

for comparison of experimental with calculated data (Figure 4.1).

For the Mg-Al-Mn system the reliability is checked in detail [2005Ohn].

The liquidus surface of the Mg-rich corner is shown in Figure 4.2. The

same experimental data are plotted in Figures 3a and 3b as comparison

between calculated results and experimental data.

400 600 800 1000 1200 1400

400

600

800

1000

1200

1400

MgLiGd MgLiSi AlCaSi AlLiSi

MgAlCa MgAlCe MgAlGd MgAlMn MgAlSc MgAlZn MgCaSi

Calc

ula

ted invariant

Tem

pera

ture

(°C

)

Experimental invariant Temperature (°C)


49

Figure 4.2: Calculated partial liquidus surface, the thick lines indicate monovariant

reaction lines and the thin lines represents the isotherms. Superimposed are the

compositions of experimental alloys further compared to calculated data of the liquidus

surface. The primary solid phase is specified in some experimental data.

This comparison in Figure 4.3 enables easy identification of those groups

of experimental data that are not consistent with the bulk of

experimental work. There is a reasonable agreement with this bulk of

experimental data and the calculated values. Moreover, there is a

reasonable agreement with the primary solidifying phases as shown in

Figure 4.2.


50

Figure 4.3: Comparison between calculated results and experimental data for all

alloy samples in the Mg-Al-Mn system. (a) Liquidus temperature at a given composition,

(b) Solubility of Mn in liquid at a given temperature and Al composition. The straight

line in Figs. (a) and (b) is a visual aid corresponding to perfect agreement between

experimental values and the calculated results from the present thermodynamic model.

550 600 650 700 750 800 850 900550

600

650

700

750

800

850

900(a)

[10] [9] [8] [6] [5] [4] [3]

Calc

. T

em

pera

ture

(°C

)

Exp. Temperature (°C)

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.50.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5(b)

[10] [9] [8] [6] [5] [4] [3]

Calc

. solu

bili

ty o

f M

n in liq

uid

(w

t.%

)

Exp. solubility of Mn in liquid (wt.%)


51

Figure 4.4a: Calculated partial Mg−Al−Zn liquidus surface and experimental alloy

compositions. The thick lines indicate monovariant reaction lines and the dashed lines

represent isotherms at an interval of 50°C.

Figure 4.4b: Comparison between calculated and experimental liquidus temperature

for all alloy samples in the Mg-Al-Zn system. The straight line is a visual aid

corresponding to perfect agreement between experimental and calculated results.

350 400 450 500 550 600 650350

400

450

500

550

600

650

[5]

[6]

[7]

[8]

[13]

[this work]

DSC1

DSC2

DTA

exp

. liq

uid

us t

em

pe

ratu

re,

°C

calc. liquidus temperature, °C

0 5 10 15 20 25 300

5

10

15

20

25

30

>>

>>

400°C

500°C

Mg

-Mg17

Al12

(Mg)

550°C

600°C

[5], [6], [7]

[8], [13], [this work]

wt.

% Z

n

wt.% Al


52

The experimental data for the commercially very important Mg-Al-Zn

alloys are shown in Figures 4.4a and 4.4b [2006Ohn1]. The liquidus

surface of the Mg-rich corner is given in Figure 4.4a. The same

experimental data is plotted in Figure 4.4b as comparison between

calculated results and experimental data. A similar comparison was done

for the Mg-rich phase equilibria of the Mg-Mn-Zn system [2006Ohn2].

Technical important liquidus and Solidus temperatures of Mg-rich Mg-

Al-Mn-Zn Alloys (AZ series) were investigated by [2006Ohn3].

Measured liquidus temperatures for other ternary Mg-alloy systems are

compared in Figure 4.5 with calculations from the magnesium database.

These miscellaneous Mg-X1-X2 systems include the alloying elements Al,

Ca, Ce, Gd, Li, Sc, and Si.

Additionally a selected comparison of experimental data and calculated

phase equilibria is given below. This demonstrates the feasibility to

perform reasonable calculations with PanMagnesium even in some very

high alloyed regions with vanishing Mg-content as outlined in Table 4.6.

For the Al-Li-Si system a comparison between calculated and

experimentally measured DTA data is given in Figure 6 [2001Gro6].

Figure 4.7 shows a calculated vertical section in the Al-Ce-Si system at

constant 90at%Al including the DSC/DTA signals measured [2004Gro].


53

Figure 4.5: Liquidus temperatures for various ternary magnesium alloys outside the

Mg-Al-Mn-Zn system, with alloying elements Al, Ca, Ce, Gd, Li, Sc, Si: Comparison

between calculated and experimental data.

Figure 4.6: Comparison between calculated and experimentally measured DTA data

for the Al-Li-Si system [2001Gro6].

400 600 800 1000 1200 1400

400

600

800

1000

1200

1400

Ca

lcu

late

d liq

uid

us T

em

pe

ratu

re (

°C)

Experimental liquidus Temperature (°C)

Me

as

ure

d t

em

pe

ratu

re, °C

500500

700

700

900

900

Calculated temperature, °C

DTA signal


54

Figure 4.7: Calculated vertical section Al90Ce10 - Al90Si10 at constant 90at%Al

including the DSC/DTA signals measured in [2004Gro].

The good agreement between experimental and calculated results, as

shown in above figures indicates the reliability of the current

PanMagnesium thermodynamic database. Additional validation is given

in recent comprehensive studies [2012Sch, 2013Gro].

4.7 References

[1998Lia] 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).

[1999Gro] Gröbner, J., Schmid-Fetzer, R., Pisch, A., Cacciamani, G., Riani, P., Ferro, R.: Experimental Investigations and Thermodynamic Calculation in the Al-Mg-Sc System. Z.

Metallkd. 90(11), (1999), S. 872-880.

2 4 6 8

400

600

800

1000

1200

Al 90Ce 0Si 10

Al 90Ce 10Si 0

U11

E1

E2

1 +

(Al)

1 +

2

+ (Al)

L + 2 + (Al)

L + (Al)

Al11

Ce3 (l)

+ 1 + (Al)

2 + (Al) + (Si)

L + 1 +

Al11

Ce3(l)

L + Al

11Ce

3(l)

L + 1

cooling; strong peak heating; strong peak cooling; weak peak heating; weak peak

Te

mp

era

ture

[°C

]

at.% Si


55

[2000Pis2] Pisch, A., Gröbner, J., Schmid-Fetzer, R.: Application of Computational Thermochemistry to Al- and Mg-alloy

processing with Sc additions. Mat. Sci. Eng. A 289, (2000), S. 123-129.

[2001Gro2] Gröbner, J., Pisch, A., Schmid-Fetzer, R.: Selection of Promising Quaternary Candidates from Mg-Mn-(Sc, Gd, Y, Zr) for Development of Creep-resistant Magnesium Alloys. J.

Alloys Comp. 320/2, (2001) 296-301.

[2001Gro4] Gröbner, J., Kevorkov, D., Schmid-Fetzer, R.: Thermodynamic Calculation of Al-Gd and Al-Gd-Mg Phase

Equilibria Checked by Key Experiments. Z. Metallkd. 92 (2001) S. 22-27.

[2001Gro6] Gröbner, J., Kevorkov, D., Schmid-Fetzer, R.: The Al-Li-Si System, Part 2: Experimental study and Thermodynamic Calculation of the polythermal equilibria. J. Solid State

Chem. 156 (2001) S. 506-511.

[2001Kev1] Kevorkov, D., Gröbner, J., Schmid-Fetzer, R.: The Al-Li-Si

system, Part 1: A new structure type Li8Al3Si5 and the ternary solid state phase equilibria. J. Solid State Chem. 156 (2001) S. 500-505.

[2001Kev2] Kevorkov, D.G., Pavlyuk, V.V., Dmytriv, G.S., Bodak, O.I., Gröbner, J., Schmid-Fetzer, R.: The ternary Gd-Li-Mg system: Phase diagram study and computational evaluation.

J. Phase Equilibria 22 (1) (2001) S. 34-42.

[2001Kev3] Kevorkov, D., Schmid-Fetzer, R.: The Al-Ca System Part 1:

Experimental Investigation of Phase Equilibria and Crystal Structures. Z. Metallkd. 92 (2001) S. 946-952.

[2001Kev4] Kevorkov, D.: Thermodynamics and Phase Equilibria of the

Mg-Al-Li-Si System, Ph. D. Thesis TU Clausthal 2001.

[2001Sch] Schmid-Fetzer, R., Gröbner, J.: Focused Development of Magnesium Alloys Using the Calphad Approach. Advanced

Engineering Materials 3 (12) (2001) 947-961.

[2002Gro1] Gröbner, J., Schmid-Fetzer, R., Pisch, A., Colinet, C.,

Pavlyuk, V.V., Dmytriv, G.S., Kevorkov, D.G., Bodak, O.I: Phase equilibria, calorimetric study and thermodynamic


56

modelling of Mg-Li-Ca alloys, Thermochimica Acta 389 (2002) 85-94.

[2002Gro2] Gröbner, J., Schmid-Fetzer, R.:Thermodynamic Modeling of Al-Ce-Mg Phase Equilibria Coupled with Key Experiments,

Intermetallics 10 (2002) 415-422.

[2003Gro1] Gröbner, J., Kevorkov, D., Chumak, I. and Schmid-Fetzer, R.: Experimental Investigation and Thermodynamic

Calculation of Ternary Al-Ca-Mg Phase Equilibria, Z. Metallkd. 94 (2003) 976-982.

[2003Gro2] Gröbner, J., Kevorkov, D.and Schmid-Fetzer, R.: A new

Thermodynamic data set for the binary System Ca-Si and Experimental Investigation in the ternary System Ca-Mg-Si,

Intermetallics 11 (2003) 1065-1074.

[2004Bru] Brubaker, C.O., Liu, Z.-K., A computational thermodynamic model of the Ca–Mg–Zn system, J. Alloys Comp. 370, 114-

122 (2004).

[2004Gro] J. Gröbner, D. Mirkovic, Rainer Schmid-Fetzer:

Thermodynamic Aspects of Constitution, Grain Refining and Solidification Enthalpies of Al-Ce-Si Alloys. Metall. Mater. Trans. A 35A, 3349-3362 (2004).

[2004Kev] Kevorkov, D., Schmid-Fetzer, R. and Zhang F.: Phase Equilibria and Thermodynamics of the Mg-Si-Li System and Remodeling of the Mg-Si System, J. Phase Equil. Diff. 25

(2004) 140-151.

[2005Ohn] M. Ohno, R. Schmid-Fetzer: Thermodynamic assessment of

Mg-Al-Mn phase equilibria, focusing Mg-rich alloys. Z. Metallkde. 96, 857-869 (2005).

[2005Sch] R. Schmid-Fetzer, A. Janz, J. Gröbner and M. Ohno: Aspects

of quality assurance in a thermodynamic Mg alloy database. Advanced Engineering Materials 7 , 1142-1149 (2005).

[2006Ohn1] M. Ohno, D. Mirkovic and R. Schmid-Fetzer: Phase equilibria

and solidification of Mg-rich Mg-Al-Zn alloys. Materials Science & Engineering A, 421, 328-337 (2006).


57

[2006Ohn2] M. Ohno and R. Schmid-Fetzer: Mg-rich phase equilibria of Mg-Mn-Zn alloys analyzed by computational

thermochemistry. Int. J. Materials Research (Z. Metallkunde) 97, 526-532 (2006).

[2006Ohn3] M. Ohno, D. Mirkovic and R. Schmid-Fetzer: Liquidus and Solidus Temperatures of Mg-rich Mg-Al-Mn-Zn Alloys. Acta Materialia, 54, 3883–3891 (2006).

[2006Ohn4] M. Ohno, A. Kozlov, R. Arroyave, Z.K. Liu, and R. Schmid-Fetzer: Thermodynamic modeling of the Ca-Sn system based on finite temperature quantities from first-principles and

experiment. Acta Materialia, 54, 4939-4951 (2006).

[2012Sch] R. Schmid-Fetzer, J. Gröbner: Thermodynamic database for

Mg alloys — progress in multicomponent modeling. Metals, 2, 377-398 (2012). (Special Issue "Magnesium Technology"), Open Access, www.mdpi.com/2075-4701/2/3/377,

dx.doi.org/10.3390/met2030377

[2013Gro] J. Gröbner, R. Schmid-Fetzer: Key issues in a

thermodynamic Mg alloy database. Metall. Mater. Trans. A, A44, 2918-2934 (2013) dx.doi.org/10.1007/s11661-012-1483-z

[2015Sch] R. Schmid-Fetzer: Progress in thermodynamic database development for ICME of Mg alloys, in Magnesium Technology 2015, TMS (The Minerals, Metals & Materials

Society), (2015) accepted


58

5. PanMolybdenum


Mo-rich alloys


Mo

Al B

Cr

Fe

Hf

Mn O

Re

Si

Ti

Zr


59

5.1 Components


Major alloying elements Al, B, Cr, Hf, Mn, Mo, Re, Si, Ti

Minor alloying elements: Fe, O and Zr










Element Composition range (at.%)

Mo 50 ~ 100

Si, Ti 0 ~ 30

B, Cr 0 ~ 20

Al, Hf, Mn, Re 0 ~ 10

Fe, O, Zr 0 ~ 5

5.3 Phases

Total of 162 phases are included in the database and a few key phases

are listed in Table 5.2. Information on all the other phases may be

displayed in the TDB Viewer of Pandat or can be found at

http://www.computherm.com.



60



Al4Mo3Ti3 (4)(3)(3) (Al)(Mo)(Ti)

Al63Mo37 (0.63)(0.37) (Al)(Mo)

Al8FeMo3 (8)(1)(3) (Al)(Al,Fe)(Mo)

B4Mo (0.8)(0.2) (B)(Mo)

B5Mo2 (2)(5) (Mo)(B,Va)

Bcc (1)(3) (Al,B,Cr,Fe,Hf,Mn,Mo,O,Re,Si,Ti,Zr)(B,O,Va)

Delta (3)(1) (Al,Cr,Fe,Mo,Re,Ti)(Al,Cr,Fe,Hf,Mo,Ti)

Eta (0.75)(0.25) (Fe,Ti)(Al,Cr,Hf,Mo,Ti)

Fcc (1)(1) (Al,B,Cr,Fe,Hf,Mn,Mo,Re,Si,Ti,Zr)(B,O,Va)

Laves_C14 (2)(1) (Al,Cr,Fe,Hf,Mo,Ti,Zr)(Al,Cr,Fe,Hf,Mo,Ti,Zr)

Laves_C15 (2)(1) (Al,Cr,Fe,Hf,Mo,Ti,Zr,Si)(Al,Cr,Fe,Hf,Mo,Ti,Zr)

Liquid (1) (Al,B,Cr,Fe,Hf,Mn,Mo,O,Re,Si,Ti,Zr)

Mo1O2_S (1)(2) (Mo)(O)

Mo1O3_S (1)(3) (Mo)(O)

Mo3Si (0.75)(0.25) (Cr,Fe,Hf,Mo,Re,Si,Ti,Zr)(Al,Cr,Fe,Re,Si)

Mo5Si3 (0.625)(0.375) (Cr,Mo,Re,Si,Ti,Zr)(Al,B,Mo,Si)

Mo5SiB2 (0.625)(0.125)(0.25) (Fe,Hf,Mn,Mo,Re,Ti,Zr)(B,Si)(B)

MoSi6Ti2 (1)(2) (Mo,Ti)(Si)

MoSiZr (1)(1)(1) (Mo)(Si)(Hf,Mo,Zr)

Mu_Phase (7)(2)(4) (Al,Cr,Fe,Mn,Mo,Re,Si)(Cr,Mo,Re,Ti) (Cr,Fe,Mo,Re,Ti)

Sigma (10)(4)(16) (Al,Fe,Mn,Re,Si)(Cr,Mo,Re) (Al,Cr,Fe,Mn,Mo,Re,Si)


61


Key elements of the system are listed as: Mo-B-Cr-Hf-Mn-Re-Si-Ti. The



meaning:

: Full description


: Extrapolation

Table 5.3: Key Binary Systems for the PanMolybdenum

B Cr Hf Mn Mo Re Si Ti

Al Al-B Al-Cr Al-Hf Al-Mn Al-Mo Al-Re Al-Si Al-Ti

B B-Cr B-Hf B-Mn B-Mo B-Re B-Si B-Ti

Cr Cr-Hf Cr-Mn Cr-Mo Cr-Re Cr-Si Cr-Ti

Hf Hf-Mn Hf-Mo Hf-Re Hf-Si Hf-Ti

Mn Mn-Mo Mn-Re Mn-Si Mn-Ti

Mo Mo-Re Mo-Si Mo-Ti

Re Re-Si Re-Ti

Si Si-Ti

Table 5.4: Key Ternary Systems for the Major Components Mo-B-Hf-Si-Ti

Hf Si Ti

Mo-B Mo-B-Hf Mo-B-Si Mo-B-Ti

Mo-Hf Mo-Hf-Si Mo-Hf-Ti

Mo-Si Mo-Si-Ti


62


The current PanMo database was validated by large amounts of phase

equilibrium data available for Mo alloys. A few examples are given here.

Figure 5.1 shows the calculated liquidus projection of the Mo-Si-B

ternary system. The calculated isothermal lines are also shown in the

same figure.

Figure 5.1: Calculated liquidus projection of the Mo-Si-B ternary system superimposed

with the isothermal lines.

Figure 5.2 shows the calculated isothermal section of the Mo-Si-B

ternary system at 1600oC, which demonstrates the equilibrium between

the ternary T2 phase and the binary phases.

Figures 5.3 and 5.4 show the calculated isothermal sections of the Mo-

Si-Ti ternary system with the experimental data of [2003Yan] at 1425oC

and 1600oC, respectively. Blue lines are the calculated phase

boundaries. Symbols are the phase equilibrium data measured using

x(B

)

x(Si)

0.0

0.2

0.3

0.5

0.7

0.9

0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10

0.2

0.4

0.6

0.8

1

x(Si)

x(B

)

Mo

B

Si

(Mo)

Liquidus Projection

2500oC

2400oC

2300oC

MoSi2

MoB

T2

T1

Mo2B

MoB2

Mo2B5

(B)

BnSi

B6Si


63

EPMA. It can be seen that the experimentally measured phase

equilibrium data are in good agreement with the thermodynamic

calculations using PanMo thermodynamic database.

Figure 5.2: Calculated isothermal section of the Mo-Si-B ternary system 1600oC

Figure 5.3: Calculated isothermal section of the Mo-Si-Ti ternary system at 1600oC with

experimental data of [2003Yan] plotted on it.

x(B

)

x(SI)

0.0

0.2

0.3

0.5

0.7

0.9

0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10

0.2

0.4

0.6

0.8

1

x(SI)

x(B

)

MO

B

SI

T=1600oC

Mo2B

MoB

MoB2

Mo2B5

T2

BnSi

B6Si

L

Mo3Si T1 MoSi2

x(S

i)

x(Ti)

0.0

0.2

0.3

0.5

0.7

0.9

0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10

0.2

0.4

0.6

0.8

1

x(Ti)

x(S

i)

Mo

Si

Ti

T=1600oC Calculationtie-linetie-triangle


64

Figure 5.4: Calculated isothermal section of the Mo-Si-Ti ternary system at 1425oC with

experimental data of [2003Yan] plotted on it

In addition to the validation of phase equilibria, the current database has

also been subjected to extensive validation of solidification data of

commercial aluminum alloys. Figure 5.5 presents the calculated fraction

of solid vs. temperature of the Mo-Si-Ti alloys as well as the solidification

sequence using the Scheil model. The back scattered images of the as-

cast microstructure of these Mo-Si-Ti alloys from [2003Yan] are also

shown in the same figure. The predicated microstructures of the Mo-Si-Ti

alloys using the Scheil model agree well with experimental observations.

x(S

i)

x(Ti)

0.0

0.2

0.3

0.5

0.7

0.9

0.0 0.2 0.4 0.6 0.8 1.00 0.2 0.4 0.6 0.8 10

0.2

0.4

0.6

0.8

1

x(Ti)

x(S

i)

Mo

Si

Ti

T=1425oCCalculationTie-lineTie-triangle


65

Figure 5.5(a) Scheil simulation of solidification sequence of the Mo40Si20Ti40 alloy

Figure 5.5(b) A back scattered image of the as-cast microstructure of the

Mo40Si20Ti40 alloy

(b)


66

Figure 5.5(c) Scheil simulation of the solidification sequence of the Mo40Si25Ti35 alloy

Figure 5.5(d) A back scattered image of the as-cast microstructure of the

Mo40Si25Ti35 alloy

(d)


67

Figure 5.5(e) Scheil simulation of the solidification sequence of the Mo5Si25Ti75 alloy

Figure 5.5(f) A back scattered image of the as-cast microstructure of the Mo5Si25Ti70

alloy

(f)


68

5.6 Reference

[2003Yan] Y. Yang, Y.A. Chang, L. Tan, Y. Du, Materials Science and

Engineering A361 (2003), p.281–293


69

6. PanNiobium


Nb-rich alloys


Nb

Al Cr

Fe

Hf

Mo Re

Si

Ti

W

Zr


70

6.1 Components


Al, Cr, Fe, Hf, Mo, Nb, Re, Si, Ti, W and Zr







wider composition range.


Element Composition range (at.%)

Nb 50 ~ 100

Si, Ti 0 ~ 30

Cr 0 ~ 20

Al, Hf 0 ~ 10

Fe, Mo, Re, W, Zr 0 ~ 5

6.3 Phases

Total of 84 phases are included in the database and a few key phases are

listed in Table 6.2. Information on all the other phases may be displayed

in the TDB Viewer of Pandat or can be found at

http://www.computherm.com.



71



BCC_A2 (1)(3) (Al,Cr,Fe,Hf,Mo,Nb,Re,Si,Ti,W,Zr)(Va)

CrHfSi (1)(1)(1) (Cr)(Hf)(Si)

CrSi (1)(1) (Cr,Fe)(Si)

CrSi2 (1)(2) (Cr,Si,Ti)(Cr,Si)

FCC_A1 (1)(1) (Al,Cr,Fe,Hf,Mo,Nb,Re,Si,Ti,W,Zr)(Va)

HCP_A3 (1)(0.5) (Al,Cr,Fe,Hf,Mo,Nb,Re,Si,Ti,W,Zr)(Va)

Liquid (1) (Al,Cr,Fe,Hf,Mo,Nb,Re,Si,Ti,W,Zr)

NbSi2 (0.333333)(0.66

6667)

(Hf,Mo,Nb,Ti)(Al,Si)

Nb3Si (0.75)(0.25) (Hf,Nb,Ti,Zr)(Al,Si)

Nb5Si3 (0.625)(0.375) (Cr,Hf,Nb,Ti,Zr)(Al,Si)

Sigma (8)(4)(18) (Al,Fe,Re,Si,Ti)(Cr,Fe,Mo,Nb,W)(Al,Cr,Fe,Mo,Nb,R

e,Si,Ti,W)

T (6)(5) (Cr,Ti)(Si)

Ti2AlNb (0.75)(0.25) (Nb,Ti)(Al)


72


Key elements of the system are listed as: Nb-Al-Cr-Fe-Hf-Mo-Re-Si-Ti.

The modeling status for the constituent binaries and ternaries of these

key elements are given in Tables 6.3-6.4. The color represents the

following meaning:

: Full description


: Extrapolation

Table 6.3: Key Binary Systems for the PanNiobium

Cr Fe Hf Mo Nb Re Si Ti

Al Al-Cr Al-Fe Al-Hf Al-Mo Al-Nb Al-Re Al-Si Al-Ti

Cr Cr-Fe Cr-Hf Cr-Mo Cr-Nb Cr-Re Cr-Si Cr-Ti

Fe Fe-Hf Fe-Mo Fe-Nb Fe-Re Fe-Si Fe-Ti

Hf Hf-Mo Hf-Nb Hf-Re Hf-Si Hf-Ti

Mo Mo-Nb Mo-Re Mo-Si Mo-Ti

Nb Nb-Re Nb-Si Nb-Ti

Re Re-Si Re-Ti

Si Si-Ti

Table 6.4: Current Status of Key Ternary Systems in Nb-Si-X, Nb-Ti-X,

Nb-Cr-X(X=Al, Cr, Fe, Hf, Mo, Si, Ti, W, Zr)

Al Cr Fe Hf Mo Si Ti W Zr

Nb-Cr Nb-Cr-Al Nb-Cr-Fe Nb-Cr-Hf Nb-Cr-Mo Nb-Cr-Si Nb-Cr-Ti Nb-Cr-W Nb-Cr-Zr

Nb-Si Nb-Si-Al Nb-Si-Cr Nb-Si-Fe Nb-Si-Hf Nb-Si-Mo Nb-Si-Ti Nb-Si-W Nb-Si-Zr

Nb-Ti Nb-Ti-Al Nb-Ti-Cr Nb-Ti-Fe Nb-Ti-Hf Nb-Ti-Mo Nb-Ti-Si Nb-Ti-W Nb-Ti-Zr


73


The current PanNb database was validated by large amounts of phase

equilibrium data available for Nb alloys. A few examples are given here.

Figure 6.1 shows the calculated liquidus projection of Nb-Ti-Si together

with the experimental data [1997Bew]. The different symbol of

experimental data denotes that the primary solidification phase observed

in the as-cast microstructure of the alloy. The two invariant reactions at

the metal-rich region of Nb-Ti-Si are L+Nb5Si3Ti5Si3+Nb3Si at 1599°C

and L+Nb3SiTi5Si3+Bcc at 1359°C.

Figure 6.1: Calculated liquidus projection of Nb-Ti-Si together with experimental data

[1997Bew]


74

Figures 6.2-6.3 show the calculated isothermal section of Nb-Ti-Si at

1500°C and 1340°C, respectively. The experimental data are also plotted

for comparison. The phase compositions are from EPMA measurements.

The detail of experiments can be found in literature [1998Bew]. Different

shapes of the symbols denote the different phase regions where the alloys

are located. The green lines are tie lines.

Figure 6.2: Calculated isothermal section of Nb-Ti-Si at 1500°C together with

experimental data [1998Bew]


75

Figure 6.3: Calculated isothermal section of Nb-Ti-Si at 1340°C together with

experimental data [1998Bew]

Figure 6.4 shows the calculated liquidus projection of Nb-Cr-Si overlaid

by experimental data. Again, the different symbol of experimental data

[2007Bew] denotes that the primary solidification phase observed in the

as-cast microstructure of the alloy. Figure 6.5 shows the calculated

isothermal section of Nb-Cr-Si at 1100°C. In PanNb, a ternary phase

Nb9Si2Cr3, was included in the thermodynamic description of the Nb-Cr-

Si system for the first time.


76

Figure 6.4: Calculated liquidus projection of Nb-Cr-Si together with experimental data

[2007Bew, 2009Bew]

Figure 6.5: Calculated isothermal section of Nb-Cr-Si at 1100°C


77

Figure 6.6 shows the calculated liquidus projection of the Nb-Si-Hf

overlaid by experimental data [1999Bew]. Again, the different symbol of

experimental data denotes that the primary solidification phase observed

in the as-cast microstructure of each alloy. The three invariant reactions

at the metal-rich region of Nb-Hf-Si are L + Hf5Si3 Nb5Si3_LT + Hf2Si at

2035°C, L + Nb3Si Nb5Si3_LT + Bcc at 1836°C and L + Nb5Si3_LT

Hf2Si + Bcc at 1822°C. Figure 6.7 shows the calculated isothermal

section of Nb-Hf-Si at 1500°C together with experimental data.

Figure 6.6: Calculated liquidus projection of Nb-Hf-Si together with experimental data

[1999Bew, 2003Yan]


78

Figure 6.7: Calculated isothermal section of Nb-Hf-Si at 1500°C together with

experimental data [2001Zha]

Comparisons between the calculated phase compositions (in italic font)

and the EPMA measurements for two Nb-Cr-Ti-Si alloys are shown in

Table 6.6. These measured phase compositions were not used in model

parameter optimization. Instead, they were only used for validation of the

calculated results. In view of this, the calculated phase compositions

from the current thermodynamic description agree well with the

experimental measurements. However, the users should be cautious on

the discrepancy between the calculated and measured Cr and Nb

compositions for the Laves_C14 phase.


79

Table 6.5: Comparisons between the EMPA measured and the calculated (italic font in

parentheses) phase compositions [2003Yan]

Sample Phase Nb (at.%) Cr (at.%) Ti (at.%) Si (at.%) Nb-10Cr-

23Ti-15Si

Bcc_a2 58.2

(60.9)

13.3

(11.9)

27.4

(26.1)

1.2 (1.1)

Nb5Si3 42.2 (41.5)

0.6 (1.5) 21.2 (19.5)

36.1 (37.5)

Laves_C14 29.1 (21.9)

47.1 (55.5)

14.7 (12.7)

9 (9.9)

Nb-11Cr-23Ti-

13Si

Bcc_a2 59.4 (61.2)

13.5 (12.0)

26 (25.7) 1.2 (1.1)

Nb5Si3 43.7 (41.6)

0.5 (1.6) 19.5 (19.3)

36.2 (37.5)

Laves_C14 26 (22.1) 51 (55.5) 13 (12.5) 10 (9.9)

Figures 6.8(a)-(b) show the simulated solidification paths for the Nb-

11Cr-23Ti-13Si, and Nb-21Cr-23.5Ti-15.5Si alloys. The BSE images of

the as-cast microstructures of these two alloys are shown in Figure

6.8(c)-(d), respectively. The phase observed in the BSE images is well

predicted by the lever-rule simulation and the early stage of the Scheil

simulation. The additional phases predicted by the Scheil model were not

identified in the BSE images, which maybe either due to the small

amount presented in the microstructure or the micro-segregation in real

cooling condition is not as severe as assumed by Scheil simulation.


80

Figure 6.8: Calculated solidification paths with experimental observation (a) and (c) for

alloy) Nb-11Cr-23Ti-13Si; (b) and (d) for alloy Nb-21Cr-23.5Ti-15.5Si

Figures 6.9 (a) and (b) show the solidification path simulations under the

Scheil and lever-rule condition for the six component Nb-22Ti-2Hf-4Cr-

3Al-16Si alloy, and the BSE image of the as-cast microstructure of the

same alloy. The microstructure consists of two phases (Nb) and Nb5Si3,

which is well predicted by the lever-rule simulation as shown by the dash

line in Fig. 6.9 (a). The Scheil simulation predicted the formation of Ti5Si3

and Laves_C14 in addition to (Nb) and Nb5Si3. However, the total mole

percentage of Ti5Si3 and Laves_C14 is predicted to be less than 5%.

Again, the additional phases predicted by the Scheil model were not

identified in the BSE images, which maybe either due to the small

amount presented in the microstructure or the micro-segregation in real

cooling condition is not as severe as assumed by Scheil simulation.

T=1600°

C


81

Figure 6.9: Calculated solidification path for alloys Nb-22Ti-2Hf-4Cr-3Al-16Si with

experimental observation

6.6 References

[1997Bew] Bewlay, B. P.; Jackson, M. R.; Lipsitt, H. A., Journal of

Phase Equilibria (1997), 18(3), 264-278.

[1998Bew] Bewlay, B. P.; Jackson, M. R.; Bishop, R. R., Journal of

Phase Equilibria (1998), 19(6), 577-586.

[2007Bew] Bewlay, B. P.; Yang, Y.; Casey, R. L.; Jackson, M. R.; Chang,

Y. A., Materials Research Society Symposium Proceedings,

(2007), 980, 333-338.

[2009Bew] Bewlay, B.P.; Yang, Y.; Caesy, R. L.; Jackson M.R., Chang Y.

A., Intermetallics (2009), 17(3), 120-127.

[1999Bew] Bewlay, Bernard P.; Bishop, Rachel R.; Jackson, Melvin R.,

Zeitschrift fuer Metallkunde (1999), 90(6), 413-422.

[2003Yan] Yang, Y.; Chang, Y. A.; Zhao, J.-C.; Bewlay B. P.,

Intermetallics, 11(5) (2003) 407-415.

[2001Zha] Zhao, J.-C.; Bewlay, B. P.; Jackson, M. R., Intermetallics

(2001), 9(8), 681-689.

liq


82

7. PanNickel

Thermodynamic Database for Nickel-Based

Superalloys


Ni

Al B C

Co

Cr

Cu

Fe

Hf

Ir

Mn Mo N

Nb

Pt

Re

Ru

Si

Ta

Ti

W Zr


83

7.1 Components

Total of 22 components are included in the database.

Major alloying elements: Al, Co, Cr, Fe, Ir, Mo, Ni, Pt, Re, Ru and W

Minor alloying elements: B, C, Cu, Hf, Mn, N, Nb, Si, Ta, Ti and Zr











Ni 50-100

Al,Co,Cr,Fe 0-22

Ir,Mo,Re,Ru,W 0-12

Hf,Nb,Ta,Ti 0-5

B,C,Cu,Mn,N,Si,Zr 0-0.5

Pt 0-40

7.3 Phases



Information on all the other phases may be displayed through the TDB

viewer and can be found at www.computherm.com.



84



B2 (1)(1) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Va)

Bcc (1)(3) (Al,Co,Cr,Cu,Fe,Hf,Ir,Mn,Mo,Nb, Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)(B,C,N,Va)

Delta (3)(1) (Al,Co,Cr,Fe,Mo,Nb,Ni,Re,Ta,Ti) (Al,Co,Cr,Fe,Hf,Mo,Nb,Ni,Ta,Ti,W)

Eta (0.75)(0.25) (Co,Fe,Ni,Ti)(Al,Cr,Hf,Mo,Nb,Ni,Ta,Ti)

Fcc (1)(1) (Al,Co,Cr,Cu,Fe,Hf,Ir,Mn,Mo,Nb, Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr) (B,C,N,Va)

Hcp (1)(0.5) (Al,Co,Cr,Cu,Fe,Hf,Ir,Mo,Nb, Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)(B,C,N,Va)

L12_FCC (0.75)(0.25)(1) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr) (Al,Co,Cr,Fe,Hf,Ir,Mn,Mo,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)(Va)

Liquid (1) (Al,B,C,Co,Cr,Cu,Fe,Hf,Ir,Mn,Mo, N,Nb,Ni,Pt,Re,Ru,Si,Ta,Ti,W,Zr)

M23C6 (20)(3)(6) (Co,Cr,Fe,Ni,Re)(Co,Cr,Fe,Mo,Nb,Ni,Re,Ta,Ti,W)(B,C)

M3Si (3)(1) (Co,Cr,Fe,Mo,Nb,Ni,Ta,Ti,Zr)(Si)

M5Si3 (0.625)(0.375) (Cr,Fe,Mo,Nb,Ta,Ti,W,Zr)(Si)

M6C (2)(2)(2)(1) (Co,Fe,Ni)(Cr,Mo,Nb,W) (Co,Cr,Fe,Mo,Nb,Ni,W)(C)

M7C3 (7)(3) (Co,Cr,Fe,Mo,Nb,Ni,Re,W)(B,C)

MSi (0.5)(0.5) (Co,Cr,Fe,Hf,Nb,Ni,Ti,Zr)(Si)

Mu_Phase (7)(2)(4) (Co,Cr,Fe,Mo,Nb,Ni,Re,Ta) (Co,Cr,Mo,Nb,Ni,Re,Ta,Ti,W) (Co,Cr,Fe,Mo,Nb,Ni,Re,Ta,Ti,W)

Sigma (8)(4)(18) (Al,Co,Fe,Mn,Ni,Re,Ru,Si) (Co,Cr,Mo,Nb,Ni,Ta,W) (Al,Co,Cr,Fe,Mn,Mo,Nb,Ni,Re,Ru,Si,Ta,W)


85


Key elements of the system are listed as: Ni-Al-Co-Cr-Fe-Ir-Mo-Pt-Re-Ru-

W. The modeling status for the constituent binaries and ternaries of

these key elements are given in Tables 7.3-7.4. The color represents the

following meaning:

: Full description


: Extrapolation

Table 7.3 lists the binaries in the system. Thermodynamic descriptions

are fully developed for the binaries in green color, which means that

there is no composition and temperature limits if calculations are carried

out for these binary systems. Only major phases are considered for the

binaries in yellow color.

Table 7.3: Key binary systems for the Ni-Al-Co-Cr-Fe-Ir-Mo-Pt-Re-Ru-W

subset

Co Cr Fe Ir Mo Ni Pt Re Ru W

Al Al-Co Al-Cr Al-Fe Al-Ir Al-Mo Al-Ni Al-Pt Al-Re Al-Ru Al-W

Co Co-Cr Co-Fe Co-Ir Co-Mo Co-Ni Co-Pt Co-Re Co-Ru Co-W

Cr Cr-Fe Cr-Ir Cr-Mo Cr-Ni Cr-Pt Cr-Re Cr-Ru Cr-W

Fe Fe-Ir Fe-Mo Fe-Ni Fe-Pt Fe-Re Fe-Ru Fe-W

Ir Ir-Mo Ir-Ni Ir-Pt Ir-Re Ir-Ru Ir-W

Mo Mo-Ni Mo-Pt Mo-Re Mo-Ru Mo-W

Ni Ni-Pt Ni-Re Ni-Ru Ni-W

Pt Pt-Re Pt-Ru Pt-W

Re Re-Ru Re-W

Ru Ru-W


86

Table 7.4: Key ternary systems for the Ni-Al-Co-Cr-Fe-Ir-Mo-Pt-Re-Ru-

W subset

Co Cr Fe Pt Ir Mo Re Ru W

Ni-Al Ni-Al-Co Ni-Al-Cr Ni-Al-Fe Ni-Al-Pt Ni-Al-Ir Ni-Al-Mo Ni-Al-Re Ni-Al-Ru Ni-Al-W

Ni-Co Ni-Co-Cr Ni-Co-Fe Ni-Co-Pt Ni-Co-Ir Ni-Co-Mo Ni-Co-Re Ni-Co-Ru Ni-Co-W

Ni-Cr Ni-Cr-Fe Ni-Cr-Pt Ni-Cr-Ir Ni-Cr-Mo Ni-Cr-Re Ni-Cr-Ru Ni-Cr-W

Ni-Fe Ni-Fe-Pt Ni-Fe-Ir Ni-Fe-Mo Ni-Fe-Re Ni-Fe-Ru Ni-Fe-W


This database focuses on the nickel-rich corner of multicomponent nickel

alloys, and has been extensively tested and validated by a large number

of commercial nickel alloys. Table 7.5 lists the alloys and references used

for testing the current database. In the table, fT ,

s

fT , and '

fT represent

liquidus, solidus ( starts to form from liquid), and solvus ( starts to

precipitate in the phase matrix) temperatures, respectively. 'f

represents the volume fraction of the phase, and )( inXx , ' )( inXx

represent the equilibrium compositions of component X in the and

phases, respectively. The recommended composition ranges given in

Table 7.1 are the ones that have been extensively tested. Users need to

be careful when using the database beyond the suggested ranges.


87

Table 7.5: Experimental Data Used for Testing the Current Nickel

Database

Alloy Experimental Information References

Udimet-700 '

fT , Tvsf . ' ,

TvsinWMoTiCrAlx . ' ),,,,(

[1971Mol]

Ni-14Cr-6.5~12Al-4Ti-1~5Mo

'

fT [1972Loo]

Ni-4~13Al-6.5~20.5Cr-0.25~4.5Ti-0~6Mo-0~4W

Catf o850 ' ,

' ),,,,( andinWMoTiCrAlx

[1974Dre]

IN-939 ' ),,,,,( andinWTaTiCrCoAlx [1983Del]

Udimet-520 ' ),,,,,( andinWMoTiCrCoAlx [1983Mag]



N-18 '

fT [1988Duc]

IN-100 '

fT [1988Duc]

MERL-76 '

fT [1988Duc]

RENE-95 '

fT [1988Duc]

ASTROLOY '

fT [1988Duc]

Nimonic-105 ' ),,,,( andinMoTiCrCoAlx [1991Tri]

BJH, BJJ, BJK, BJL, BJM, BJP

fT ,

s

fT , '

fT [1992Dha]

2D8625, 2D8638, 2D8639, 2D8640

fT ,

s

fT , '

fT [1992Dha]

MA6000 fT ,

s

fT , '

fT [1992Dha]

CMSX-2 fT ,

s

fT , '

fT [1992Dha]

SRR-99 ' ),,,,,( andinWTaTiCrCoAlx [1992Sch]

Modified IN738LC ' ),,,,,( andinMoWTaCrCoAlx [1993Zha]

MC2 ' ),,,,,,( andinMoWTiTaCrCoAlx [1994Duv]

Ni-Al-Re-X(X: Cr, Mo, W, Ti, Ta, Nb, Co)

' ),,( andinXREAlx [1994Miy]

Rene N6 fT ,

s

fT , '

fT , 'f ,

' ),,,,,,( andinMoWRETaCrCoAlx

[1998Rit] [1999Rit] [2001Cop]


88

This database can be used to calculate phase equilibria for multi-

component alloys, such as the equilibrium between and . It can be

used to predict phase transformation temperatures, such as liquidus,

solidus and solvus. The fraction of each phase as a function of

temperature and partitioning of components in different phases can also

be calculated. In addition to equilibrium calculations, Scheil simulations

can also be carried out using this database. Some calculation results are

presented in Figures 7.1 to 7.10.

Figure 7.1 shows comparison between calculated and experimentally

measured liquidus and solidus temperatures for nickel-based

superalloys, while Figure 7.2 is for that of the solvus temperatures of the

phase. Figure 7.3 shows comparison between calculated and

experimentally determined amounts of the phase. Figures 7.4 to 7.10

are comparisons between the calculated and experimentally measured

equilibrium compositions for Al, Co, Cr, Mo, Re, Ti, and W in and

phases, respectively. These figures show reasonable agreement between

the calculated values using the current nickel database and the

experimentally determined ones.


89


liquidus and solidus temperatures

Figure 7.2: Comparison between the calculated and experimentally measured solvus

temperatures of the phase

1600

1620

1640

1660

1680

1700

1720

1740

1600 1620 1640 1660 1680 1700 1720 1740

Measured (K)

Calc

ula

ted

(K

)

01Cop-Liquidus

01Cop-Solidus

92Dha-Liquidus

92Dha-Solidus

Diagonal

1100

1200

1300

1400

1500

1600

1700

1100 1200 1300 1400 1500 1600 1700

Measured (K)

Calc

ula

ted

(K

)

01Cop

92Dha

88Duc

71Mol

Diagonal


90


amounts of the phase


equilibrium compositions of Al in and phase

0

20

40

60

80

100

0 20 40 60 80 100Measured

Ca

lcu

late

d

01Cop

84Kha

74Dre

72Loo

Diagonal

0

5

10

15

20

25

0 5 10 15 20 25

Measured (Al at%)

Ca

lcu

late

d (

Al

at%

)

01Cop -g

94Miy -g

93Zha -g

92Sch -g

01Cop -g_p

94Miy -g_p

93Zha -g_p

92Sch -g_p

84Kha -g_p

74Dre -g_p

Diagonal

'

'

'

'

'

'


91


equilibrium compositions of Co in and phases


equilibrium compositions of Cr in and phases

0

5

10

15

20

25

30

0 5 10 15 20 25 30

Measured (Co at%)

Ca

lcu

late

d (

Co

at%

)

01Cop -g

94Miy -g

93Zha -g

92Sch -g

91Tri -g

01Cop -g_p

94Miy -g_p

93Zha -g_p

92Sch -g_p

91Tri -g_p

Diagonal

'

'

'

'

'

0

5

10

15

20

25

30

35

40

0 5 10 15 20 25 30 35 40

Measured (Cr at%)

Ca

lcu

late

d (

Cr

at%

)

01Cop -g

94Miy -g

92Sch -g

91Tri -g

74Dre -g

01Cop -g_p

94Miy -g_p

92Sch -g_p

74Dre -g-p

Diagonal

'

'

'

'


92


equilibrium compositions of Mo in and phases


equilibrium compositions of Re in and phases

0

2

4

6

8

10

0 2 4 6 8 10

Measured (Mo at%)

Ca

lcu

late

d (

Mo

at%

)

01Cop -g

94Duv -g

93Zha -g

74Dre -g

01Cop -g-p

94Duv -g-p

93Zha -g-p

Diagonal

'

'

'

0

1

2

3

4

5

6

0 1 2 3 4 5 6

Measured (Re at%)

Ca

lcu

late

d (

Re a

t%)

01Cop-g

94Miy-g

01Cop-g_p

94Miy-g_p

Diagonal

t

()

()

'

'


93


equilibrium compositions of Ti in and phases


equilibrium compositions of W in and phases

0

3

6

9

12

15

0 3 6 9 12 15

Measured (Ti at%)

Ca

lcu

late

d (

Ti

at%

)

94Miy -g

94Duv -g

92Sch -g

94Miy -g-p

94Duv -g-p

93Zha -g-p

92Sch -g-p

74Dre -g-p

Diagonal

'

'

'

'

'

0

1

2

3

4

5

6

0 1 2 3 4 5 6Measured (W at%)

Ca

lcu

late

d (

W a

t%)

01Cop-g

93Zha-g

92Sch-g

83Del-g

74Dre

01Cop-g_p

92Sch-g_p

83Del-g_p

94Miy-g-p

Diagonal

()

()

()

()

'

'

'

'


94

7.6 References

[1971Mol] E. H. van der Molen, J. M. Oblak and O. H. Kriege, Metal. Trans., 2 (1971) 1627-1633.

[1972Loo] W. T. Loomis, J. W. Freeman and D. L. Sponseller, Metal. Trans., 3 (1972) 989-1000.

[1974Dre] R. L. Dreshfield and J. F. Wallace, Metal. Trans., 5 (1974) 71-

78.

[1983Del] K. M. Delargy and G. D. W. Smith, Metal. Trans., 14A (1983) 1771-1783.

[1983Mag] M. Magrini, B. Badan and E. Ramous, Z. Metallkde., 74 (1983) 314-316.

[1988Duc] C. Ducrocq, A. Lasalmonie and Y. Honnorat, in Superalloys 1988, Ed. S. Reichman, D. N. Duhl, G. Maurer, S. Antolovich

and C. Lund, (The Metallurgical Society, 1988) 63-72.

[1991Tri] K. Trinckauf and E. Nembach, Acta Metall. Mater., 39(12)

(1991) 3057-3061.

[1992Dha] S.-R. Dharwadkar, K. Hilpert, F. Schubert and V. Venugopal, Z. Metallkde., 83 (1992) 744-749.

[1992Sch] R. Schmidt and M. Feller-Kniepmeier, Scripta Metal. Mater., 26 (1992) 1919-1924.

[1993Zha] J. S. Zhang, Z.Q. Hu, Y. Murata, M. Morinaga and N. Yukawa, Metal. Trans., 24A (1993) 2443-2450.

[1994Duv] S. Duval, S. Chambreland, P. Caron and D. Blavette, Acta Metall. Mater., 42(1) (1994) 185-194.

[1994Miy] S. Miyazaki, Y. Murata and M. Morinaga,, Iron and Steel (Japan) 80(2) (1994) 78-83.

[1998Rit] F. J. Ritzert, D. Arenas, D. Keller and V. Vasudevan,

NASA/TM 1998-206622.

[1999Rit] F. J. Ritzert, D. Keller and V. Vasudevan, NASA/TM 1999-209277.

[2001Cop] E. H. Copland, N. S. Jacobson and F. J. Ritzert, NASA/TM 2001-210897.


95

8. PanNoble


Noble metal alloys


Noble

Ag Al Au

B

Bi

C

Co

Cr

Cu

Fe

Ge

In

Ir Mn

Ni Os P

Pb

Pd

Pt

Rh

Ru

S

Sb

Se

Si

Sn

Ti Zn


96

8.1 Components

A total of 29 components are included in the database as listed here:

Ag, Al, Au, B, Bi, C, Co, Cr, Cu, Fe, Ge, In, Ir, Mn, Ni, Os, P, Pb, Pd, Pt,

Rh, Ru, S, Sb, Se, Si, Sn, Ti, and Zn.











Al, Co, Cr, Cu, Fe, Mn, Ni 0 ~ 100

Bi, In, Pb, Se, Sn, Zn 0 ~ 50

Ag, Au, Ir, Pd, Pt, Sb, Ti 0 ~ 30

Ge, Os, Rh, Ru, Si 0 ~ 10

B, C, P, S 0 ~ 3

8.3 Phases

A total of 623 phases are included in the database and a few key phases

are listed in Table 8.2. Information on all the other phases may be

displayed through TDB viewer of Pandat or can be found at

www.computherm.com.



97



B2 (1)(1) (Ag,Al,Co,Cr,Cu,Fe,In,Ir,Mn,Ni,Pd,Ru,Ti,Zn)(Al,Co,Cr,Cu,F

e,Ir,Mn,Ni,Pd,Ru,Zn,Va)

Bcc (1)(3) (Ag,Al,Au,B,Bi,Co,Cr,Cu,Fe,Ge,In,Ir,Mn,Ni,Os,P,Pb,Pd,Pt,R

h,Ru,S,Sb,Si,Sn,Ti,Zn)(C,Va)

CBCC_A12 (1)(1) (Al,Bi,Co,Cr,Cu,Fe,Mn,Ni,Si,Sn,Ti,Zn)(C,Va)

CUB_A13 (1)(1) (Ag,Al,Bi,Cr,Cu,Co,Fe,Ge,Mn,Ni,Si,Sn,Ti,Zn)(C,Va)

D019 (0.75)(0.25) (Al,Ni,Sn,Ti)(Al,Ni,Sn,Ti)

Fcc (1)(1) (Ag,Al,Au,B,Bi,Co,Cr,Cu,Fe,Ge,In,Ir,Mn,Ni,Os,P,Pb,Pd,Pt,R

h,Ru,S,Sb,Si,Sn,Ti,Zn)(C,Va)

Gamma (4)(1)(8) (Ag,Ni,Si,Zn)(Ag,Cu,Ni,Zn)(Cu,Zn)

L12 (0.75)(0.25) (Al,Co,Cr,Cu,Fe,Ge,Ir,Mn,Ni,Pt,Ru,Si,Ti)(Al,Co,Cr,Cu,Fe,Ge

,Ir,Mn,Ni,Pt,Ru,Si,Ti)

Laves_C14 (2)(1) (Co,Fe,Ti)(Co,Fe,Ti)

Laves_C15 (2)(1) (Cr,Cu,Fe,Ni,Ti)(Cr,Cu,Fe,Ni,Ti)

Laves_C36 (2)(1) (Cu,Ni,Ti)(Cu,Ni,Ti)

Liquid (1)

(Ag,Al,Au,B,Bi,Bi2Se3,C,Co,Cr,CrS,Cr3Ge,CrSe,Cu,Cu2S,C

u2Se,Fe,FeS,FeSe,Ge,Ge3Mn5,In,Ir,Mn,MnS,MnSe,Ni,NiS,O

s,P,Pb,PbS,PbSe,Pd,Pt,PtSn,Rh,Ru,S,Sb,Se,SeNi,SeSn,Se2Si,

SeZn,Si,Sn,Ti,Zn,ZnS)

Mn5Si3 (2)(3)(3) (Cr,Fe,Si,Ti)(Cr,Si,Sn,Ti)(Cr,Fe,Ti)

Ni3Sn2 (0.5)(0.25)(0.25) (Ni,Sn)(Au,Ni)(Au,Ni)

Sigma (8)(4)(18) (Al,Co,Fe,Mn,Ni,Ru)(Cr)(Al,Co,Cr,Fe,Mn,Ni,Ru)


98


The thermodynamic modeling status for the constituent binaries and

ternaries of current database are given in Tables 8.3. The color

represents the following meaning:

: Full description


: Extrapolation

Table 8.3: Thermodynamic modeling status for the constituent binaries

Al Au B Bi C Co Cr Cu Fe Ge In Ir Mn Ni Os P Pb Pd Pt Rh Ru S Sb Se Si Sn Ti Zn

Ag

Al

Au

B

Bi

C

Co

Cr

Cu

Fe

Ge

In

Ir

Mn

Ni

Os

P

Pb

Pd

Pt

Rh

Ru

S

Sb

Se

Si

Sn

Ti


99

Table 8.4: Thermodynamically modeled constituent ternaries


The current thermodynamic database can be used to calculate the phase

diagrams not only for the noble-metal-rich systems (Ag-, Au-, Cu-, Ir-,

Pd- and Pt-) but also other common alloying systems, such as Pb and/or

Sn-rich solders. Extensive tests and validations have been carried out on

the current thermodynamic database using the published experimental

data in the literature. A few examples are given in Figures 8.1-8.3. Figure

8.1 shows the Pt-Sn binary phase diagram with experimental phase

boundary data plotted on it. Figure 8.2 shows two isoplethal sections in

the of the Ag-Au-Bi ternary system: (a) Ag-Au-85 at.%Bi; (b) Au-Bi-20

Ag-Al-Au Ag-Al-Cu Ag-Al-Ge Ag-Al-Si Ag-Al-Sn Ag-Al-Zn Ag-Au-Bi

Ag-Au-Cu Ag-Au-Ge Ag-Au-Pb Ag-Au-Si Ag-Au-Sn Ag-Bi-Cu Ag-Bi-In

Ag-Bi-Pb Ag-Bi-Sb Ag-Bi-Sn Ag-Bi-Zn Ag-Cu-Ni Ag-Cu-Ni Ag-Cu-Pb

Ag-Cu-Zn Ag-In-Pd Ag-In-Sb Ag-In-Sn Ag-Pb-Sb Ag-Pb-Sn Ag-Sb-Sn

Ag-Sn-Zn Al-Bi-Cu Al-Bi-Zn Al-C-Co Al-C-Mn Al-C-Ni Al-Co-Cr

Al-Co-Cu Al-Co-Fe Al-Co-Mn Al-Co-Ni Al-Cr-Cu Al-Cr-Fe Al-Cr-Ni

Al-Cu-Fe Al-Cu-Mn Al-Cu-Ni Al-Cu-Sb Al-Cu-Si Al-Cu-Sn Al-Cu-Zn

Al-Fe-Mn Al-Fe-Ni Al-Fe-Si Al-Fe-Zn Al-In-Sb Al-In-Sn Al-Pb-Zn

Al-Mn-Ni Al-Si-Sn Al-Si-Zn Al-Sn-Zn Au-Ge-Sb Au-Ge-Sn Au-In-Sb

Au-In-Sn Au-Ni-Sn Au-Sb-Si Au-Si-Sn B-Co-Fe B-Cu-Fe B-Fe-Ni

B-Ni-Si Bi-Cu-Ni Bi-Cu-Pb Bi-Cu-Sb Bi-Cu-Se Bi-Cu-Sn Bi-Cu-Zn

Bi-In-Pb Bi-In-Sb Bi-In-Sn Bi-Sb-Sn Bi-Sb-Zn Bi-Se-Sn Bi-Se-Zn

Bi-Sn-Zn C-Co-Fe C-Co-Ni C-Cr-Fe C-Cu-Fe C-Fe-Ni Co-Cr-Cu

Co-Cr-Fe Co-Cr-Ni Co-Cu-Fe Co-Cu-Mn Co-Cu-Ni Co-Mn-Ni Cr-Cu-Fe

Cr-Cu-Mn Cr-Cu-Ni Cr-Cu-Si Cr-Cu-Sn Cr-Cu-Ti Cr-Fe-Mn Cr-Fe-Ni

Cr-Fe-P Cr-Fe-S Cr-Fe-Si Cr-Mn-Ni Cr-Mn-S Cr-Ni-S Cr-Ni-Si

Cu-Fe-Mn Cu-Fe-Ni Cu-Fe-P Cu-Fe-S Cu-Fe-Sb Cu-Fe-Si Cu-Fe-Zn

Cu-In-Sn Cu-Mn-Ni Cu-Mn-Zn Cu-Ni-P Cu-Ni-Pb Cu-Ni-Sb Cu-Ni-Sn

Cu-Ni-Ti Cu-Ni-Zn Cu-P-Sn Cu-Pb-Sb Cu-Pb-Zn Cu-S-Pb Cu-Sb-Se

Cu-Sb-Sn Cu-Sb-Zn Cu-Se-Zn Cu-Si-Ti Cu-Si-Zn Cu-Sn-Ti Cu-Sn-Zn

Cu-Ti-Zn Fe-Mn-Ni Fe-Mn-S Fe-Mn-Si Fe-Ni-S Fe-Ni-Si Fe-Si-Sn

In-Pb-Zn In-Sb-Sn In-Sn-Zn Pb-Sb-Sn Pb-Sb-Zn Mn-S-Ni Ni-Si-Ti

Ni-Si-Zn Ni-Sn-Zn


100

at.%Ag. The experimentally measured phase boundary data are also

plotted on them for comparison. Figure 8.3 shows comparison between

the calculated and measured liquidus temperatures for some Cu-rich

alloys.

Figure 8.1: Comparison between the calculated Pt-Sn phase diagram with the

experimental data


101

Figure 8.2: Comparison between the calculated isopleths and experimentally measured

data of the Ag-Au-Bi ternary system (a) Ag-Au-85 at.%Bi; (b) Au-Bi-20 at.%Ag


102

Figure 8.3: Comparison between the calculated and experimentally measured liquidus

temperatures of [1982Bac]

8.6 References

[1994Dur] Ph. Durussel, R. Massara, P. Feschotte, J. Alloy Compd., 215 (1994), pp. 175–179

[1907Doe] F. Doerinckel, Z. Anorg. Chem., 54 (1907), pp. 333–366

[1998Anr] P. Anres, M. Gaune-Escard, J.P. Bros, E. Hayer, J. Alloys

Compd., 280 (1998), pp. 158–167

[2005Zor] E. Zoro, D. Boa, C. Servant, B. Legendre, J. Alloys Compd., 398 (2005), pp. 106–112

[1982Bac] L. Backerud, l.M. Liljenvall, H. Steen, “Solidification characteristics of some copper alloys”, International Copper Research Association, Inc., 1982


104

9.1 General Information

This database includes 79 elements and covers a total of 742 binary

systems. The binary systems having been assessed are highlighted in

Table 9.1. A total of 1939 phases including various multicomponent

solution phases and many important intermetallic compounds have been

assessed in PanSolution database. The composition ranges are limited to

the assessed binary systems. Extrapolation to the ternaries may not be

accurate.

Pansolution database can be used as a reference library for binary phase

diagrams. User can obtain a lot of useful information via calculations,

such as phase composition range, invariant reactions, liquidus

temperatures and so on. User may also examine phase stabilities in

ternary or high order systems via simple assumption of extrapolation.

The assessed binary phase diagrams in PanSolution database can also

be accessed through the following website:

http://ipandat.computherm.com.

http://ipandat.computherm.com/


105

Table 9.1. Assessed binary systems in PanSolution database


106

10. PanTitanium

Thermodynamic Database for Titanium-Based Alloys


Ti

Al B

C

Cr

Cu

Fe

H

Mn

Mo N Nb

Ni

O

Si

Sn

Ta

Ti

V

Zr


107

10.1 Components


Major alloying elements: Al, Cr, Cu, Fe, Mo, Nb, Ni, Sn, Ta, Ti, V and Zr

Minor alloying elements: B, C, H, N, O, Mn and Si


The suggested composition range for each element is listed in Table 10.1. It

should be noted that this given composition range is rather conservative. It

is derived from the chemistries of the multicomponent commercial alloys

that have been used to validate the current database. In the subsystems,

many of these elements can be applied to a much wider composition range.

In fact, some subsystems are valid in the entire composition range as given

in section 10.4.



Ti 75-100

Al,V 0-11

Mo,Nb,Ta, Zr 0-8

Cr,Sn 0-5

Cu, Fe,Ni 0-3

B, C, H, N, O, Mn, Si 0-0.5

10.3 Phases

A total of 126 phases are included in the current database, and Table 10.2

lists those that are important for commercial titanium alloys. Information on

all the other phases may be displayed through TDB viewer of Pandat and

can be found at www.computherm.com.



108

Table 10.2: Phase Name and Related Information


A15_Nb3Al (3)(1) (Cr,Nb,Si,Ti)(Al,Cr,Nb,Si)

Bcc (1)(3) (Al,Cr,Cu,Fe,Mo,Nb,Ni,Si,Sn,Ta,Ti,V,Zr) (B,C,H,N,O,Va)

Cr3Si_A15 (3)(1)(3) (Cr,Nb,Si,Ti)(Cr,Nb,Si)(Va)

DO19_Ti3Al (0.75)(0.25)(0.5) (Al,Cr,Mo,Nb,Sn,Ta,Ti,V,Zr) (Al,Cr,Mo,Nb,Si,Sn,Ta,Ti,V,Zr)(O,Va)

DO22_TiAl3 (3)(1) (Al,Mo,Ti,V)(Cr,Mo,Nb,Ta,Ti,V)

Diamond_A4 (1) (Al,C,Si,Sn,Ti)

Fcc (1)(1) (Al,Cr,Cu,Fe,Mo,Nb,Ni,Si,Sn,Ta,Ti,V,Zr) (B,C,H,N,O,Va)

Hcp (1)(0.5) (Al,Cr,Cu,Fe,Mo,Nb,Ni,Si,Sn,Ta,Ti,V,Zr) (B,C,H,N,O,Va)

L10_TiAl (1)(1) (Al,Cr,Mo,Nb,Si,Ta,Ti,V) (Al,Cr,Mo,Nb,Ta,Ti,V)

Laves_C14 (2)(1) (Al,Cr,Fe,Mo,Nb,Si,Ta,Ti,Zr) (Al,Cr,Fe,Mo,Nb,Ta,Ti,Zr)

Laves_C15 (2)(1) (Al,Cr,Si,Ti,Zr)(Al,Cr,Si,Ti,Zr)

Laves_C36 (2)(1) (Al,Cr,Ni,Zr)(Al,Cr,Ni,Zr)

Liquid (1) (Al,B,C,Cr,Cu,Fe,H,Mo,N,Nb,Ni,O,Si,Sn,Ta,Ti,V,Zr)

Sigma (8)(4)(18) (Al,Fe,Ni)(Cr,Mo,Nb,Ta,Ti,V) (Al,Cr,Fe,Mo,Nb,Ni,Ta,Ti,V)

10.4 Sub-System Information

The composition limits given in Table 10.1 are for multicomponent

commercial titanium alloys in general. Complete and partial thermodynamic


109

descriptions are developed for many binary systems as listed in Table 10.3.

This means the current database works in a much wider composition range

in many sub-systems.

Table 10.3 lists all the binaries for the major components and some N-X and

Si-X binary systems. Thermodynamic descriptions are fully developed for the

binaries in green color, which means that there is no composition limits if

calculations are carried out for these binary systems. Only major phases are

considered for the binaries in yellow color. Partial of the system is modeled

for the binaries in red color. The number in front of one of the elements

specifies the valid composition range. For example, Al-5B indicates that this

system is modeled from pure Al to 5wt% of B. No model parameters are

developed for those binaries in white color.

In addition to the binaries, thermodynamic description for the key ternary

Ti-Al-V system is also developed.

: Full description


: Partial description for certain composition range

: Extrapolation

Table 10.3: Current Status of Key Binary Systems

Cr Cu Fe Mo Nb Ni Si Sn Ta Ti V Zr

Al Al-Cr Al-Cu Al-Fe Al-Mo Al-Nb Al-Ni Al-Si Al-Sn Al-Ta Al-Ti Al-V Al-Zr

Cr Cr-Cu Cr-Fe Cr-Mo Cr-Nb Cr-Ni Cr-Si Cr-Sn Cr-Ta Cr-Ti Cr-V Cr-Zr

Cu 2Cu-Fe Cu-Mo Cu-Nb Cu-Ni Cu-Si Cu-Sn Cu-Ta Cu-Ti Cu-V Cu-Zr

Fe Fe-Mo Fe-Nb Fe-Ni Fe-5Si Fe-Sn Fe-Ta Fe-Ti Fe-V Fe-Zr

Mo Mo-Nb Mo-Ni Mo-8Si Mo-Sn Mo-Ta Mo-Ti Mo-V Mo-Zr

N N-Nb N-Ni N-Si N-Sn N-Ta N-Ti N-V N-Zr

Nb Nb-Ni Nb-5Si Nb-Sn Nb-Ta Nb-Ti Nb-V Nb-Zr

Ni Ni-Si Ni-Sn Ni-Ta Ni-Ti Ni-V Ni-Zr

Si Si-Sn 5Si-Ta Si-Ti 25Si-V 3Si-Zr

Sn Sn-Ta Sn-Ti Sn-V Sn-Zr

Ta Ta-Ti Ta-V Ta-Zr

Ti Ti-V Ti-Zr

V V-Zr


110


Since this database has been designed for use with conventional - types of

titanium alloys, it has been focused at the Ti-rich corner. This database has

been tested by a large number of - type of titanium alloys, such as Ti64,

Ti6242 and Ti6246. Table 10.4 lists the alloys and references used for

validating the current database. The suggested composition ranges given in

Table 1 are based on the compositions of these testing alloys. Users need to

be careful while using the database beyond the suggested ranges.

Table 10.4: Experimental Data Used for Testing the Current Titanium

Database

Alloy Experimental Information References

Ti64

transus, approach curve, partitioning

of Al and V in and .

[1966Cas,1979Las, 1986Kah,1986Ro, 1991Lee,2003Fur, 2003Sem,2003Ven]

Ti-144A transus, approach curve, and/or partition coefficient

[2003Ven]

Ti-155A transus, approach curve, and/or partition coefficient

[2003Ven]

Ti-6246 transus [2003Fur]


IMI 834 transus [2003Fur]


Ti-10-2-3 transus [2003Fur]

Ti-6-6-2 transus [2003Fur]


Ti-6Al-2Nb-1Ta-0.8Mo

transus [1984Lin]

Corona X approach curve [2003Boy]

Ti-4.5Al-5Mo-1.5Cr(Corona 5)

transus [1984Yod]

Ti-10-2-3 transus, approach curve [1980Due]

IMI 550 transus, approach curve, partitioning

of Al, Mo, Sn and Si in and .

[2001Kha]

, +, and alloys listed in the handbook

transus [1994Boy]


111

This database can be used to calculate phase equilibria for multi-

component alloys, such as equilibrium between and . It can be used to

predict phase transformation temperatures, such as -transus. The fraction

of each phase as a function of temperature, partitioning of components in

different phases can also be calculated. In addition to equilibrium

calculations, Scheil simulations can also be carried out using this database.

Some calculated examples are given below.

Beta transus, the temperature at which starts to form from , is an

important reference parameter in the selection of processing conditions,

such as heat treatment process, for the conventional - type of titanium

alloys. This temperature has been calculated for a large number of Ti64 and

other titanium alloys using PanTi database. Figure 10.1 shows a comparison

between the predicted and observed beta transus temperatures for about 40

Ti64 heats, reasonable agreement is obtained. The accuracy of the prediction

depends on the reliability of the database and the accuracy of the input

chemistry of the alloy. The calculated beta transus temperature is found to

be very sensitive to the amount of the interstitial elements, such as C, H, N,

and O. It is seen from Figure 10.1 that the predicted beta transus

temperatures are in general higher than the observed ones. This can be

explained by the fact that the calculated beta transus temperature

corresponds to the temperature at which just starts to form, while its

amount is 0%. It is very difficult to catch this exact temperature by

experiments, and normally the measured temperature may corresponds to

which 1~2% of phase has formed. Taking this factor into consideration, the

transformation temperatures corresponding to 2% of phase are calculated

for the same alloys and are compared with observed values as shown in

Figure 10.2. It is seen that better agreement is obtained.


112

Figure 10.1: Comparison between predicted and observed beta transus for more than 40

Ti64 heats. The calculated transformation temperatures correspond to 0% of phase

Figure 10.2: Comparison between predicted and observed beta transus for more than 40

Ti64 heats. The calculated transformation temperatures correspond to 2% of phase

Figure 10.3 shows a similar comparison for other titanium alloys, including

Ti6222, Ti6242, Ti6246, Ti17 and so on, and reasonable agreement is


113

obtained. The agreement can be improved if the transformation

temperatures corresponding to 2% of phase are used for comparison.

Figure 10.3: Comparison between predicted and observed beta transus for other titanium

alloys. The calculated transformation temperatures correspond to 0% of phase formed.

The relative amounts of and phases are critical in the determination of

alloy properties for an - alloy. Beta approach curve, the volume fraction of

beta phase as a function of temperature, is therefore important in the

selection of final heat treatment temperature. Beta approach curves for two

Ti64 heats are calculated as plotted in Figures 10.4 and 10.5. The

experimental data [2003Sem, 1966Cas] are also plotted on the diagrams for

comparison; very good agreements are obtained.

It should point out that the calculated phase fractions are mole fractions,

while the measured values are volume fractions. However, since the molar

volume of the phase is very close to that of the phase, the error induced

due to the direct comparison between them is small. This can be seen in

750 800 850 900 950 1000 1050 1100

750

800

850

900

950

1000

1050

1100

Ca

lcu

late

d (

oC

)

Measured (oC)

6246 Ti

6242 Ti

IMI834

Ti-17

Ti 10-2-3

Ti 6-6-2


114

Figure 10.4 in which both the mole factions and the volume fractions of

phase are plotted.

Figure 10.4: Beta approach curve for a Ti64 alloy with experimental data from [2003Sem]

Figure 10.5: Beta approach curve for a Ti64 alloy with experimental data from [1966Cas].

720 760 800 840 880 920 960 1000

0.0

0.2

0.4

0.6

0.8

1.0

Fra

ctio

n o

f B

eta

Ph

ase

Temperature [oC]

Measured [03Sem]

Calculated, mole

Calculated, volume

600 650 700 750 800 850 900 950 1000

0.0

0.2

0.4

0.6

0.8

1.0

Fra

ctio

n o

f B

eta

Ph

ase

Temperature [oC]

Measured [66Cas]

Calculated


115

In addition to Ti64, beta approach curves are also calculated for other

titanium alloys. Figure 10.6 shows the beta approach curve for one Ti6242

alloy, and the experimental data are from Semiatin [2005Sem].

Figure 10.6: Beta approach curve for a Ti-6242 alloy with experimental data from

[2005Sem].

Equilibrium phase compositions are useful in understanding the partitioning

of elements in different phases. These are calculated and compared with the

experimental measurements for Ti64 and Ti6242 alloys. Examples are given

in Figures 10.7 to 10.9. Figure 10.7 shows the equilibrium compositions of

Al and V in and for one Ti64 alloy. In general, the calculated equilibrium

compositions agree with the experimental data very well. The calculated V

concentrations in the phase are higher than the measurements at low

temperatures. This is due to the fact that the grains were too small to allow

an accurate analysis [1979Las]. Figures 10.8 and 10.9 show the equilibrium

compositions of Al, Mo, and Ti in and for the Ti6242 alloy.

700 750 800 850 900 950 1000 1050

0.0

0.2

0.4

0.6

0.8

1.0

F

ractio

n o

f B

eta

Ph

ase

Temperature [oC]

Measured [05Sem]

Calculated, mole


116

Figure 10.7: Equilibrium compositions of Al and V in the alpha and beta phases for a Ti64

alloy with the experimental data from [2003Sem].

Figure 10.8: Equilibrium compositions of Al and Mo in the alpha and beta phases for a

Ti6242 alloy with the experimental data from [2005Sem].

Figures 10.10 and 10.11 show the calculated fractions for IMI550 and

Corona-X alloys, respectively. Both calculations agree with experimental

data very well.

700 750 800 850 900 950 1000

0

5

10

15

20

Co

mp

ositio

ns [

wt%

]

Temperature [oC]

Al, Measured [03Sem]

V, Measured [03Sem]

Al, Calculated

V, Calculated

700 750 800 850 900 950 1000

0

5

10

15

20

25

Co

mp

ositio

ns [

wt%

]

Temperature [oC]

Al Alpha

Mo Alpha

Al Beta

Mo Beta

Pandat Al Alpha

Pandat Mo Alpha

Pandat Al Beta

Pandat Mo Beta


117

Figure 10.9: Equilibrium compositions of Ti in the alpha and beta phases for a Ti6242

alloy with experimental data from [2005Sem].

Figure 10.10: Alpha Fraction curve for an IMI550 alloy with experimental data [2001Kha].

800 850 900 950 1000

70

75

80

85

90

Co

mp

ositio

ns [

wt%

]

Temperature [oC]

Ti Alpha

Ti Beta

Pandat Ti Alpha

Pandat Ti Beta

750 800 850 900 950 1000

0.0

0.2

0.4

0.6

0.8

1.0

Fra

ctio

n o

f A

lph

a P

ha

se

Temperature [oC]

Ti-IMI550

SEM [01Kha]

Optical [01Kha]

Calculated


118

Figure 10.11: Alpha Fraction curve for a Corona-X alloy with experimental data [2001Kha].

10.6 References

[1966Cas] R. Castro and L. Seraphin, Mem. Sci. Rev. Met., 63 (1966), 1025-1058.

[1979Las] A.L. Lasalmonie and M.Loubradou, J. Mat. Sci., 14 (1979), 2589-

2595.

[1980Due] T.W. Duerig, G.T. Terlinde and J.C. Williams, Met. Trans. A, 11A

(1980), 1987-1998.

[1984Lin] F. S. Lin, E. A. Starke, Jr., S. B. Chakrabortty and A. Gysler,

Met. Trans., 15A (1984), 1229-1246.

[1984Yod] G.R. Yoder, F.H. Froes and D. Eylon, Met. Trans., 15A (1984),

183-197.

[1986Kah] A.I. Kahveci and G.E. Welsch, Scripta Met., 20 (1986), 1287-1290.

[1986Ro] Y. Ro, H. Onodera, and K. Ohno, Trans. Iron Steel Inst. Japan, 26(4) (1986), 322-327.

750 800 850 900 950

0.0

0.2

0.4

0.6

0.8

Fra

ctio

n o

f A

lph

a P

ha

se

Temperature [oC]

Ti-Corona-X

Exp [03Boy]

Calculated


119

[1991Lee] Y.T. Lee, M. Peters and G. Welsch, Met. Trans., 22A (1991), 709-714.

[1994Boy] R. Boyer, G. Welsch and E. W. Collings, Materials Properties Handbook: Titanium Alloys, ASM International, Materials Park,

OH, 1994.

[2001Kha] K.K. Kharia and H.J. Rack, Met. Trans., 32A (2001), 671-679.

[2003Boy] R. Boyer, Boeing, private communication, 2003.

[2003Fur] D. Furrer, LADISH, private communication, 2003.

[2003Sem] S.L. Semiatin, S.L. Knisley, P.N. Fagin, F. Zhang and D.R.

Barker, Met. Trans., 34A (2003), 2377-2386.

[2003Ven] V. Venkatesh, TIMET, private communication, 2003.

[2005Sem] S.L. Semiatin, AFRL, private communication, 2005.


120

11. PanBMG

Thermodynamic Database for Bulk Metallic Glass


BMG

Al

Cu

Ni

Si

Ti

Zr


121

11.1 Components


Major alloying elements: Al, Cu, Ni, Si, Ti, and Zr



The PanBMG database is a full description of the six-component system,

which includes 15 binaries and 20 ternaries.



Al 0-100

Cu 0-100

Ni 0-100

Si 0-100

Ti 0-100

Zr 0-100

11.3 Phases

Total of 122 phases are included in the database, which account for all the

stable phases appearing in the alloy system. The name, the structure, and

model type of major phases are given in Table 11.2. Information on all the

other phases may be displayed through TDB viewer of Pandat and can be

found at www.computherm.com.



122



Al5CuTi2 (0.75)(0.25) (Al,Cu)(Ti)

Al5CuZr2 (0.625)(0.125)(0.25) (Al)(Cu)(Zr)

Al6Cu3Ni (0.6)(0.3)(0.1) (Al)(Cu)(Ni)

AlCu2Ti (0.75)(0.25) (Al,Cu)(Ti)

AlCu2Zr (0.25)(0.5)(0.25) (Al)(Cu)(Zr)

AlCuTi (0.6667)(0.3333) (Al,Cu)(Ti)

AlCuZr (0.667)(0.333) (Al,Cu)(Zr)

B2 (0.5)(0.5) (Al,Cu,Ni,Ti,Zr)(Cu,Ni,Ti,Zr,VA)

Bcc (1)(3) (Al,Cu,Ni,Si,Ti,Zr)(VA)

Cu2TiZr (0.5)(0.25)(0.25) (Cu)(Ti)(Zr)

Cu3Si4Zr2 (0.3334)(0.4444)(0.2222) (Cu)(Si)(Zr)

Cu4Si2Zr3 (0.4444)(0.2222)(0.3334) (Cu)(Si)(Zr)

Cu4Si4Zr3 (0.3636)(0.3636)(0.2728) (Cu)(Si)(Zr)

Fcc (1)(1) (Al,Cu,Ni,Si,Ti,Zr)(Va)

Gamma_D83 (1)(1) (Al,Cu,Ni,Si)(Va)

Hcp (1)(0.5) (Al,Cu,Ni,Si,Ti,Zr)(Va)

L12 (0.75)(0.25)(1) (Al,Cu,Ni,Si,Ti,Zr)(Al,Cu,Ni,Si,Ti,Zr)(Va)

Laves_C14 (2)(1) (Al,Ni,Ti)(Al,Ni,Ti)

Liquid (1) (Al,Cu,Ni,Si,Ti,Zr)

Ni4Si9Zr7 (0.2)(0.45)(0.35) (Ni)(Si)(Zr)

NiSiZr (0.3333)(0.3333)(0.3334) (Ni)(Si)(Zr)

NiTi (0.5)(0.5) (Cu,Ni)(Al,Ti,Zr)

NiTi2 (0.333333)(0.666667) (Cu,Ni)(Al,Ti)

NiTiZr (1)(1)(1) (Ni)(Ti)(Zr)


123


All the binary systems and ternary systems in the PanBMG database were

critically assessed and thermodynamic descriptions were validated

extensively against experimental information. All the equilibrium phases in

each binary system and ternary system were covered in the database.

Complete phase diagrams can be calculated for all binary and ternary

systems in the Al-Cu-Ni-Si-Ti-Zr system. The binary systems and ternary

systems included in the PanBMG database are listed in Tables 11.3 and

11.4.

: Full description


: Extrapolation

Table 11.3 Binary Systems Included in the PanBMG Database

Cu Ni Si Ti Zr

Al Al-Cu Al-Ni Al-Si Al-Ti Al-Zr

Cu Cu-Ni Cu-Si Cu-Ti Cu-Zr

Ni Ni-Si Ni-Ti Ni-Zr

Si Si-Ti Si-Zr

Ti Ti-Zr

Table 11.4: Ternary Systems Included in the PanBMG Database

Ni Si Ti Zr

Al-Cu Al-Cu-Ni Al-Cu-Si Al-Cu-Ti Al-Cu-Zr

Al-Ni Al-Ni-Si Al-Ni-Ti Al-Ni-Zr

Al-Si Al-Si-Ti Al-Si-Zr

Al-Ti Al-Ti-Zr

Cu-Ni Cu-Ni-Si Cu-Ni-Ti Cu-Ni-Zr

Cu-Si Cu-Si-Ti Cu-Si-Zr

Cu-Ti Cu-Ti-Zr

Ni-Si Ni-Si-Ti Ni-Si-Zr

Ni-Ti Ni-Ti-Zr

Si-Ti Si-Ti-Zr


124

A calculated Cu-Zr binary phase diagram and a calculated liquidus

projection for the Al-Ni-Zr system are shown in Figures 10.1 and 10.2,

respectively.

Figure 11.1: Calculated Cu-Zr binary phase diagram

Figure 11.2: Calculated liquidus projection for Al-Ni-Zr ternary system


125

Some sub-quaternary systems of this database have been critically

assessed and thermodynamically modeled. Figure 10.3 shows the

comparison between the calculated integral enthalpy of mixing of liquid

Al17Ni66Si17—Cu alloys at 1575K and the experimental data from [2000Wit].

Figure 11.3: Comparison between the calculated and experimental integral enthalpy of

mixing of liquid Al17Ni66Si17—Cu alloys at 1575K


Since the major application of the PanBMG database is to predict the

composition region of low-lying liquidus surfaces of the Zr-Al-Cu-Ni-Si-Ti

system where bulk metallic glass (BMG) tends to form, the database is

validated by comparing the predicted composition region with the low-lying

liquidus surfaces and experimentally identified bulk metallic glass forming

region. The low-lying liquidus surfaces are indicated by the temperatures of

the invariant reactions occurring on the liquidus surface, which can be

automatically calculated by Pandat. Examples of these comparisons for Zr-

Cu-Ni-Ti and Zr-Al-Cu-Ni-Ti are given below.


126

Using the PanBMG database, the invariant temperatures for all the five-

phase equilibria in the Cu-Ni-Ti-Zr alloys with one of these phases being a

liquid phase were calculated. Figure 11.4 compares the calculated liquid

composition of the invariant reactions with the lowest temperatures and

experimentally identified regions for BMG formation [2001Yan]. The

calculated liquid compositions of these invariant reactions are denoted as

solid circles and the experimentally identified BMG forming compositions by

Lin and Johnson [1995Lin] are denoted by open squares.

0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.4

0.6

0.8

1.0

X(Zr)

X(Cu+Ni)X(Ti)

Calculated

Lin, Johnson

Figure 11.4: Comparison of the thermodynamically predicted and experimentally identified

[1995Lin] liquid compositions of the five-phase invariant reactions with one of phases being

liquid in the Zr-Cu-Ni-Ti system

Figure 11.5 shows that thermodynamically predicted liquid alloy

compositions with low-lying liquidus surface illustrate a region of the

quinary composition space, in which a series of new Zr-rich alloys were

subsequently found experimentally to form bulk metallic glasses with

diameters up to 14mm by using the conventional copper mold dropping

casting (or suction casting) method. Five representative novel glass-forming

alloys are denoted as G1-G5 in Figure 11.5 as well. Strikingly, the calculated


127

compositional region is noted to be in good agreement with those

experimental results [1999Joh, 1996Xin, 2000Pel, 1999Xin, 2003Zha,

2005Cao, 2005Ma] (presented as green dots in Figure 11.5).

Figure 11.5: Comparison of the thermodynamically predicted and experimentally identified

liquid compositions of the six-phase invariant equilibria with one of phases being liquid in

the Zr-Al-Cu-Ni-Ti system

Figure 11.6 shows a calculated isopleth of the quinary Zr-Al–Cu–Ni–Ti phase

diagram with 8.5%Al, 31.3%Cu, and 4.0%Ni, using the PanBMG database.

The concentration of Ti varies from 0 to 15% with a corresponding

concentration of Zr from 56.2% to 41.2%. In other words, Ti was used to

partially replace Zr in a quaternary base alloy Zr56.2Cu31.3Ni4.0Al8.5. This

quaternary alloy was identified to be a bulk glass-forming alloy (with a

critical casting diameter for glass formation of 6 mm) based on the calculated

low-lying liquidus surface of the quaternary Zr–Al-Cu-Ni system. As shown

in this isopleth, the calculated liquidus at the origin of the compositional

coordinate, i.e., the base alloy Zr56.2Cu31.3Ni4.0Al8.5, decreases rapidly to a

minimum of about 4.9%Ti and then increases again. Thus, the liquidus

depression reaches a maximum of 102K at 4.9%Ti replacement. Accordingly,


128

a series of alloys of Zr56.2-xTixCu31.3Ni4.0Al8.5 with values of x varying from 0

to 12, were prepared with the expectation that the alloy with 4.9%Ti would

exhibit the highest Glass Forming Ability (GFA).

Figure 11.6: (a) The critical casting diameter as a function of Ti concentration in a series

of alloys Zr56.2-xTixCu31.3Ni4.0Al8.5(x=0–12), showing A* (containing 4.9%Ti) is the bulkiest

glass-forming alloy; (b) The calculated isopleth with the compositions of Cu, Ni, and Al fixed

at 31.3%, 4.0%, and 8.5%, respectively. The shaded area denotes the experimentally

observed bulk glass-forming range

Figure 11.7: Surface appearance of the glassy alloys rods obtained in a recent study based

on the thermodynamic calculations


129

11.6 References

[1995Lin] X. H. Lin and W. L. Johnson, J Appl. Phys., 1995; 78 (11), 6514.

[1996Xin] L. Q. Xing, P. Ochin, M. Harmelin, F. Faudot, J. Bigot and J. P. Chevalier, Mater Sci Eng, 1996, A220(1-2), 155-161.

[1999Joh] W. L. Johnson, MRS Bulletin, 1999, 24(10), 42.

[1999Xin] L. Q. Xing, J. Eckert, W. Loser, L. Schultz, Appl Phys Lett, 1999, 74(5), 664.

[2000Pel] J. M. Pelletier, J. Perez and J. L. Soubeyroux, J Non-Cryst Solids 2000, 274(1-3), 301-306.

[2000Wit] V. T. Witusiewicz, I. Arpshofen, H. J. Seifert, F. Sommer, F. Aldinger, Thermochimica Acta, 356(2000), 39-57.

[2001Yan] X.-Y. Yan, Y. A. Chang, Y. Yang, F.-Y. Xie, S.-L. Chen, F. Zhang,

S. Daniel, M.-H. He, Intermetallics, 2001, 9, 535-538.

[2003Zha] Y. Zhang, D. Q. Zhao, M. X. Pan and W. H. Wang, J Non-Cryst Solids, 2003, 315(1,2), 206.

[2005Cao] H. Cao, D. Ma, K-C Hsieh, L. Ding, W. G. Stratton, P. M. Voyles,

Y. Pan and Y. A. Chang, unpublished.

[2005Ma] D. Ma, H. Cao, L. Ding, Y. A. Chang, K. C. Hsieh and Y. Pan, Applied Physics Letters, 87, 171914 (2005).


130

12. ADAMIS

Alloy Database for Micro-Solders

Materials Design Technology Co.,Ltd.

2-5 Odenmacho, Nihonbashi, Chuo-ku

Tokyo 103-0011 JAPAN

ADAMIS

Solder

Ag Al

Au

Bi

Cu

In Ni

Pb

Sb

Sn

Zn


131

Copyright © Materials Design Technology Co.,Ltd.

12.1 Components


Major elements: Ag, Al, Au, Bi, Cu, In, Ni, Pb, Sb, Sn, and Zn.



should be noted that the ADAMIS solder database has been tested with

many commercial micro-soldering alloys, such as Sn-Ag-X, Sn-Cu-X, Sn-In-

X, Sn-Zn-X based alloys, and also Cu-X-Y based alloy systems.


12.3 Phases

Total of 122 phases are included in the database, which account for most of

the phases appearing in the commercial micro-soldering alloys. The name,

the structure, and model type of major phases are given in Table 12.2.


Ag 0-100

Al 0-100

Au 0-100

Bi 0-100

Cu 0-100

In 0-100

Ni 0-100

Pb 0-100

Sb 0-100

Sn 0-100

Zr 0-100


132

Information on all the other phases may be displayed through TDB viewer

of Pandat and can be found at www.computherm.com.



Liquid (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)

BCC (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)

BCT_A5 (1) (Ag,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)

Fcc (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)

Hcp (1) (Ag,Al,Au,Bi,Cu,In,Ni,Pb,Sb,Sn,Zn)

RhombohedralA7 (1) (Ag,Au,Bi,Cu,In,Pb,Sb,Sn,Zn)

Tetragonal_A6 (1) (Bi,In,Pb,Sb,Sn,Zn)

AgCuZn_Eps (1) (Ag,Al,Cu,Zn)

AgCuZn_Gamma (0.15385)(0.15385) (0.23077)(0.46154)

(Ag,Cu,Zn)(Ag,Cu,Zn)(Ag,Cu)(Zn)

AgZn_Zeta (1) (Ag,Sn,Zn)

Ag3SnSb (0.75)(0.25) (Ag,Sb)(Ag,Bi,Sb,Sn)

BiInPbSn_Bea (1) (Bi,In,Pb,Sn)

Cu77InSn (0.77)(0.23) (Cu)(In,Sn)

Cu7In3 (0.7)(0.3) (Cu)(In,Sn)

CuInSn_Eta (0.545)(0.122)(0.333) (Cu)(Cu,In,Sn)(In,Sn)

Cu3Sn (0.75)(0.25) (Cu)(In,Sn)

Cu41Sn11 (0.788)(0.212) (Cu)(In,Sn)

Gama (0.654)(0.115)(0.231) (Cu)(Cu,In)(In,Sn)

InSn_Gamma (1) (Bi,In,Sb,Sn)

AuIn (0.5)(0.5) (Au)(In,Sb,Sn)

AuIn2 (0.33333)(0.66667) (Au)(In,Sb,Sn)

AlCu_GammaH (0.3077)(0.0769)(0.6154) (Al,Zn)(Al,Cu,Zn)(Ag,Cu)

Sn2Ni3 (0.5)(0.25)(0.25) (Ni,Sn)(Au,Ni)(Au,Ni)



133


Tohoku University started to carry out research and experiment for the

solder-semiconductor systems since 1980’s, and based on which the

ADAMIS solder database was developed.

Table 12.3 lists all the 55 binary systems. Thermodynamic descriptions for

all these binaries are critically assessed as colored by green. Table 12.4 lists

all the ternary systems that are assessed for this system. Thermodynamic

descriptions for the ternaries in green color are critically assessed; while

those in yellow color are also developed, but are not yet fully validated.

ADAMIS database can be used to predict various thermodynamic properties

for Sn-Ag-X, Sn-Cu-X, Sn-In-X, Sn-Zn-X based alloy, and also Cu-X-Y based

alloy systems.

: Full description


: Extrapolation

Table 12.3: Current Status of Binary Systems of ADAMIS database

Al Au Bi Cu In Ni Pb Sb Sn Zn

Ag Ag-Al Ag-Au Ag-Bi Ag-Cu Ag-In Ag-Ni Ag-Pb Ag-Sb Ag-Sn Ag-Zn

Al Al-Au Al-Bi Al-Cu Al-In Al-Ni Al-Pb Al-Sb Al-Sn Al-Zn

Au Au-Bi Au-Cu Au-In Au-Ni Au-Pb Au-Sb Au-Sn Au-Zn

Bi Bi-Cu Bi-In Bi-Ni Bi-Pb Bi-Sb Bi-Sn Bi-Zn

Cu Cu-In Cu-Ni Cu-Pb Cu-Sb Cu-Sn Cu-Zn

In In-Ni In-Pb In-Sb In-Sn In-Zn

Ni Ni-Pb Ni-Sb Ni-Sn Ni-Zn

Pb Pb-Sb Pb-Sn Pb-Zn

Sb Sb-Sn Sb-Zn

Sn Sn-Zn


134

Table 12.4: Current Status of Ternary systems of ADAMIS database

Ag-Bi-Cu Ag-Bi-In Ag-Bi-Pb Ag-Bi-Sb Ag-Bi-Sn Ag-Bi-Zn

Ag-Cu-In Ag-Cu-Pb Ag-Cu-Sb Ag-Cu-Sn Ag-Cu-Zn Ag-In-Pb

Ag-In-Sb Ag-In-Sn Ag-In-Zn Ag-Pb-Sb Ag-Pb-Sn Ag-Pb-Zn

Ag-Sb-Sn Ag-Sb-Zn Ag-Sn-Zn

Bi-Cu-In Bi-Cu-Pb Bi-Cu-Sb Bi-Cu-Sn Bi-Cu-Zn Bi-In-Pb

Bi-In-Sb Bi-In-Sn Bi-In-Zn Bi-Pb-Sb Bi-Pb-Sn Bi-Pb-Zn

Bi-Sb-Sn Bi-Sb-Zn Bi-Sn-Zn

Cu-In-Pb Cu-In-Sb Cu-In-Sn Cu-In-Zn Cu-Pb-Sb Cu-Pb-Sn

Cu-Pb-Zn Cu-Sb-Sn Cu-Sb-Zn Cu-Sn-Zn

In-Pb-Sb In-Pb-Sn In-Pb-Zn In-Sb-Sn In-Sb-Zn In-Sn-Zn

Pb-Sb-Sn Pb-Sb-Zn Pb-Sn-Zn

Sb-Sn-Zn


The current database is validated by the large amount of experimental work

carried out at Tohoku University. Some calculated phase diagrams are

compared with experimental data as shown in Figures 12.1-12.5.

Figure 12.1: Ternary Sn-Ag-Cu 400 C Isotherm with the experimental data [2000Ohn]


135

Figure 12.2: Ternary Sn-Ag-Cu 600 C Isotherm with the experimental data [1959Geb]

Figure 12.3: Vertical section diagram of the Ag-Cu-Sn ternary with 10mass% Sn, the

experimental data [1959Geb] are plotted for comparison


136

Figure 12.4: Vertical section diagram of the Ag-Cu-Sn ternary with 25mass% Sn, the

experimental data [1959Geb] are plotted for comparison

Figure 12.5: Projection of liquidus surface in Sn-rich portion of the Sn-Ag-Cu ternary


137

12.6 Applications

Alloy design and processing optimization for micro-soldering alloys.

Multi-component phase diagram calculations, such as liquidus

projection, isothermal section and isopleth.

Solidification sequence simulation using the Scheil model to predict the

microstructure of multi-component solder alloys at the as-cast state.

Equilibrium line calculation to predict the microstructure information,

such as equilibrium phases, phase fraction, phase composition and

phase transformation temperature.

Thermodynamic property calculations, such as specific heat and latent

heat.

12.7 References

[1959Geb] E.Gebhardt and G.Petzow, Z. Metallkd., 50 (1959), 597-605.

[1999Ohn] I.Ohnuma, X.J.Liu, H.Ohtani, and K.Ishida, J. Electron. Mater., 28 (1999), 1164-1171.

[2000Ohn] I.Ohnuma, M.Miyashita, K.Anzai, X.J.Liu, H.Ohtani, R.Kainuma, and K.Ishida, J. Electron. Mater., 29 (2000), 1137-1144.


138

13. MDT Copper


Cu-rich alloys

Materials Design Technology Co.,Ltd.

2-5 Odenmacho, Nihonbashi, Chuo-ku

Tokyo 103-0011 JAPAN

Copyright © Materials Design Technology Co.,Ltd.

Cu

Al B

Bi

C

Cr

Fe

Mn

Ni P Pb

S

Sb

Se

Si

Sn

Ti

Zn


139

13.1 Components


Major alloy elements: Cr, Cu, Fe, Ni, Pb, Si, Sn, Zn

Minor alloy elements: Al, B, Bi, C, Mn, P, S, Sb, Se and Ti



should be noted that this given composition range is rather conservative. It

is derived from the chemistries of the multicomponent commercial alloys

that have been used to validate the current database. In the subsystems,

many of these elements can be applied to a much wider composition range.

In fact, some subsystems are valid in the entire composition range as given

in section 13.4.



Cu 50 ~ 100

Al, Mn 0 ~ 3

Cr, Fe 0 ~ 10

Ni 0 ~ 35

Bi, P, Se 0 ~ 2

Pb, Sb, Si 0 ~ 5

Sn 0 ~ 14

Zn 0 ~ 45

B, C, S, Ti 0 ~ 0.5

13.3 Phases

Total of 260 phases are included in the database and a few key phases are

listed in Table 13.2. Information on all the other phases may be displayed

through TDB viewer of Pandat and can be found at www.computherm.com.




140


Al2Cu (0.667)(0.333) (Al)(Al,Cu)

AlCu_Delta (0.4)(0.6) (Al)(Cu)

AlCu_Eps1 (0.4)(0.6) (Al,Cu)(Al,Cu)

AlCu_Eps2 (0.5)(0.5) (Al,Cu)(Cu)

AlCu_Eta (0.5)(0.5) (Al,Cu)(Cu)

AlCu_Zeta (0.45)(0.55) (Al)(Cu)

Bcc (1)(3) (Al,B,Bi,Cr,Cu,Fe,Mn,Ni,P,Pb,Si,Sn,Ti,Zn)(C,Va)

Cu3Se2 (3)(2) (Cu)(Se)

Cu3Ti2 (0.6)(0.4) (Cu)(Ti)

Cu41Sn11_LEE (0.788)(0.212) (Cu)(Sn)

Cu4Ti (0.8)(0.2) (Cu,Ti)(Cu,Ti)

Cu4Ti3 (0.571)(0.429) (Cu)(Ti)

Cu56Si11 (0.835821)(0.164179) (Cu,Zn)(Si)

CuInSn_Eta (0.545)(0.122)(0.333) (Cu)(Cu,Sn)(Sn)

Fcc (1)(1) (Al,B,Bi,Cr,Cu,Fe,Mn,Ni,P,Pb,Si,Sn,Ti,Zn)(C,Va)

Gammabrass (1) (Al,Cu,Fe,Ni,Si,Zn)

Hcp (1)(0.5) (Al,B,Bi,Cr,Cu,Fe,Mn,Ni,Pb,Si,Sn,Ti,Zn) (C,Va)

Laves_C15 (2)(1) (Cr,Cu,Fe,Ni,Ti)(Cr,Cu,Fe,Ni,Ti)

Laves_C36 (2)(1) (Cu,Ni,Ti)(Cu,Ni,Ti)

Liquid (1) (Al,B,Bi,Bi2Se3,C,Cr,CrSe,Cu,Cu2Se,Fe,FeSe,Mn,Ni,P,Pb,Se,MnSe,PbSe,Si,Sn,SeNi,SeSn,Se2Si,SeZn,Ti,Zn)


141


Key elements of the system are listed as: Cu-Cr-Fe-Ni-Pb-Si-Sn-Zn. The



meaning:

: Full description


: Extrapolation

Table 13.3: Key Binary Systems for the MDT Cu Database

Cr Cu Fe Ni Pb Si Sn Zn

Al Al-Cr Al-Cu Al-Fe Al-Ni Al-Pb Al-Si Al-Sn Al-Zn

Cr

Cr-Cu Cr-Fe Cr-Ni Cr-Pb Cr-Si Cr-Sn Cr-Zn

Cu

Cu-Fe Cu-Ni Cu-Pb Cu-Si Cu-Sn Cu-Zn

Fe

Fe-Ni Fe-Pb Fe-Si Fe-Sn Fe-Zn

Ni Ni-Pb Ni-Si Ni-Sn Ni-Zn

Pb Pb-Si Pb-Sn Pb-Zn

Si Si-Sn Si-Zn

Sn Sn-Zn

Table 13.4: Ternary Systems for the Key Cu-Cr-Fe-Ni-Sn-Zn Subset

Fe Ni Sn Zn

Cu-Cr Cu-Cr-Fe Cu-Cr-Ni Cu-Cr-Sn Cu-Cr-Zn

Cu-Fe Cu-Fe-Ni Cu-Fe-Sn Cu-Fe-Zn

Cu-Ni Cu-Ni-Sn Cu-Ni-Zn

Cu-Sn Cu-Sn-Zn


142


Figure 13.1: Calculated isothermal section diagrams of the Fe-Cu-Cr system at (a) 1273K,

(b) 1373K, and (c) 1573K with the experimental data [1997Oht, 2002Wan]

mas

s% C

r

mass% Cu

0.0

17.3

34.6

52.0

69.3

86.6

0 20 40 60 80 1000 20 40 60 80 1000

20

40

60

80

100

mass% Cu

mass

% C

r

FE

CR

CU

FCC_A1+Liq

BCC_A2+Liq

mas

s% C

r

mass% Cu

0.0

17.3

34.6

52.0

69.3

86.6

0 20 40 60 80 1000 20 40 60 80 1000

20

40

60

80

100

mass% Cu

mass

% C

r

FE

CR

CU

FCC_A1+Liq

BCC_A2+Liq

mas

s% C

r

mass% Cu

0.0

17.3

34.6

52.0

69.3

86.6

0 20 40 60 80 1000 20 40 60 80 1000

20

40

60

80

100

mass% Cu

mass

% C

r

FE

CR

CU

FCC_A1+FCC_A1

BCC_A2+FCC_A1

(a) 1273K

(b) 1373K

(c) 1573K


143

Figure 13.2: Calculated isothermal section diagrams of the Fe-Cu-Si system at (a) 1173K,

(b) 1573K, and (c) 1723K with the experimental data [1997Oht, 1999Him, 2002Wan]

mas

s% C

r

mass% Cu

0.0

17.3

34.6

52.0

69.3

86.6

0 20 40 60 80 1000 20 40 60 80 1000

20

40

60

80

100

mass% Cu

mass

% C

r

FE

SI

CU

Liq

Liq1Liq2

Liq1+Liq2

BCC

FCC

(c) 1723K

mas

s% S

i

mass% Cu

0.0

17.3

34.6

52.0

69.3

86.6

0 20 40 60 80 1000 20 40 60 80 1000

20

40

60

80

100

mass% Cu

mass

% S

i

FE

SI

CU

(Si)+Liq

Liq2

Liq1

FCC_A1

BCC_A2BCC_A2+LIQUID

Liq1+Liq2

FeSi+Liq2

FeSi+Liq1+Liq2

(b) 1573K

mas

s% S

i

mass% Cu

0.0

17.3

34.6

52.0

69.3

86.6

0 20 40 60 80 1000 20 40 60 80 1000

20

40

60

80

100

mass% Cu

mass

% S

i

FE

SI

CU

FeSi2+(Si)+Liq

BCC_A2+FCC_A1

FeSi2+FeSi+Liq

FeSi+Liq

Fe5Si3+FeSi+FCC_A1Fe5Si3+BCC_A2+FCC_A1

(a) 1173K


144

13.6 References

[1997Oht] H.Ohtani, H.Suda, K.Ishida, ISIJ International, 37 (1997), 207-

216.

[1998Kai] R.Kainuma, N.Satoh, X.J.Liu, I.Ohnuma, K.Ishida, J. Alloys Compounds, 266 (1998), 191-200. (Cu-Al-Mn)

[1998Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, S.M.Hao, and K.Ishida, Z. Metallkunde, 98 (1998), 828-835. ( Cu-Al-Fe)

[1999Him] M.Hino, T.Nagasaka, and T.Washizu, J. Phase Equilibria, 20 (1999), 179-186.

[2000Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, K.Ishida, CALPHAD, 24 (2000), 149-167.

[2002Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, K.Ishida, J. Phase Equilibria, 23 (2002), 236-245.

[2004Wan] C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma, K.Ishida, J. Phase Equilibria, 25 (2004), 320-328.

[2005Jia] M.Jiang, C.P.Wang, X.J.Liu, I.Ohnuma, R.Kainuma,

G.P.Vassilev, K.Ishida, J. Physics Chem. of Solids, 66 (2005), 246-250. (Cu-Ni-Zn)

modelling of phases in mg-db - computherm llc · computherm llc thermodynamic databases 8 1.3...

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