engineering the max phases and their composites for ...engineering the max phases and their...
TRANSCRIPT
Engineering the MAX phases and Their
Composites for Extreme Environments
Miladin Radovic
Laboratory for High Temperature Materials
Texas A&M University
International Forum: Multifunctional Material Systems in Extreme EnvironmentsTexas A&M University, College Station, TX 2-3 May, 2016
2
MAX Phases
M: Early transition metal
A: Group A (IIIA and IVA)
X: C and/or N
Mn+1AXn (n=1, 2, 3)
211 312
413
0
1000
2000
3000
4000
5000
0
20
40
60
80
100
120
140
160
180
200
199
0
199
2
199
4
199
6
199
8
200
0
200
2
200
4
200
6
200
8
201
0
201
2
201
4
201
6
Nu
mb
er
of
cit
ati
on
s
Nu
mb
er
of
pu
bli
sh
ed
pa
pe
rs
1967 – Nowotny discovered most of the
phases ternary phases (Monatch.
Chem. 98, 1967, Prog. Solid State
Chem, 2, 1970)
1996 – Barsoum and El-Raghy sensitized
the first phase pure, bulk MAX
phase (J. Am. Ceram. Soc., 79,
1996)
2016 – 70+ pure MAX phases and 100+
solid solutions synthesized
Ti2AlC, Ti3AlC2, Ti3SiC2, Cr2AlC
Source: Web of Science
3
Applications
4
MAX Phases
Metal-like properties:
Good thermal and electrical
conductors
Damage Tolerant
Very resistant to thermal shock
Superb machinability
Behave plastically at higher
temperatures with very
respectable properties.
Ceramic-like properties:
Oxidation and corrosion
resistant – self healing
Refractory
Low density and high stiffness
Low thermal expansion
Some of the fatigue and creep
resistance
Barsoum, M.W. and Radovic, M., Annual Reviews in Materials Research, Vol.41, 2011
Radovic, M., and Barsoum, M.W. , JACerS Bulletin, 2013
5
MAX Phases
Metal-like properties:
Good thermal and electrical
conductors
Damage Tolerant
Very resistant to thermal shock
Superb machinability
Behave plastically at higher
temperatures with very
respectable properties.
Ceramic-like properties:
Oxidation and corrosion
resistant – self healing
Refractory
Low density and high stiffness
Low thermal expansion
Some of the fatigue and creep
resistanceHu, C., et al. Scripta
Materialia 64.8 (2011): 765-768.
Gilbert C.J., et al. Scr.
Mater. 238 (200) 761–67
Barsoum, M.W. and Radovic, M., Annual Reviews in Materials Research, Vol.41, 2011
Radovic, M., and Barsoum, M.W. , JACerS Bulletin, 2013
MAX Phases
Metal-like properties:
Good thermal and electrical
conductors
Damage Tolerant
Very resistant to thermal shock
Superb machinability
Behave plastically at higher
temperatures with very
respectable properties.
Ceramic-like properties:
Oxidation and corrosion
resistant – self healing
Refractory
Low density and high stiffness
Low thermal expansion
Some of the fatigue and creep
resistance
0
100
200
300
400
500
600
0 200 400 600 800 1000 1200 1400 1600
Ret
aine
d Fl
exur
al S
tren
gth
(MPa
)
Quench Temperature (°C)
Nb2AlC
V2AlC
Ti3SiC
2 FG
Ti3SiC
2 CG
Ti3AlC
2
Ta2AlC
Ti3(Si
0.5Ge
0.5)C
2
Ti4AlN
3
Fig. 12
Barsoum, M.W. and Radovic, M., Annual Reviews in Materials Research, Vol.41, 2011
Radovic, M., and Barsoum, M.W. , JACerS Bulletin, 2013
MAX Phases
Metal-like properties:
Good thermal and electrical
conductors
Damage Tolerant
Very resistant to thermal shock
Superb machinability
Behave plastically at higher
temperatures with very
respectable properties.
Ceramic-like properties:
Oxidation and corrosion
resistant – self healing
Refractory
Low density and high stiffness
Low thermal expansion
Some of the fatigue and creep
resistance
Ti3SiC2 tested in tension: (a) initial samples, and samples tested at, b)
1050 oC, 60 MPa, aborted after 50 h; (c) 1200 oC, 60 MPa, tf = 3.86 h; (d)
1050 oC, 40 MPa, tf = 252 h; (e) 1000 oC, 60 MPa, tf = 230 h; (f) 1200 oC,
20 MPa, tf = 32 h; (g) 1200 oC and 60 MPa, tf = 3.86 h; (h) 1000oC, 40
MPa, aborted after 830 h (Radovic et. al, J. Alloys and Compounds,
2002)
Ti2AlC tested in compression (Benitez, R. et al. in preparation)
Barsoum, M.W. and Radovic, M., Annual Reviews in Materials Research, Vol.41, 2011
Radovic, M., and Barsoum, M.W. , JACerS Bulletin, 2013
MAX Phases
Metal-like properties:
Good thermal and electrical
conductors
Damage Tolerant
Very resistant to thermal shock
Superb machinability
Behave plastically at higher
temperatures with very
respectable properties.
Ceramic-like properties:
Oxidation and corrosion
resistant – self healing
Refractory
Low density and high stiffness
Low thermal expansion
Some of the fatigue and creep
resistance
Barsoum, M.W. and Radovic, M., Annual Reviews in Materials Research, Vol.41, 2011
Radovic, M., and Barsoum, M.W. , JACerS Bulletin, 2013
Virtual 2D sections through the tomographic
datasets showing the sequence of crack
growth and healing steps in Ti2AlC at 1500
K in air.
Sundberg, M., et. al. Ceramics
International 30, 1899-1904 (2004).
Sloof, Willem G., et al. Scientific
reports 6 (2016).
Basu, S., Obando, N., Gowdy, A, Karaman, I,
and Radovic, M., J. of the Electrochem.
Society, Vol. 159, (2012)
MAX Phases
Metal-like properties:
Good thermal and electrical
conductors
Damage Tolerant
Very resistant to thermal shock
Superb machinability
Behave plastically at higher
temperatures with very
respectable properties.
Ceramic-like properties:
Oxidation and corrosion
resistant – self healing
Refractory
Low density and high stiffness
Low thermal expansion
Some of the fatigue and creep
resistance
Barsoum, M.W. and Radovic, M., Annual Review s in Materials Research, Vol.41, 2011
Radovic, M., and Barsoum, M.W. , JACerS Bulletin, 2013
10
Sundberg, M., Malmqvist, G., Magnusson, A., & El-Raghy,
T.,Ceramics International 30, 1899-1904 (2004).Basu, S., Obando, N., Gowdy, A, Karaman, I, and Radovic, M., J. of
the Electrochem. Society, Vol. 159, (2012)
Alumina forming MAX phases
Many of Mn+1AlXn (such as Ti2AlC, Ti3AlC3, Cr2AlC) form stable and protective alumina
(Al2O3) oxide layer in air up to 1450 oC.
SEM of the oxide layer formed on Ti2AlC, during
oxidation at 1400 oC.Ti2AlC – no spallation of oxide layer
after 10,000 heating-cooling cycles up
to 1450 oC.
11
Alumina forming MAX phases
Ti2AlC – cyclic oxidation is comparable to the
best know alumina formers but it can be used to
1450 oC.
Byeon, J.W., Hopkins, M., Liu, J., Fischer,
W., Park, K.B., Brady, M.P., Radovic, M.,
El-Raghy, T., Sohn, Y.H., Oxidation of
Metals, Vol. 68, (2007)
Good cycling stability of oxide layer because of
almost identical thermal expansion of Ti2AlC and
alumina, and thus low stresses in the oxide layer.
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0 20 40 60 80 100 120 140
Air1000
oC
1100 oC
1200 oC
1300 oC
Time (hours)
(a)
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0 20 40 60 80 100 120 140
Water Vapor1000 oC
1100 oC
1200 oC
1300 oC
Time (hours)
(b)
Basu, S., Obando, N., Gowdy, A, Karaman, I, and Radovic, M., J. of
the Electrochem. Society, Vol. 159, (2012)
Almost identical oxidation kinetics
in both air and steam.
12
Alumina forming MAX
phases - Self Healing
Self-healing of cracks in Ti2AlC by alumina (Al2O3) formation:
(a) Crack path after four cycles of healing at 1,200◦C for 2 h, and
subsequent fracture. (b) Crack path after seven cycles of healing, and
subsequent fracture. (c) OM image of a crack fractured eight times
before annealing in air at 1,200◦C for 100 h showing the complete
filling of the crack. (d) Flexural strength of the virginal Ti2AlC, after
creating crack damage and after crack healing, respectively.
Yang, H. J., et al. "Self-healing performance of Ti2AlC ceramic." Journal of Materials
Chemistry 22.17 (2012): 8304-8313.
Li, Shibo, et al. "Multiple crack healing of a Ti2AlC ceramic." Journal of the
European Ceramic Society 32.8 (2012): 1813-1820.
Sloof, Willem G., et al. "Repeated crack healing in MAX-phase ceramics revealed by 4D in situ
synchrotron X-ray tomographic microscopy." Scientific reports 6 (2016).
Virtual 2D sections through the
tomographic datasets showing the
sequence of crack growth and healing
steps in Ti2AlC at 1500 K in air
13
MAX Phases – Mechanical Properties
KinkingBasal Slip - Low critical resolved shear stress
L. Farber, I. Levin and M. W.
Barsoum Phil. Mag. Let. 1999.
Barsoum, M.W. and Radovic, M., Annual Reviews in Materials Research, Vol.41, 2011
Kinking - Low critical resolved shear stress
14
Ti2AlC - Hysteretic behavior
Kinking
0 0.0025 0.0050 0.0075 0.0100 0.01250
250
500
750
1000
1250
Str
ess
(MP
a)
Strain (mm/mm)
Ti2AlC: Fine Grain
200 MPa
400 MPa
600 MPa
800 MPa
1000 MPa
1200 MPa
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Room temperature stress-strain hysteresis in Ti2AlC revisited. Acta Materialia, 105, 294-305
Benitez, R., H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Effects of Microstructure on the Mechanical Properties of Ti2AlC in Compression. Acta Materialia, in review
In collaboration with Dr. Gwenaelle ProustUniversity of Sydney
15
Ti2AlC - Hysteretic behavior
Kinking
0 0.0025 0.0050 0.0075 0.0100 0.01250
250
500
750
1000
1250
Str
ess
(MP
a)
Strain (mm/mm)
Ti2AlC: Fine Grain
200 MPa
400 MPa
600 MPa
800 MPa
1000 MPa
1200 MPa
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Room temperature stress-strain hysteresis in Ti2AlC revisited. Acta Materialia, 105, 294-305
Benitez, R., H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Effects of Microstructure on the Mechanical Properties of Ti2AlC in Compression. Acta Materialia, in review
Kinking Non-Linear Elastic (KNE) Model
Micro-cracking (MC) Model
B. Poon, L. Ponson, J. Zhao, G.
Ravichandran. Damage accumulation and
hysteretic behavior of MAX phase
materials, Journal of the Mechanics and
Physics of Solids 59 (2011) 2238-2257.
M.W. Barsoum, T. Zhen, A. Zhou, S.
Basu, S.R. Kalidindi. Microscale
modeling of kinking nonlinear elastic
solids, Physical Review B - Condensed
Matter and Materials Physics 71 (2005)
1-8.
A. Zhou, M.W. Barsoum. Nonlinear
elastic deformation of MAX phases, Key
Engineering Materials 434-435 (2010)
149-153.
Reversible Flow (RF) Model
N.G. Jones, C. Humphrey, L.D. Connor,
O. Wilhelmsson, L. Hultman, H.J. Stone,
F. Giuliani, W.J. Clegg. On the relevance
of kinking to reversible hysteresis in
MAX phases, Acta Materialia 69 (2014)
149-161.
In collaboration with Dr. Gwenaelle ProustUniversity of Sydney
16
Ti2AlC - Hysteretic behavior
Kinking
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Room temperature stress-strain hysteresis in Ti2AlC revisited. Acta Materialia, 105, 294-305
Benitez, R., H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Effects of Microstructure on the Mechanical Properties of Ti2AlC in Compression. Acta Materialia, in review
Wd
• I-II – onset of glide in soft grains
• II-III – onset kinking and formation of
low angle kink boundaries
• III-IV – onset microcracking
17
Ti2AlC - Hysteretic behavior
Kinking
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Room temperature stress-strain hysteresis in Ti2AlC revisited. Acta Materialia, 105, 294-305
Benitez, R., H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Effects of Microstructure on the Mechanical Properties of Ti2AlC in Compression. Acta Materialia, in review
• As-Sintered
• After 500 MPa
=100 µm; Copy of Schmid Factor L-Y; Step=0.2 µm; Grid1250x1250
=100 µm; Schmid Factor L-Y + GB; Step=0.2 µm; Grid1250x1250
18
Ti2AlC - Hysteretic behavior
Kinking
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Room temperature stress-strain hysteresis in Ti2AlC revisited. Acta Materialia, 105, 294-305
Benitez, R., H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). Effects of Microstructure on the Mechanical Properties of Ti2AlC in Compression. Acta Materialia, in review
Hall- Petch model
CRSS= 7 MPa
Frank-Stroh model
𝑆𝑙𝑜𝑝 yields value of 737 𝑀𝑃𝑎 𝜇𝑚
Zener-Stroh model
th= 20 GPa, (theoretical values
15-25 GPa)
19
Ti2AlC – High temperature behavior
Incre
asin
g g
rain
siz
e
In collaboration with Dr. Gwenaelle ProustUniversity of Sydney
Invconel 718
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). In preparation
20
Ti2AlC – High temperature behavior
IPF GBs BC + UI SF + GBs
As
Sin
tere
d
20
°C
50
0 M
Pa
70
0 °
C
87
0 M
Pa
11
00
°C
32
0 M
Pa
Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). In preparation
21
Kinking
Dynamic: 300 s-1Quasi-Static: 10-4 s-1
0 200 400 600 800 1000 1200 14000
300
600
900
1200
1500
1800
Quasi-Static
Quasi-Static
Dynamic
Ultim
ate
Co
mp
ressiv
e S
tre
ng
th (
MP
a)
Temperature (°C)
In Collaboration with
Arun Shukla, URI
Ti2AlC – High temperature behavior
Parrikar, P. N., Benitez, R., Gao, H., Radovic, M., & Shukla, A. (2016). Mechanical response of fine grained Ti2AlC under extreme thermo-
mechanical loading conditions. Materials Science and Engineering: A, 658, 176-184.
22
Ti2AlC – Solid Solution Hardening
In collaboration with Dr. Raymundo Arroyave Texas A&M University
Density Functional Theory (DFT
The minimum critical stress along the c
direction is calculated from the cleavage
energy, which corresponds to the
intrinsic hardness
0.0 0.2 0.4 0.6 0.8 1.0
600
800
1000
1200
1400
100um Barsoum et al (1996)
20-50um Bao et al (2004)
En
gin
ee
rin
g s
tre
ss
(M
Pa
)
Ti3(Al
1-xSi
x)C
2
FG
CG
7um
12.5um
25um
10-30um Wang&Zhou et al.
Ti3AlC
2
23
Ti2AlC – Solid Solution Hardening
In collaboration with Dr. Raymundo Arroyave Texas A&M University
A. Talapatra, T. Duong, W. Son, H. Gao, M. Radovic , R. Arroyave, A high throughput combinatorial study of the effect of M
site alloying on the solid solution behavior of M2AlC MAX phases, Acta Materialia, in review (2016)
1.8 x 106 possible solid solutions!
Only <100 synthesized and some of them
characterized.
Caster expansion for:
(Ti,M)AlC and (V,M)AlC
M=Ca, Sc, Cr, Mn, Fe, Co, Ni, Zn, Zr, Hf
(Ti; V )2AlC
Ti2AlC - EBC
Mn+1AlXn (such as Ti2AlC, Ti3AlC3, Cr2AlC) can be used as protective coatings for
different alloys.
Example:
Ti6242 - Ti2AlC2
Ti2AlC -Ti6242 couple after oxidation at
800 oC for 50 hours.
Ti2AlCTi6242
TiO2
In collaboration with Dr. Adam Pilchak, AFRL
and Dr. Ibrahim Karaman, TAMU
Ti6242 Ti2AlC2
TiAl
Ti3Al
24
Ti2AlC – Metal Composites
Composites with:
Mg, Al, Cu, Ag, W, Ni, Co, TiAl, etc.
Problem:
Reactivity of the
MAX phases with
other metals
Most of the MAX phase – Metal composites are
metastable and far from equilibrium!
To trick Thermodynamics one has to
deal with Kinetics!
In collaboration with and Dr. Ibrahim Karaman, TAMU and Dr. Gwenaelle Proust,
University of Sydney
25
Ti2AlC – Metal Composites
25
Hu, L., Kothalkar, A., O'Neil, M., Karaman, I., & Radovic, M. (2014). Current-activated, pressure-assisted infiltration: a novel, versatile route for producing interpenetrating
ceramic–metal composites. Materials Research Letters,2(3), 124-130.
Liangfa Hu, Morgan O’Neil, Veysel Erturun, Rogelio Benitez, Gwénaëlle Proust, Ibrahim Karaman, and Miladin Radovic, High-performance metal/carbide composites with
far-from-equilibrium compositions and controlled microstructures, (2016) Scientific Reports, in review
Ti2AlC – Metal Composites
25
Hu, L., Kothalkar, A., O'Neil, M., Karaman, I., & Radovic, M. (2014). Current-activated, pressure-assisted infiltration: a novel, versatile route for producing interpenetrating
ceramic–metal composites. Materials Research Letters,2(3), 124-130.
Liangfa Hu, Morgan O’Neil, Veysel Erturun, Rogelio Benitez, Gwénaëlle Proust, Ibrahim Karaman, and Miladin Radovic, High-performance metal/carbide composites with
far-from-equilibrium compositions and controlled microstructures, (2016) Scientific Reports, in review
[1] Wang, Gauthier-Brunet, Bei, Laplanche, Bonneville, Joulain, Dubois,
Mater. Sci. Eng. A 2011, 530, 168.
[2] Liu, Huang, Wang, Li, Trans. Nonferrous Met. Soc. China, 2013, 23,
2826.
[3] Kouzeli, Dunand, Acta Mater. 2003, 51, 6105.
28
Students:
Liangfa Hu
Rogelio Benitez
Ankush Kothalkar
Huili Gao
Junwei Xiao
Peipei Gao
Amy Bolon
Yexiao Chen
Mathew Westwick
Yexiao Chen
Postdoc:
Dr. Sandip Basu (2010-2011)
Collaborators:
Dr. Ibrahim Karaman (Texas A&M)
Dr. Dimitris Lagoudas (Texas A&M)
Dr. Raymundo Arroyave (Texas A&M)
Dr. Arun Shukla (Univ. of Rhode Island)
Dr. Edgar Lara-Curzio (Oak Ridge National Laboratory)
Dr. Nakhiah Goulbourne (Univ. of Michigan)
Dr. Michel Barsoum (Drexel University)
Dr. Gwenaelle Proust (Univ. of Sydney)
Funding agencies:
- National Science Foundation (DMR, CMMI)
- Air Force Office of Scientific Research
- Airforce Research Laboratory
- Department of Energy - Oak Ridge National Laboratory
- University of Sydney, International Program Development Fund
Acknowledgments
29
Questions