engineering the max phases and their composites for ...engineering the max phases and their...

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

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1000

2000

3000

4000

5000

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40

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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



conductors

Damage Tolerant









Refractory




resistanceHu, C., et al. Scripta

Materialia 64.8 (2011): 765-768.

Gilbert C.J., et al. Scr.

Mater. 238 (200) 761–67



MAX Phases



conductors

Damage Tolerant









Refractory




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



MAX Phases



conductors

Damage Tolerant









Refractory




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)



MAX Phases



conductors

Damage Tolerant









Refractory




resistance



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



conductors

Damage Tolerant









Refractory




resistance

Barsoum, M.W. and Radovic, M., Annual Review s in Materials Research, Vol.41, 2011


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.


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


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



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.


16


Kinking



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


Kinking



• 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


Kinking



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


Invconel 718

Benitez, R., Kan, W. H., Gao, H., O'Neal, M., Proust, G., & Radovic, M. (2016). In preparation

20


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


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


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


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

engineering the max phases and their composites for ...engineering the max phases and their...

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