12 August 2013 1

Tailoring of Atomic-Scale Interphase Complexions

for Mechanism-Informed Material Design

Martin P. Harmer

Office of Naval Research Multidisciplinary University Research Initiative Project

ONR Topic Chief: David Shifler

ONR Grant N00014-11-1-0678 Start: June 1, 2011 End: May 31, 2016 Budget: $1.5M per year

MURI Team Members

2 12 August 2013

Martin P. Harmer Helen M. Chan Jeffrey M. Rickman

Gregory S. Rohrer Anthony D. Rollett Michael Widom

Jian Luo Shen J. Dillon Andrea J. Harmer

13 Graduate Students 3 Postdoctoral Research Associates 5 Females 9 U.S. citizens

Collaborators: Eduardo Saiz Gutierrez (Imperial College), Rick Vinci (Lehigh), Ed Webb (Lehigh)

Meetings & Conferences

3 12 August 2013

Conferences • MS&T, Columbus, OH, October 18, 2011 • TMS, Orlando, FL, March 11-15, 2012 • Gordon Conference, New Hampshire, August 2012 • Bear Creek International Workshop on Interfaces,

Macungie, PA, October 2-6, 2012 • MS&T, Pittsburgh, PA, October 2012 • TMS, San Antonio, TX, March 2013

Meetings • Pre-Kick Off Meeting Web Conference, June 10, 2011 • Kickoff Meeting, Lehigh University, June 23, 2011 • Web Conference, October 31, 2011 • Pre-Review Planning Meeting, CMU, November 28, 2011 • 1st Review Meeting, Washington, DC, December 15, 2011 • Sub-Group Meeting, February 12, 2012 • Pre-Review Planning Meeting, Lehigh University, May 17, 2012 • ONR Program Review, High Temperature and Cellular Materials, Charleston, SC, May 31, 2012 • 2nd Review Meeting, Lehigh University, June 8, 2012 • Pre-Review Planning Meeting, CMU and Online, December 3, 2012 • 3rd Review Meeting, Washington, DC, December 18, 2012 • Pre-Review Planning Meeting, Lehigh University, April 9, 2013 • ONR Program Review, High Temperature and

Cellular Materials, Bozeman, MT, May 30, 2013 • 4th Review Meeting, San Diego, CA, June 7, 2013

(cancelled)

Journal Articles (23) Submitted, under review, or in preparation (5) • J.M. Rickman, H.M. Chan, M.P. Harmer, and J Luo. "Grain-boundary layering transitions in a model bicrystal," submitted June 2013. • Patrick R. Cantwell, Ming Tang, Shen J. Dillon Jian Luo, Gregory S. Rohrer and Martin P. Harmer, “Grain Boundary Complexions Overview,” submitted to Acta

Materialia, May 2013. • K. Tai, B. Huang, and S. J. Dillon, "Vapor-solid-metal: A new approach to oxide nanowire growth," submitted. • Q. Gao and M. Widom, arXiv:1304.3353v1 (2013). • C.-Y. Lin, M. Widom, R. F. Sekerka, arXiv:1302.2413 (2013).

2013 (16) • H. Beladi and G.S. Rohrer, Metallurgical and Materials Transactions A, 44A (2013) 115-124. • H. Beladi and G.S. Rohrer, Acta Materialia, 61 (2013) 1404-1412. • W. Cao, A. Kundu, Z. Yu, M.P. Harmer and R.P. Vinci, Scripta Materialia, 69 (2013) 81-84. • A.D. Darbal, K.J. Ganesh, X. Liu, S.-B. Lee, J. Ledonne, T. Sun, B. Yao, A.P. Warren, G.S.Rohrer, A.D. Rollett, P.J. Ferreira, K.R. Coffey, and K. Barmak, Microscopy and

Microanalysis, 19, 1 (2013) 111-119. • S. Curiotto, H. Chien, H. Meltzman, S. Labat, P. Wynblatt, G.S. Rohrer, W.D. Kaplan, D. Chatain, Journal of Materials Science, 48 (2013) 3012-3026. • R. M. Feenstra, N. Srivastave, Q. Gao, M. Widom, G. Diaconescu, T. Ohta, G. L. Kellogg, J. T. Robinson and I. V. Vlassiouk, Physical Review B, 87 (2013) 041406(R). • S. Ma, P.R. Cantwell, T.J. Pennycook, N. Zhou, M. P. Oxley, D.N. Leonard, S.J. Pennycook, J.Luo, M.P. Harmer, Acta Materialia, 61, 5 (2013) 1691-1704. • K. Tai, L. Feng, and S.J. Dillon, Journal of Applied Physics, 113 (2013) 193507. • K. Tai, and S.J. Dillon, Acta Materialia, 61 (2013) 1851-1861. • K. Tai, A. Lawrence, M.P. Harmer and S.J. Dillon, Applied Physics Letters, 102 (2013) 034101. • X. Yuan, X. Song, H. Chien, J. Li, G.S. Rohrer, Materials Letters, 92 (2013) 86–89. • Zhiyang Yu, Qian Wu, Jeffrey M. Rickman, Helen M. Chan, Martin P. Harmer, Scripta Materialia, 68, 9 (2013) 703–706. • A. Kundu, K. M. Asl, J. Luo, and M.P. Harmer, Scripta Materialia, 68, 2 (2013) 146-149. • S. Curiotto, H. Chien, H. Meltzman, S. Labat, P.Wynblatt, G.S. Rohrer, W.D. Kaplan, D. Chatain, Journal of Materials Science, 48 (2013) 3013-3026. • S.A. Bojarski, J. Knighting, S. Ma, W. Lenthe, M.P. Harmer, G.S. Rohrer, Materials Science Forum, 753 (2013) 87-92. • N. Srivastava, Q. Gao, M. Widom, R. M. Feenstra, S. Nie, K. F. McCarty and I. V. Vlassiouk, Physical Review B, 87 (2013) 245414.

2012 (1) • J. Luo, Journal of American Ceramic Society, 95, 8 (2012) 2358–2371.

2011 (1) • J. Luo, H. Cheng, K. Meshinchi Asl, C..J. Kiely, and M. P. Harmer, Science, 333 (2011) 1730-1733.

Journal Articles & Website

4 12 August 2013

Scientific Purpose & Background

5 12 August 2013

Grain Boundaries Fabrication and Processing Cold-working, annealing, recrystallization… Related Phenomena and Properties Ductility, creep, oxidation… …but how much do we really know?

How do we explain discontinuities in grain boundary-related properties? • Abnormal grain growth? • Embrittlement? • Nanocrystalline thermal (in)stability?

Scientific Background: Phase-like Behavior of GBs

6 12 August 2013

Complexion

The interfacial analogue to a bulk phase

Aberration-Corrected Scanning Transmission Electron Microscopy

Scientific Background: Phase-like Behavior of GBs

7 12 August 2013

Grain Boundary Mobility in Doped Al2O3

SJ Dillon, M Tang, WC Carter, MP Harmer, Acta Mater. 55 (2007) 6208

monolayer

trilayer

Goals of the Program & General Approach

8 12 August 2013

Grain Boundary Complexion Diagrams Analogous to Bulk Phase Diagrams • 5 additional thermodynamic degrees of freedom Multi-disciplinary approach • Experiments: grain growth, diffusion, conductivity

thermal properties… • Simulation: Density functional theory (DFT), molecular

dynamics (MD)… • Theory: Thermodynamic computational methods

New & Improved Materials

Metal-Complexionized Ceramics • Metallic complexions at ceramic grain boundaries

Thermally Stable Nanocrystalline Metals • Understanding mechanism of thermal stability

Metal-Complexionized Ceramics

12 August 2013 9

Plotting Complexion Diagrams

Electron Microscopy

GB Diffusivity

GB Mobility

Mechanical Properties

DFT Simulations Thermodynamic Models

Accomplishments: Liquid Metal Embrittlement

10 12 August 2013

Science Paper Ni-Bi Embrittlement

Ni-Bi Complexion Diagram

Cu-Bi Complexion Diagram

Accomplishments: Al2O3-HfO2

11 12 August 2013

Currently Under Investigation: Hf-doped Polycrystalline Al2O3

3D Model + HAADF-STEM Simulations

This is a general grain boundary!

DFT Simulations

12 August 2013 12

Acta Mat Overview: Grain Boundary Complexions

Acta Materialia Overview Submitted May 3, 2013 “Grain Boundary Complexions” Patrick R. Cantwell, Ming Tang, Shen J. Dillon, Jian Luo, Gregory S. Rohrer, Martin P. Harmer

G.D. Hibbard et al., Scripta Mat. 47 (2002) 83-87

Potential Breakthroughs

13 12 August 2013

1450 °C

1150 °C

Oxidation rate reduced 4x @ 1450 °C Oxidation rate reduced 40x @ 1100 °C

Understanding Oxidation in Al2O3-HfO2

Metal-Complexionized Ceramics

Understanding the Mechanism of Nanocrystalline Thermal Stability

Scientific Barriers & Grand Challenge

14 12 August 2013

Internal Interfaces are Difficult to Study! Surface Science & Surface “Phase” Transitions • A relatively mature field…

The Phase-Like Behavior of Grain Boundaries • Discussed since at least 1968 (EW Hart) • Experimental study difficult, even with aberration-corrected STEM

Grand Challenge:

Grain Boundary Complexion Diagrams • Analogous to bulk phase diagrams • Bulk phase diagrams have been developed intensively over decades • Grain boundaries have 5 more thermodynamic degrees of freedom!

Sub-Challenge: Studying Complexions at Equilibrium • Does rapid quenching reveal the high-T complexions? • Need in-situ TEM hot stage experiments • Need other experimental techniques, too

1200°C @ 106 °C/sec

In-Situ TEM Hot Stage

Al2O3-Y2O3 Complexion Diagram

12 August 2013 15

Backup slides…

12 August 2013 16

Future Work

1) In-situ Hot Stage STEM • Nanocrystalline thermal stability (and instability initiation at GBs) • Direct observation of complexion transitions

2) TTT Diagrams

• How do complexions nucleate and grow? • “Sandwich” experiments

3) Complexion Diagrams • HfO2-doped Al2O3

• Oxidation kinetics

4) Nanocrystalline thermal stability: Ni-W, Cu-Zr, W-Ti • Sputtered and electroplated • We observe multiple bulk phases in electroplated samples…

5) Metal-Compexionized Ceramics (MCCs) • At grain boundaries in Al2O3 • Dopants under exploration: Cu, Ni, Cu-Ti, Ni-Al, Cu-Nb

6) Electrically-conductive Al2O3 by Complexion Engineering • ITO-doped Al2O3

12 August 2013 17

Nanocrystalline Thermal Stability

v =Mgk

GB velocity

GB mobility GB energy

GB curvature

Driving force for grain growth

Which explains thermal stability and instability? Thermodynamics: Kinetics: M

gB. K. VanLeeuwen, K. A. Darling, C. C. Koch, R. O. Scattergood, B. G. Butler, Thermal stability of nanocrystalline Pd81Zr19. Acta Mater. 58, 4292 (2010).

12 August 2013 18

STEM-HAADF

500 nm

Ni-W Specimen Info Electroplated Ni-W Nominally 20 wt. % W Annealed 700C 4 hours Ar-H2

Initial STEM-HAADF and EDS indicates 5 phases: Ni-W (Ni-rich) normal grains

of ~30 nm dia. Abnormal grains of…

Ni-W (W-rich) WOx

FeOx

Nanoparticles of WC (~10 nm dia.) in periodic rows

Nanocrystalline Thermal Stability

12 August 2013 19

Isothermal TTT diagram for complexion transitions in Y-doped Al2O3

T > Tc

T < Tc

ln(time)

1/Tc

1/T

emp

high low

1450 °C

1500 °C

1600 °C

8 h

1350 °C

Complexion 1

EA1 EA2

DG1 DG2

C-plane-GB

A-plane-GB

C-plane

A-plane