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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
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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
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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
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Scientific Purpose & Background
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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
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Complexion
The interfacial analogue to a bulk phase
Aberration-Corrected Scanning Transmission Electron Microscopy
Scientific Background: Phase-like Behavior of GBs
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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
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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
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Plotting Complexion Diagrams
Electron Microscopy
GB Diffusivity
GB Mobility
Mechanical Properties
DFT Simulations Thermodynamic Models
Accomplishments: Liquid Metal Embrittlement
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Science Paper Ni-Bi Embrittlement
Ni-Bi Complexion Diagram
Cu-Bi Complexion Diagram
Accomplishments: Al2O3-HfO2
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Currently Under Investigation: Hf-doped Polycrystalline Al2O3
3D Model + HAADF-STEM Simulations
This is a general grain boundary!
DFT Simulations
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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
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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
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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
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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
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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).
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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