Energy Landscapes and Thermodynamic Control of Synthesis Pathways in Complex Ceramics
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Energy Landscapes and Thermodynamic Control of Synthesis Pathways in Complex Ceramics
Wed, 27/03/2019 - 13:30 to 14:30
Location:
Speaker:
Alexandra Navrotsky
Affiliation:
University of California
Synopsis:
Many complex ceramic materials can be synthesized in a variety of structural states, with polymorphism, grain size and order-disorder on several length scales among the parameters desirable to be controlled. Such control can be achieved by choosing appropriate initial synthesis conditions and progressing downhill in free energy by appropriate thermal treatment. Understanding the relations among structure, processing and thermodynamic driving forces versus kinetic barriers is critical to choosing a path to desired products. This talk shows how calorimetric study of the closely spaced energetics of various intermediate states provides insight and control into the products formed. Three very different examples illustrate common underlying thermodynamic principles of control. The first is polymorphism and synthesis of new structures in mechanochemical synthesis of metal organic frameworks. The second is control of order-disorder linking pyrochlore, weberite, defect fluorite and amorphous structures, with radiation damage, grinding, and low and high temperature processing as variables. The third is particle size control at the nanoscale in producing thermodynamic crossovers of polymorph stability in simple oxides. In each case, new materials with distinct and interesting properties can be produced by stopping the reactions at intermediate states.
Biography:
Alexandra Navrotsky's research interests lie at the intersection of solid state chemistry, geochemistry, and materials science. The fundamental question that gives unity to a diverse set of studies (over two hundred papers) on materials ranging from oxide superconductors to silicates deep in the Earth's mantle is "why does a given structure form for a specific composition, pressure and temperature?" The "why" involves relating thermodynamic properties, structural parameters, and chemical bonding in a systematic fashion. At Arizona State University in the 1970's and 80's, at Princeton from 1985 to 1997, and at UC Davis since 1997, Navrotsky has built a unique high temperature calorimetry facility, designed and improved on the instrumentation, and developed and applied methods for measuring the energetics of crystalline oxides, of glasses, amorphous, and nanophase and porous materials, of hydrous phases and carbonates, and, more recently, of nitrides and oxynitrides. The thermochemical data obtained are essential to understanding materials compatibility and reactivity in both technological and geological application, but, more fundamentally, the energetics offer insight into chemical bonding, order-disorder reactions, and phase transitions.
Education, Awards and Professional Highlights
• W. David Kingery Award, American Ceramic Society (2016)
• V.M. Goldschmidt Award, Geochemical Society (2016)
• Alfred R. Cooper Distinguished Lecture, The American Ceramic Society, Materials Science & Technology Conference (2013)
• William Mong Distinguished Lecture, University of Hong Kong (2013)
• Cecil and Ida Green Senior Fellowship at the Geophysical Laboratory of the Carnegie Institute of Washington (2012)
• Featured Manuscript in the Journal of the American Ceramics Society - Thermochemistry of Lanthana- and Yttria-Doped Thoria (2011)
• American Philosophical Society (2011)
• International Union of Pure and Applied Chemistry, Fellow (2009)
• Best University Paper Award, DOE Geoscience Grantee Meeting (2009)
• Roebling Medal of Mineralogical Society of America (2009)
• Outstanding Engineering Senior Career Research Award – University of California, Davis (2007)
• Sloan Faculty Distinguished Service Award - University of California, Davis (2007)
• Harry H. Hess Medal, American Geophysical Union (2006)
• Rossini Award, International Association of Chemical Thermodynamics (2006)
• Spriggs Phase Equilibria Award, American Ceramic Society (2005)
• Urey Medal, European Association of Geochemistry (2005)
• Fellow, The Minerological Society, Great Britain (2004)
• Highly Cited Researchers Award, ISI Thomson Scientific (2002)
• Benjamin Franklin Medal in Earth Science (2002)
• Best Paper Award of the Nuclear and Environmental Technology Division, American Ceramic Society (2001)
• American Ceramic Society Fellow (2001)
• Ceramic Educational Council Outstanding Educator Award (2000)
• Hugh Huffman Memorial Award, The Calorimetry Conference (2000)
• Alexander M. Cruickshank Award, Gordon Research Conference (2000)
• Geochemical Society Fellow (1997)
• Ross Coffin Purdy Award, American Ceramic Society Fellow (1995)
• Doctor Honoris Causa, University of Uppsala, Sweden (1995)
• President, Mineralogical Society of America (1992-1993)
• Member, National Academy of Sciences (1993)
• American Geophysical Union Fellow (1988)
• Mineralogical Society of America Award and Fellow (1981)
• Alfred P. Sloan Fellow (1973)
• Ph.D. University of Chicago (1967)
Representative Publications
• "Calorimetric Study of Alkali Metal Ion (K+, Na+, Li+) Exchange in a Clay-like MXene" G. Sharma, E. Muthuswamy, M. Naguib, Y. Gogotsi, A. Navrotsky, and D. Wu, J. Phys. Chem. C, 121 15145-15153 (2017)
• "Calorimetric Measurements of Surface Energy of Amorphous HfO2 nanoparticles Produced by Gas Phase Condensation" G. Sharma, S. V. Ushakov, H. Li, R. H. R. Castro, and A. Navrotsky, J. Phys. Chem. C, 121 10392-10397 (2017).
• "Experimental and Theoretical Evaluation of the Stability of True MOF Polymorphs Explains Their Mechano-chemical Interconversions" Z. Akimbekov, A. Katsenis, G. Nagabushana, G. Ayoub, M. Arhangelskis, A. Morris, T. Friscic, A. Navrotsky; J. Am. Chem. Soc. 139 7952-7957 (2017)
• "Hot Matters – Experimental Methods for High-Temperature Property Measurement" A. Navrotsky and S. V. Ushakov, Am. Ceram. Soc. Bull., 96, 22-28 (2017).
• "Thermodynamics of Manganese Oxides: Sodium, Potassium, and Calcium Birnessite and Cryptomelane" N. Birkner and A. Navrotsky, Proc. Natl. Acad. Sci. USA, 114, E1046-E1053 (2017).
• "A Combined Experimental and Theoretical Study of Enthalpy of Phase Transition and Fusion of Yttria above 2000 °C using “Drop-n-Catch” Calorimetry and First-Principles Calculations" D. Kapush, S. V. Ushakov, A. Navrotsky, Q. Hong, H. Liu and A. v. d. W., Acta Mater., 124, 204-209 (2017).
• "Thermodynamic Properties of Polymorphs of Fluorosulfate Based Cathode Materials with Exchangeable Potassium Ions" R. Shivaramaiah, L. Lander, G.P. Nagabhushana, G. Rousse, J.-M. Tarascon, and A. Navrotsky, ChemPhysChem, 17, 3365-3368 (2016).
• "Energetics of Uranothorite (Th1-xUxSiO4) Solid Solution" X. Guo, S. Szenknect, A. Mesbah, N. Clavier, C. Poinssot, D. Wu, H. Xu, N. Dacheux, R. Ewing and A. Navrotsky, Chem. Mater., 28, 7117-7124 (2016).
• "Crystal Structures, Surface Stability and Water Adsorption Energies of La-Bastnasite via Density Functional Theory and Experimental Studies" S. Goverapet Srinivasan, R. Shivaramaiah, P. Kent, A. Stack, A. Navrotsky, R. Riman, A. Anderko, V. Bryantsev, J. Phys. Chem. C, 120, 16767-16781 (2016).
• "Thermodynamic Stability of low-k Amorphous SiOCH Dielectric Films" J. Chen, S. W. King, E. Muthuswamy, A. Koryttseva, D. Wu, and A. Navrotsky, J. Am. Ceram. Soc., 99, 2752-2759 (2016