Purdue University Purdue e-Pubs Open Access Dissertations Theses and Dissertations Spring 2015 Sintering techniques for microstructure control in ceramics Andrew T. Rosenberger Purdue University Follow this and additional works at: https://docs.lib.purdue.edu/open_access_dissertations Part of the Materials Science and Engineering Commons Recommended Citation Rosenberger, Andrew T., "Sintering techniques for microstructure control in ceramics" (2015). Open Access Dissertations. 552. https://docs.lib.purdue.edu/open_access_dissertations/552 This document has been made available through Purdue e-Pubs, a service of the Purdue University Libraries. Please contact [email protected] for additional information. 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Rosenberger In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy May 2015 Purdue University West Lafayette, Indiana ii ACKNOWLEDGEMENTS I would like to thank my advisor Lia Stanciu for providing guidance and support during my time at Purdue. I am likewise grateful to a numerous faculty here in the Materials Engineering department, including Prof. Rod Trice, Prof. Kevin Trumble, Prof. David Johnson, and Prof. Elliott Slamovich for their invaluable input, advice, and other assistance. Finally, special thanks to the department technicians David Meyer, Patti Metcalf, Jameson Root, and Timothy VanMeter for training me on much of the equipment necessary for this research, as well as assisting me countless times in maintaining it. My time at Purdue was greatly enriched by my fellow graduate and undergraduate students in the MSE department. I would like to especially thank those who spent time to help ease my transition from physics to engineering, taught me many new practical skills, and were always available to brainstorm ideas or discuss my research. Special thanks also to those undergraduates who worked as research assistants with me, as well as those who were a part of the classes I TA’d. You were all responsible for making my first teaching experiences uniformly excellent. Finally, I would like to thank all of you for companionship and friendship over these past few years. Thanks to all of you Purdue MSE is both a wonderful working and social environment. iii I owe my current position to my parents, who took the time and effort to ensure I received a quality education in my younger years and pushed me to expand my academic career. My mom taught me from fifth grade through high school and gave me the skills and opportunity to start college when I did. Dad provided advice on the engineering and science disciplines, and also gave me invaluable guidance and assistance on my research as a graduate student. Thank you both. iv TABLE OF CONTENTS Page LIST OF TABLES ............................................................................................................ vii LIST OF FIGURES ......................................................................................................... viii LIST OF ABBREVIATIONS .......................................................................................... xiv ABSTRACT .................................................................................................................... xvii CHAPTER 1. INTRODUCTION .................................................................................... 1 1.1 Sintering ...................................................................................................................... 1 1.1.1 Sintering Aids .................................................................................................. 2 1.1.2 Reaction Sintering ........................................................................................... 5 1.1.3 Hot Pressing ..................................................................................................... 6 1.1.4 Field-Assisted Sintering................................................................................... 9 1.1.4.1 Spark Plasma Sintering ............................................................................... 9 1.1.4.2 Flash Sintering .......................................................................................... 12 1.1.4.3 Conclusion on Field-Assisted Sintering ................................................... 14 1.2 Materials Studied ....................................................................................................... 15 1.2.1 Zirconium Diboride Ultra High Temperature Ceramics ............................... 15 1.2.1.1 Silicon Carbide and Zirconium Carbide Secondary Phases ..................... 17 1.2.1.2 Sintering Techniques Applied to Zirconium Diboride Composites ......... 25 1.2.2 Solid State Lithium Ion Batteries .................................................................. 32 CHAPTER 2. ZRB2 – SIC AND ZRB2 – ZRC CERAMICS WITH HIGH SECONDARY PHASE CONTENT ................................................................................. 36 2.1 Experimental Design ................................................................................................. 36 2.2 Results ....................................................................................................................... 40 2.2.1 ZrB2 – SiC Composites .................................................................................. 40 v Page 2.2.2 ZrB2–ZrC Composites ................................................................................... 43 2.3 Discussion ................................................................................................................. 47 2.3.1 Properties of ZrB2 – SiC Samples ................................................................. 47 2.3.2 Properties of ZrB2 – ZrC Samples ................................................................. 48 2.3.3 Comparison of SiC and ZrC Systems ............................................................ 50 2.4 Conclusion ................................................................................................................. 51 CHAPTER 3. REACTIVE HOT PRESSING AND PROPERTIES OF ZR1−xTIxB2– ZRC COMPOSITES ......................................................................................................... 53 3.1 Experimental Procedure ............................................................................................ 53 3.2 Experimental Results ................................................................................................. 55 3.3 Discussion and Analysis ............................................................................................ 62 3.3.1 ZrB2 – TiC Reaction Mechanisms ................................................................. 62 3.3.2 Thermal Conductivity .................................................................................... 65 3.3.3 Mechanical Properties ................................................................................... 66 3.4 Conclusion ................................................................................................................. 68 CHAPTER 4. OXIDATION OF ZRB2 – SIC – ZRC COMPOSITES AS A FUNCTION OF ZRC CONTENT AND THE ZRC:SIC RATIO .................................... 70 4.1 Stagnant Air Oxidation Experimental ....................................................................... 70 4.2 Stagnant Air Oxidation Results and Discussion ........................................................ 72 4.3 Ablation Study Experimental .................................................................................... 90 4.4 Ablation Results and Discussion ............................................................................... 91 4.5 Conclusion ................................................................................................................. 99 CHAPTER 5. FIELD-ASSISTED SINTEIRNG OF SOLID STATE LITHIUM ION BATTERY MATERIALS ...................................................................................... 100 5.1 Flash Sintering Furnace Design .............................................................................. 100 5.2 LATP Solid Electrolyte Experiments ...................................................................... 103 5.3 LATP Results and Discussion ................................................................................. 104 5.4 LATP Conclusion .................................................................................................... 112 5.5 Cathode Electrolyte Interface Experiments ............................................................. 113 vi Page 5.6 Cathode Electrolyte Interface Results and Discussion ............................................ 115 CHAPTER 6. CONCLUSIONS AND FUTURE WORK ..........................................