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THE DEVELOPMENT AND IMPLEMENTATION OF HIGH- THROUGHPUT TOOLS FOR DISCOVERY AND CHARACTERIZATION OF PROTON EXCHANGE MEMBRANES A Dissertation Presented to The Academic Faculty by Keith Gregory Reed In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the School of Chemical and Biomolecular Engineering Georgia Institute of Technology December 2009 Copyright © 2009 by Keith Gregory Reed THE DEVELOPMENT AND IMPLEMENTATION OF HIGH- THROUGHPUT TOOLS FOR DISCOVERY AND CHARACTERIZATION OF PROTON EXCHANGE MEMBRANES Approved by: Dr. J. Carson Meredith, Advisor Dr. David Bucknall School of Chemical and Biomolecular School of School of Polymer, Textile & Engineering Fiber Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. Tom Fuller Dr. Anselm Griffin School of Chemical and Biomolecular School of Polymer, Textile & Fiber Engineering Engineering Georgia Institute of Technology Georgia Institute of Technology Dr. William Koros School of Chemical and Biomolecular Engineering Georgia Institute of Technology Date Approved: October 9, 2009 I dedicate this work to my mother, whose wisdom and love have kept me pushing forward, and to my father, who I know is smiling down on me from heaven. Acknowledgements First and foremost, I must thank God for blessing me with the opportunity to have this experience. Through His love and favor, I have discovered the strength, the wisdom, and the confidence to make it this far. To my mom, for the morals and values that you have instilled upon me from a young age, I am truly grateful. To my little brother and sister, Kevin and Krisitn, I hope that my life’s journey thus far has encouraged you both to discover your passions in life, and that you remain focused in pursuing your dreams. To my Nana, you have always supported and encouraged my academic pursuits; and to Grandma, you have imparted so much wisdom upon me. I love you both so much and I am truly blessed to have you both in my life. I am especially grateful to my advisor, Dr. Carson Meredith, who gave me the opportunity to pursue my research interests and discover new ones. You have challenged my way of thinking while encouraging my progress. You pushed me to be creative yet critical in my work, and allowed me to really take ownership of this project. Your continuous support and guidance throughout my tenure at Georgia Tech has been invaluable. I am also extremely grateful to my research committee, who has shown genuine interest in my work and has given me valuable feedback throughout the years to improve my research. Your questions, your concerns, and your words of encouragement have motivated my development into a well-rounded, critical thinker. I’d like express my sincerest gratitude to Dr. Sue Ann Bidstrup-Allen, who gave me the opportunity to be more than just a graduate student, but a leader and role-model for other students. The opportunities that you have provided for me have made my Georgia Tech experience so unique. I’d also like to thank Dr. Lakeisha Taite, Dr. Keith Oden, and Dr. Comas Haynes, for showing interest in my academic progress and iv professional development. I look forward to passing along the knowledge and insight that you have bestowed upon me. I am truly grateful to the administrative staff in the ChBE Department , especially Ms. Brenda Maddox, Ms. Janice Whatley, Ms. Juanita Freeman, Ms. Phyllis Jones, Ms. Claudia Clarkson, Ms. Rochelle Moses and Ms. Josie Giles – with all of your assistance and encouragement, there was no issue that could not be easily resolved – thank you for taking care of me. I’d like to thank Dr. John Walsh, Dr. Chris Wieble, Dr. Valarie Thomas, and other faculty associated with the Ivan Allen School of Public Policy that I have had the pleasure of interacting with. You all have given me a great deal perspective on my work and allowed me to really grasp “the bigger picture” of my research. To those esteemed ChBE graduate alumni who have come before me: Dr. Akua Asa-Awuku, Dr. Joe Lahai-Sormana, Dr. Charlene Rincon, Dr. Pedro Zapata, Dr. Jing Su – for sharing your knowledge and experience with me, I am ever so grateful. Whether it was lab training, academic or non-academic guidance, or just a few laughs, you all have added much wisdom and enjoyment to my Georgia Tech experience. I can only hope that I have impacted others as you all have impacted me. I want to thank my incoming class of 2004 who has taken the journey with me, especially JR Johnson and Shara McClendon – you have both been great colleagues and amazing friends. To my Exxon Mobil mentees, both past and present: Tracie, Mallerie, Arlyne, Mayisha, Katrina, Namory, Charmaine, and Channel – encouraging your professional and academic development has also helped me to develop as person and I wish you all much success in your future endeavors. I’d like to acknowledge those students who aided me in my research efforts, especially Ryan Hart, Tori Blasucci, Hillary Huttenhower, Pamela Pollet, Ven Rajarathinam, and Cheng Chen, as well as the members of the Koros research group for generously allowing me to use their commercial resins. To Jung-Hyun Lee, for your amazing TGA and SEM work, for putting v in the extra late hours, and for offering your insight to my research, I am very grateful. Also to Ismael Gomez, I’m glad that I you decided to come to Tech and work with our group – the past two years have been a lot of fun. I know that you will accomplish great things both in and out of the lab, and I wish you much success as you continue through Tech. I also have to thank the Black Graduate Student Association and the crazy fast members of the Georgia Tech Runnin’ Wreck Running Club – you have encouraged me strive for the best in all facets of life and helped me to maintain the work-life balance that I so desperately needed throughout my time at Georgia Tech. Last but not least, I have to acknowledge the organizations that funded my research: the Department of Energy, Arkema, Inc., Honda, and Applied Materials. Also, I must thank the FACES organization, who not only provided financial support but also provided me with a wealth of insight into the world of academia. And to the rest of my family, friends, and colleagues, I am very grateful to have established fulfilling relationships with you all. vi Table of Contents Acknowledgements .......................................................................................................... iv List of Tables ................................................................................................................... xiii List of Figures .................................................................................................................. xiv Summary… ................................................................................................................... xviii Chapter 1: Introduction .................................................................................................. 1 1.1. Energy Sustainability .......................................................................................... 2 1.1.1. Energy Consumption ................................................................................... 2 1.1.2. Fossil Fuels ................................................................................................. 8 1.1.2.1. Foreign Dependence ............................................................................ 8 1.1.2.2. Natural Abundance ............................................................................. 10 1.1.2.3. Emissions ........................................................................................... 13 1.1.2.4. Extraction and Transportation ............................................................ 14 1.1.3. Alternative Energy Resources ................................................................... 15 1.1.3.1. Energy Storage, Transmission, and Conversion ................................ 17 1.2. Fuel Cells .......................................................................................................... 19 1.2.1. Phosphoric Acid Fuel Cells (PAFCs) ......................................................... 22 1.2.2. Alkaline Fuel Cells (AFCs) ......................................................................... 22 1.2.3. Molten Carbonate Fuel Cells (MCFC) ....................................................... 23 1.2.4. Solid Oxide Fuel Cells (SOFCs) ................................................................ 24 1.2.5. Proton Exchange Membrane Fuel Cells (PEMFCs) .................................. 24 1.3. Combinatorial Methods for Polymer Discovery ................................................. 26 1.3.1. Library Synthesis and Processing ............................................................. 27 1.3.2. High-Throughput Characterization ............................................................ 30 vii 1.3.2.1. Proton Conductivity and Mechanical Strength .................................... 30 1.3.2.2. Water Management ............................................................................ 31 1.4. Outline .............................................................................................................. 32 1.5. References ....................................................................................................... 34 Chapter 2: High-Throughput Mass Transport Characterization of Polymer Membranes .............................................................................. 38 2.1. Introduction ......................................................................................................