CONSTRUCTION AND CHARACTERIZATION OF HYBRID NANOPARTICLES VIA BLOCK COPOLYMER BLENDS AND KINETIC CONTROL OF SOLUTION ASSEMBLY by Yingchao Chen A dissertation submitted to the Faculty of the University of Delaware in partial fulfillment of the requirements for the degree of Doctor of Philosophy in Material Science and Engineering 2015 Spring © 2015 Yingchao Chen All Rights Reserved ProQuest Number: 3730204 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. ProQuest 3730204 Published by ProQuest LLC (2015). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, MI 48106 - 1346 CONSTRUCTION AND CHARACTERIZATION OF HYBRID NANOPARTICLES VIA BLOCK COPOLYMER BLENDS AND KINETIC CONTROL OF SOLUTION ASSEMBLY by Yingchao Chen Approved: __________________________________________________________ Darrin J. Pochan, Ph.D. Chair of the Department of Material Science and Engineering Approved: __________________________________________________________ Babatunde A. Ogunnaike, Ph.D. Dean of the College of Engineering Approved: __________________________________________________________ James G. Richards, Ph.D. Vice Provost for Graduate and Professional Education I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Darrin J. Pochan, Ph.D. Professor in charge of dissertation I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ David C. Martin, Ph.D. Member of dissertation committee I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Thomas H. Epps, III, Ph.D. Member of dissertation committee I certify that I have read this dissertation and that in my opinion it meets the academic and professional standard required by the University as a dissertation for the degree of Doctor of Philosophy. Signed: __________________________________________________________ Chaoying Ni, Ph.D. Member of dissertation committee ACKNOWLEDGMENTS I would like to begin my thanks for my advisor, Prof. Darrin Pochan, for inspiring me to think creatively, challenging me to do my best work and supporting me to finish my Ph.D. work. Prof. Pochan is always encouraging me and patient to me on my work in the past five years. I feel lucky and fun to work with Dr. Pochan that I had the precious education that will benefits my future life. I would also like to thank my committee members, Prof. David Martin, Prof. Chaoying Ni and Prof. Thomas Epps, for their support and instruction over the past few years. Their advices provided great insights into my work and their questions helped me to think over my work and shape me to be an independent researcher and good presenter. I would also thank for the help I got from all faculties in UD. I would give my great thanks to my collaborators who are experts on chemistry and synthesis. Without the help from outstanding chemists, I cannot finish my thesis. Thanks for the support from Prof. Karen Wooley and Wooley group members in Texas A&M University. Thanks for their help when I stayed in TAMU for the three weeks synthesis work. Thanks for Fuwu Zhang, Xun He, Jiong Zou, Adriana Pavia, Ang Li, Shiyi Zhang, Guorong Sun, Gye Seong and the past graduate students Prof. Ke Zhang and Kai Qi. I have learned a lot from the excellent chemists and I had great collaboration and enjoyed working with them. Most of the polymers I used in my work are from Karen Wooley lab. I would pass the good collaboration tradition to the junior students from the two research groups. I would give my thanks to Xiaojun Wang, Christopher Hurley, Andrew Goodwin, Kang, Namgoo and Prof. Jimmy Mays iv from University of Tennessee. Their hard work provides the unsaturated block copolymer for the blend system, without which I cannot generate the research. I felt I owe a full gratitude to all the Pochan group members, who has been accompany with me for the past few years study. I would like to give all my thanks to Congqi Yan, Jiahua Zhu, Sameer Sathaye, Sheng Zhong, Jessie Sun and Nikhil Sharma for their patience and answering all my questions when I started my research. I would specifically thank Sheng Zhong and Jiahua Zhu for their precious suggestions in my project. Time is one-dimensional kinetics and their advices helped me to understand it in a better way. I would like to thank the past group members Christopher Koehler for the paper revision. I would like to thank for the past group members Brendon Stewart, Honggang Cui and Zheng Zeng. I would like to thank for the current group members Jessie Sun for her help of connecting collaborations; thank for Michael Haider, Fränk Polzer for the good coordination of the lab use and national lab trip etc. I would appreciate all the encouragements, inspirations and cares from them, making my past few years study enjoyable and pleasant. I would also thank for the peers and collaborators I have worked with, met with and talked with in conferences, visiting for collaboration. I would thank for the great synthesis help and scientific discussion with Dr. Silvie Meeuwissen from Van Hest group; I thank for the diblock copolymers from Dr. Mingjiang Zhong from Matyjaszewski group at CMU; I thank for the cryo-imaging discussions and good instrument coordination with Thomas Smart from Epps group; I thank for Dr. Hao-jan Sun’s help about 3D cartoon modeling and small angle x-ray scattering experiments at Argonne National lab. I would thank for Ngoc Nguyen for his instruction on AFM characterization. I would also thanks for the excellent researchers from MSE/CHEM v department, for any smile they gave me in the hallway and any care I received. I would remember the great time talking and working with people, shaping up me as an open, creative and collaborative researcher. I would like to thank for the scientists I work with at NIST and Argonne National Lab, Dr. Paul Butler, Dr. Steve Weigand, Dr. Rita Graceffa and Olga Antipova. I would specifically thank for the continuous help from facility scientists and stuff. Thanks for Prof. Chaoying Ni, even I had thanked him as being my committee member, for the support and management of advanced microscopy lab. Thanks for Frank Kriss for the patient and kind help of any problem I had. Thanks for the help of Dr. Fei Deng, Jennifer Sloppy for the FIB, TEM, and AFM help. I cannot remember how many times I bothered them for instrument issues and problem-solving. I am shaped up to be a proficient user with problem-solving abilities from a green hand who always made mistakes. The help I got from seniors, the challenges I received from peers, good discussions, laughs and depresses had shaped up me to be a mature research person. I attribute all my excitement and self-accomplish moments, when I got good images in the dark room/ when good results popped up from the beamline, to all the help I received from people. I feel thankful and lucky working with them. Most importantly, I would like to thank my friends and family. I thank my friends for always believing me and forgiving me for being awful at keeping in touch over the past 6 years. I thank all of my friends for their support over the years, their encouragement and understanding when I met with some down points. Finally, I would like to thank my parents. Their unrequited love is my backup force for vi solving any obstacles I met with and never saying give up in my study and life. I would not be the person I am today without their love and encouragement. vii TABLE OF CONTENTS LIST OF TABLES ...................................................................................................... xiii LIST OF FIGURES ..................................................................................................... xiv ABSTRACT .............................................................................................................. xxxi 1 INTRODUCTION OF BLOCK COPOLYMER SELF-ASSEMBLY............... 1 1.1 Introduction ............................................................................................... 1 1.2 Amphiphiles .............................................................................................. 2 1.2.1 Overview ....................................................................................... 2 1.2.2 Amphiphile Applications in Industry ............................................ 3 1.3 Amphiphile Solution Assemblies .............................................................. 5 1.3.1 Fundamentals of Amphiphile Assemblies in Solution .................. 5 1.3.2 Packing Parameters and Geometries ............................................