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Rational Design of Soft Materials Through RATIONAL DESIGN OF SOFT MATERIALS THROUGH CHEMICAL ARCHITECTURES A Dissertation Presented to The Graduate Faculty of The University of Akron In Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy Heyi Liang December, 2019 RATIONAL DESIGN OF SOFT MATERIALS THROUGH CHEMICAL ARCHITECTURES Heyi Liang Dissertation Approved: Accepted: ______________________________ ______________________________ Advisor Department Chair Dr. Andrey V. Dobrynin Dr. Tianbo Liu ______________________________ ______________________________ Committee Member Interim Dean of the College Dr. Ali Dhinojwala Dr. Ali Dhinojwala ______________________________ ______________________________ Committee Member Dean of the Graduate School Dr. Matthew Becker Dr. Chand K. Midha ______________________________ ______________________________ Committee Member Date Dr. Mesfin Tsige ______________________________ Committee Member Dr. Hunter King ______________________________ Committee Member Dr. Kevin Cavicchi ii ABSTRACT Mimicking the mechanical behavior of biological tissues is crucial for tissue engineering, medical implants, and wearable devices. Many biological tissues—such as lung, skin and artery tissues—are supersoft at small deformation (Young’s Modulus E0 < 104 Pa) and stiffen with increasing deformation. This unique combination of mechanical softness and nonlinear elasticity cannot be easily duplicated by conventional synthetic elastomers composed of linear polymers. Graft polymers, consisting of linear backbones densely grafted with short side chains, endow polymeric materials with two unique features owing to their special architecture: (i) the dilution of chain entanglement by side chains, and (ii) the stretching of the backbone due to steric repulsions of side chains. These distinct features pave the way for the design of supersoft elastomers with controllable nonlinear elasticity. Through a combination of theoretical calculations and coarse-grained molecular dynamics simulations, we have developed a general material design strategy which encodes the stress-strain curve of soft materials into the architecture of graft polymer networks. Such networks can be prepared through either chemical crosslinking of bottlebrush macromolecules or self-assembly of linear-bottlebrush-linear triblock copolymers. The mechanical response of the resultant materials is controlled by architectural parameters, including network strand length, side chain length, grafting density, as well as the chain length of blocks in triblock copolymers. By utilizing this design-by-architecture strategy, iii replicas of jellyfish, artery and skin tissues based on bottlebrush poly(dimethylsiloxane) (bbPDMS) are synthesized to test our approach. iv ACKNOWLEDGEMENTS As the five-year journey of graduate school study and research coming to an end, I owe many people a debt of gratitude for their support. Most importantly, I would like to express my deepest appreciation to my advisor, Prof. Andrey Dobrynin. He guided me through this journey with great patience and paved the way to the completion of my dissertation. I enjoyed the everyday discussion with him when he always shared his invaluable experience and insightful idea about research without any reservation. Except doing research, he also provided me opportunities to mentor high school students and teach classes and generously supported me attend many conferences, from which I gain much professional experience crucial for my future career. After five-year training, I will take away not only knowledge and methodology of conducting research, but also the character of being considerable to others and the sense of humor towards life. I am also grateful to my committee Prof. Ali Dhinojwala, Prof. Matthew Becker, Prof. Mesfin Tsige, Prof. Hunter King and Prof. Kevin Cavicchi for helpful discussion on my research project. I would like to further thank Prof. Stephen Z. D. Cheng for his valuable advice on academic career development. I also had great pleasure working with Prof. Sergei Sheiko from the University of North Carolina at Chapel Hill, Dr. Gary Grest from Sandia National Laboratories and Prof. Douglas Adamson at University of Connecticut. Collaboration with them offered me valuable opportunities to explore different subject and get inspiration for my own research. Furthermore, I would like to v express my gratitude to Prof. Lin Yao and Prof. Luyi Sun at University of Connecticut for their help when I spend the first year of my graduate study in the Polymer Program at UConn. I feel luck and thankful working together with my former and current labmates: Dr. Zhen Cao, Dr. Zilu Wang, Yuan Tian, Michael Jacobs and Ryan Sayko. Without their heartwarming support and encouragement, I could not imagine how I would spend five year alone in the country thousand miles away from my homeland. Last but not least, my greatest gratitude and love goes to my family. My parents have always been very supportive to any decision I made. Even though I have not been back home for four years, the weekly video chat with them is always the greatest time every week. My grandfather, who was a chemical engineer, shared with me his experience on study aboard and conducting research which is always encouraging and inspiring. My grandmother, who was a doctor, provided continuing care of my health. I dedicate this dissertation to my family. Without their unconditional love and support, I would have never gone this far. vi TABLE OF CONTENTS Page LIST OF TABLES .............................................................................................................. x LIST OF FIGURES .......................................................................................................... xii CHAPTER I. INTRODUCTION ........................................................................................................... 1 II. COMB AND BOTTLEBRUSH GRAFT POLYMERS IN A MELT ........................... 6 2.1 Introduction .............................................................................................................. 6 2.2 Graft Homopolymers in a Melt ................................................................................ 8 2.2.1 Scaling Analysis ............................................................................................... 8 2.2.2 Comparison with Simulations ........................................................................ 15 2.3 Graft Copolymers in a Melt ................................................................................... 24 2.3.1 Scaling Analysis ............................................................................................. 24 2.3.2 Comparison with Simulations ........................................................................ 33 2.4 Comparison with Experiments ............................................................................... 40 2.5 Simulation Methods ............................................................................................... 41 2.6 Conclusions ............................................................................................................ 44 III. SCATTERING FROM MELTS OF COMBS AND BOTTLEBRUSHES ................ 47 3.1 Introduction ............................................................................................................ 47 3.2 Simulation Results ................................................................................................. 49 3.2.1 Diagram of States ........................................................................................... 50 3.2.2 Structure Factor .............................................................................................. 52 vii 3.3 Theoretical Analysis of the Static Structure Factor ............................................... 55 3.3.1 Comb regime .................................................................................................. 58 3.3.2 Bottlebrush Regime ........................................................................................ 63 3.4 Conclusions ............................................................................................................ 66 IV. ENTANGLEMENTS OF MELTS OF COMBS AND BOTTLEBRUSHES ............ 68 4.1 Introduction ............................................................................................................ 68 4.2 Entanglement Plateau Modulus of Graft Polymer Melts ....................................... 70 4.2.1 Scaling Analysis ............................................................................................. 70 4.2.2 Comparison to Experiments ........................................................................... 77 4.3 Packing Number of Graft Polymer Melts .............................................................. 86 4.3.1 Simulation Results .......................................................................................... 88 4.3.2 Comparison with Experiments ....................................................................... 92 4.4 Simulation Methods ............................................................................................... 94 4.5 Conclusions .......................................................................................................... 100 V. POLYMER NETWORKS WITH COMBS AND BOTTLEBRUSHES STRANDS 102 5.1 Introduction .......................................................................................................... 102 5.2 Scaling Analysis ..................................................................................................
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