Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2012 The Fabrication of Self-Healing Cellulose Triacetate Polymer Composites and Dicyclopentadine Polymeric Foam Artrease Spann Follow this and additional works at the FSU Digital Library. For more information, please contact [email protected] THE FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES THE FABRICATION OF SELF-HEALING CELLULOSE TRIACETATE POLYMER COMPOSITES AND DICYCLOPENTADINE POLYMERIC FOAM By ARTREASE SPANN A dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy Degree Awarded: Fall Semester, 2012 Artrease Spann defended this dissertation on September 24, 2012. The members of the supervisory committee were: Harold Kroto Professor Directing Dissertation Emmanuel Collins University Representative Ken Knappenberger Committee Member Lei Zhu Committee Member The Graduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii To my mom, my darker side of the moon – always in the shadows leaving me to shine iii ACKNOWLEDGEMENTS My doctoral research would not have been possible without God and all the wonderful people He put in my life. I owe my family a big thank you for always encouraging me. Mom, thank you for showing me college was possible and always encouraging me in my pursuit of more and more education. Thank you to the women in my family. My mom, grandmother, and aunts, have all been an inspiration throughout this process. I have realized how strong and wonderfully made I am. So much of who I am comes from the amazing women in my life. If I become only half as amazing as you all I know I will have a wonderful life ahead of me. Thank you for your strength, wisdom, and prayer. Not to be outdone the men of my family deserve an equally big thank you. My brother, uncles, and grandfather are always so proud of me. Your support is appreciated. It keeps me encouraged. A big THANK YOU goes to my big little brother, Arthur, who is and always has been my greatest cheerleader. If it was not for all of your constant pep talks I might not have tried and tried again. Thank you for always being there for me. You have grown to become a great man. I feel truly blessed that you are my brother. I would like to thank my committee, Sir Harlod Kroto, Dr. Emmanuel Collins, Dr. Ken Knappenberger, and Dr. Lei Zhu. Thank you for your knowledge and advice; I will carry it on to my next stage in life. I would like to extend an extra thank to my advisor, Harry, not only for his scientific insight and research expertise, but for his encouragement to pursue my interest outside of the lab. I am truly grateful for the opportunity to pursue the Florida Gubernatorial Fellowship and work on science education. Special thank you to our research scientist and resident genius, Steve, I definitely could not have done this without you. I hope this gets me in the ark. Thank you to Darryl being an awesome lab mate and preventing lab craziness. iv Graduate school would not have been enjoyable without my wonderful all friends. I owe Casey an extra special thank you for all the great moments over the past four years. Thank you for all the dinners, wine tastings, and dancing. Thank you to Robin, who has been encouraging me since my freshman year. Thank you for waking me up to study, when I didn’t want to, and thank you for keeping me focused. Thank to Crystal, my pif, for the constant foolishness and being the best PIF ever. Lastly, thank you to Rey for being an amazing friend, helping me find solutions to all my problems, and making sure I didn’t stress out too much, especially during this last year. Srn. v TABLE OF CONTENTS List of Tables ...................................................................................................................................x List of Figures ................................................................................................................................ xi List of Abbreviations .................................................................................................................. xvii Abstract ...................................................................................................................................... xviii 1. CHAPTER ONE: INTRODUCTION AND LITERATURE REVIEW .................................1 1.1 Introduction ....................................................................................................................1 1.2 Background: Self-Healing Materials .............................................................................2 1.2.1 Concept and Design Strategies ..........................................................................3 1.2.2 Microcapsule-Based Self-Healing System ........................................................9 1.2.3 Self-Healing System Applications ...................................................................17 1.3 Background: Carbon Nanotubes ..................................................................................18 1.3.1 Carbon Nanotube Structure..............................................................................18 1.3.2 Properties .........................................................................................................19 1.3.3 Polymer/CNT Composites ...............................................................................21 1.3.4 Polymer/CNT Composite Applications ...........................................................22 1.4 Background: Foams .....................................................................................................23 1.4.1 Microcellular Foams ........................................................................................23 1.4.2 Microcellular Foams Applications ...................................................................27 1.5 Dissertation Overview .................................................................................................27 2. CHAPTER TWO: MATERIALS AND FABRICATION METHODS ................................29 2.1 Microencapsulation ......................................................................................................29 2.1.1 Urea-Formaldehyde Microencapsulation with Polymeric Core Materials ......29 vi 2.1.2 Urea-Formaldehyde Microcapsule with Polymer Core Fabrication Process ...30 2.1.3 Urea-Formaldehyde Microcapsules with Carbon Nanofiber Incorporated Shells and Polymer Core Fabrication Process .................................................31 2.2 Self-Healing Cellulose Triacetate Composite Films....................................................32 2.2.1 Self-Healing Coatings and Film Materials ......................................................32 2.2.2 Self-Healing Film and Coating Fabrication .....................................................33 2.3 Dicyclopentadiene Microcelluar Foam ........................................................................34 2.3.1 Dicyclopentadiene Composite Foam Materials ...............................................34 2.3.2 Dicyclopentadiene Microcelluar Foam Fabrication Process ...........................34 2.3.3 Dicyclopentadiene Microcelluar Foam with Carbon Nanofibers Fabrication Process .........................................................................................................................36 2.4 Instrumentation ............................................................................................................36 2.4.1 Spincoater .......................................................................................................36 2.4.2 Scanning Electron Microscopy ........................................................................38 2.4.3 Everhart-Thornley Dectector ...........................................................................42 2.4.4 FEI Nova 400 Nano Scanning Electron Microscope .......................................43 3. CHAPTER THREE: THE FOMATION OF CARBON NANOTUBE COATED MICROCAPSULES VIA IN SITU POLYMERIZATION ..................................................45 3.1 Introduction ..................................................................................................................45 3.2 Experimental Section ...................................................................................................46 3.2.1 Materials ..........................................................................................................46 3.2.2 Microcapsule Fabrication Process ...................................................................46 3.3 Results ..........................................................................................................................47 3.3.1 Optimizing the Microcapsules Fabrication Process .........................................47 vii 3.3.2 Carbon Nanofibers Incorporation into the Microencapsulation Fabrication Process .........................................................................................................................53 3.3.3 Carbon Nanotubes Incorporation into the Microencapsulation Fabrication Process .........................................................................................................................69 3.4 Discussion ....................................................................................................................73 4. CHAPTER FOUR: THE FORMATION OF SELF-HEALING