Electrospinning Polymer Nanofibers - Electrical and Optical
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ELECTROSPINNING POLYMER NANOFIBERS - ELECTRICAL AND OPTICAL CHARACTERIZATION A dissertation presented to the faculty of the College of Arts and Science of Ohio University In partial fulfillment of the requirements for the degree Doctor of Philosophy Saima N. Khan November 2007 This dissertation titled ELECTROSPINNING POLYMER NANOFIBERS ─ ELECTRICAL AND OPTICAL CHARACTERIZATION by SAIMA N. KHAN has been approved for the Department of Physics and Astronomy and the College of Arts and Science by Martin E. Kordesch Professor of Physics and Astronomy Benjamin M. Ogles Dean, College of Arts and Science Abstract KHAN, SAIMA, Ph.D., November 2007, Physics and Astronomy ELECTROSPINNING POLYMER NANOFIBERS - ELECTRICAL AND OPTICAL CHARACTERIZATION (107 pp.) Director of Thesis: Martin E. Kordesch Electro spinning is a technique used for the production of thin continuous fibers from a variety of materials including polymers, composites and ceramics [1-3]. The extremely small diameters (~ nm) and high surface to volume and aspect ratios found in electrospun fibers can not be achieved through conventional spinning. Electrically conducting polymers are materials which simultaneously possess the physical and chemical properties of organic polymers and the electronic characteristics of metals. In this work fibers were electrospun from polymer blends of polyaniline doped with Camphorsulfonic acid (PAn.HCSA) and polyethylene oxide (PEO) in chloroform. Electrical conductivities of the fibers were measured using the four-point-probe method. The conductivities of the cast films were measured for comparison purposes. It was noticed that the conductivity of both the fibers and films increase exponentially with the concentration of (PAn.HCSA), the conductivity of the film however is higher than that of the mat for any given concentration of PAn.HCSA in PEO. Electrical conductivities of single fibers containing different PAn: HCSA concentrations were measured for the first time and were found to be the highest (3.2S/cm) among the mats and films. The effect of the non-conductive PEO on the conductivity of the polyaniline fibers was studied. Keeping the PAn.HCSA concentration constant films and fibers were obtained from blends containing PEO (300,000 g/mol) and PEO (900,000 g/mol). Higher electrical conductivities were recorded in fibers and mats containing PEO (900,000 g/mol) than those containing PEO (300,000 g/mol). Silicon Carbide (SiC) fibers were obtained by electrospinning a blend of SiC and PEO in chloroform and sintering the as spun fibers at temperatures of 800ºC and 1000ºC. The compositional analysis of the annealed samples confirmed the presence of (30-40) µm long SiC fibers with diameters in the range (1-3) µm. Optical spectra of the fibers show red emission extending to the infrared. For the first time complexes of ruthenium with picolinate and polypyridine ligands were introduced into nanofibers. Fibers containing ruthenium picolinate ([Ru (pic)2 (dmso)2]) turn orange from pale yellow on exposure to ultraviolet radiation (350nm). Fibers containing ruthenium bi-pyridine ([Ru(bpy)2](PF6)2) exhibit photoluminescence with steady state red emission upon 450 nm excitation. Approved: Martin E. Kordesch Professor of Physics and Astronomy Dedication To my father Mumtaz Khan, Who provided me a strong academic foundation and whose determination to provide me education serves as an inspirational example to a society and culture where women have always been underestimated and under-treated. He is not in this world any more but I hope he knows that I can’t be proud enough of being his daughter and that I love him as much as he loved me. Acknowledgements First and foremost I would like to express my heartfelt gratitude towards my supervisor Professor Martin E. Kordesch for his academic guidance, continuous support and encouragement throughout this project. He is a pleasant person, a remarkable teacher and a great human being. I appreciate his generosity in providing me the opportunity to attend various conferences that gave me good academic exposure. He has been very co- operative all along and gave me his precious time and advice whenever I needed it. I am very thankful to Dr. Saw Wai Hla, Dr. Alexander Neiman and Dr. P. G. Van Patten for being members of my thesis committee. I am sincerely thankful to Dr. Jeffery Rack for his help and co-operation in this work. My heartfelt gratitude extends to Dr. Aurangzeb Khan who makes me proud for being my loving husband, wonderful friend and a nice colleague. I can’t thank him enough for believing in me and making me believe in myself. I want to acknowledge the little sacrifices our lovely daughter Gulsanga Khan has been making every day, for three years now. I love her and I owe her every bit of the pride I take in my degree today. I want to offer a very special thanks to my mother and my brothers who always took pride in my academic achievements and facilitated me in all the ways possible. I offer my special thanks to my mother-in-law for her love and support. She is an extraordinary woman and truly believes in the value of education. I also want to thank my friends and relatives for their support and co-operation. 7 Table of Contents ABSTRACT....................................................................................................................... 3 DEDICATION................................................................................................................... 5 ACKNOWLEDGEMENTS ............................................................................................. 6 LIST OF FIGURES ........................................................................................................ 11 CHAPTER 1.................................................................................................................... 15 BACKGROUND AND EXPERIMENTAL TOOLS ................................................... 15 1.1 Introduction........................................................................................................... 15 1.2 Electrospinning ..................................................................................................... 16 1.3 Working principle................................................................................................. 21 1.4 Scanning electron microscope (SEM) .................................................................. 25 1.5 Transmission electron microscope (TEM)............................................................ 27 1.6 Energy dispersive x-ray spectrometry (EDX)....................................................... 29 1.7 Four-Point-Probe method of conductivity measurement...................................... 31 1.8 Cathodoluminescence ........................................................................................... 34 8 1.9 Conclusion ............................................................................................................ 34 CHAPTER2..................................................................................................................... 36 ELECTROSPINNING POLYETHYLENE OXIDE NANOFIBERS........................ 36 2.1 Introduction........................................................................................................... 36 2.2 Sample preparation and obtaining fibers .............................................................. 37 2.3 Important process parameters ............................................................................... 39 2.3.1 Applied voltage............................................................................................. 39 2.3.2 Distance between the nozzle and the collector ............................................. 42 2.4 Conclusion ............................................................................................................ 44 CHAPTER 3.................................................................................................................... 45 CONDUCTING POLYMER NANOFIBERS .............................................................. 45 3.1 Introduction........................................................................................................... 45 3.2 Different types of doping...................................................................................... 48 3.2.1 Redox doping................................................................................................ 48 3.2.2 Photo doping................................................................................................. 48 3.2.3 Charge-injection doping................................................................................ 48 3.2.4 Non-Redox doping or Protonic-acid doping................................................. 49 9 3.3 Polyaniline ............................................................................................................ 50 3.3.1 Oxidation states of polyaniline ..................................................................... 51 3.3.2 Doping polyaniline........................................................................................52 3.4 Sample preparation............................................................................................... 55 3.5 Electrospinning fibers........................................................................................... 56 3.6 Characterization of the nanofibers........................................................................ 57 3.7 Electrical Conductivity measurement..................................................................