C ONDUCTIVE POLYMERS A N D PLASTICS in Industrial Applications LarryRupprecht, Editor Society ofPlastics Engineers PlasticsDesign Library Copyright © 1999, Plastics Design Library All rights reserved ISBN 1-884207-77-4 Library of Congress Card Number 98-89320 Published in the United States of America, Norwich, NY by Plastics Design Library a division of William Andrew Inc Information in this document is subject to change without notice and does not represent a commitment on the part of Plastics Design Library No part of this document may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, recording, or any information retrieval and storage system, for any purpose without the written permission of Plastics Design Library Comments, criticism and suggestions are invited and should be forwarded to Plastics Design Library Plastics Design Library and its logo are trademarks of William Andrew Inc Please Note: Great care is taken in the compilation and production of this volume, but it should be made clear that no warranties, express or implied, are given in connection with the accuracy or completeness of this publication, and no responsibility can be taken for any claims that may arise In any individual case of application, the respective user must check the correctness by consulting other relevant sources of information The use of general descriptive names, registered names, trademarks, etc in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use Manufactured in the United States of America Plastics Design Library, 13 Eaton Avenue, Norwich, NY 13815 Tel: 607/337-5080 Fax: 607/33-5090 Table of Contents Preface vii Larry Rupprecht Electrical Conductivity in Conjugated Polymers Arthur J Epstein Polyaniline as Viewed from a Structural Perspective 11 M J Winokur, B R Mattes Processability of Electrically Conductive Polyaniline Due to Molecular Recognition 19 Terhi Vikki, Olli Ikkala, Lars-Olof Pietilä, Heidi Österholm, Pentti Passiniemi, Jan-Erik Österholm Crystallinity and Stretch Orientation in Polyaniline Camphor-Sulphonic Acid Films 25 L Abell, P Devasagayam, P N Adams A P Monkman Structure-Property Characteristics of Ion Implanted Syndiotactic Polystyrene 35 Chang-Meng Hsiung and Caiping Han, Y Q Wang, W J Sheu, G A Glass, Dave Bank Carbon Black Filled Immiscible Blend of Poly(Vinylidene Fluoride) and High Density Polyethylene: Electrical Properties and Morphology 43 Jiyun Feng, Chi-Ming Chan Conductivity/Morphology Relationships in Immiscible Polymer Blends: HIPS/SIS/Carbon Black 51 R Tchoudakov, O Breuer, M Narkis, A Siegmann Rheological Characterization of an Electrically Conductive Composite 57 Allen C Nixon Estimation of the Volume Resistivity of Conductive Fiber Composites by Two New Models 61 Mark Weber, M R Kamal Effect of Thermal Treatment on Electrical Conductivity of Polypyrrole Film Cast from Solution 69 J Y Lee, D Y Kim, C Y Kim, K T Song, S Y Kim Creation of Electrically Conducting Plastics by Chaotic Mixing 77 Radu I Danescu, David A Zumbrunnen Production of Electrically Conducting Plastics at Reduced Carbon Black Concentrations by Three-Dimensional Chaotic Mixing 85 Radu I Danescu, David A Zumbrunnen Preparation of Conducting Composites and Studies on Some Physical Properties 93 Jun-Seo Park, Sung-Hun Ryu, Ok-Hee Chung iv Table of Contents Development of Electrohydrodynamic Flow Cells for the Synthesis of Conducting Polymers P C Innis, V Aboutanos, N Barisci, S Moulton and G G Wallace Hydroxyethyl Substituted Polyanilines: Chemistry and Applications as Resists Maggie A Z Hupcey, Marie Angelopoulos, Jeffrey D Gelorme, Christopher K Ober Electroformation of Polymer Devices and Structures G G Wallace, J N Barisci, A Lawal, D Ongarato, A Partridge Microelectronic Encapsulation and Related Technologies: an Overview Stephen L Buchwalter Fabrication and Characterization of Conductive Polyaniline Fiber Hsing-Lin Wang, Benjamin R Mattes, Yuntian Zhu, James A Valdez Electrically Conductive Polyaniline Fibers Prepared by Dry-Wet Spinning Techniques Benjamin R Mattes, Hsing-Lin Wang, Dali Yang Conductive Thermoplastic Compounds for EMI/RFI Applications Larry Rupprecht Crystallization Kinetics in Low Density Polyethylene Composites Brian P Grady, W B Genetti Development of Conductive Elastomer Foams by in Situ Copolymerization of Pyrrole and N-Methylpyrrole R A Weiss, Yueping Fu, Poh Poh Gan, Michael D Bessette Neocapacitor New Tantalum Capacitor with Conducting Polymer Atsushi Kobayashi, Yoshihiko Saiki, Kazuo Watanabe Conductive Polymer-Based Transducers as Vapor-Phase Detectors Frederick G Yamagishi, Thomas B Stanford, Camille I van Ast, Paul O Braatz, Leroy J Miller, Harold C Gilbert Conductive Polyphenylene Ether/Polyamide Blends For Electrostatic Painting Applications J.J Scobbo, Jr Conductive Polymer Films for Improved Poling in Non-Linear Optical Waveguides James P Drummond, Stephen J Clarson, Stephen J Caracci, John S Zetts The Corrosion Protection of Metals by Conductive Polymers II Pitting Corrosion Wei-Kang Lu, Ronald L Elsenbaumer Studies of Electronically Conducting Polymers for Corrosion Inhibition of Aluminum and Steel Dennis E Tallman, Youngun Pae, Guoliang Chen, Gordon P Bierwagen, Brent Reems Victoria Johnston Gelling 99 109 115 121 127 135 143 153 159 167 173 181 189 195 201 v Novel Electrically Conductive Injection Moldable Thermoplastic Composites for ESD Applications Moshe Narkis, Gershon Lidor, Anita Vaxman, Limor Zuri Electrical Properties of Carbon Black-Filled Polypropylene/Ultra-High Molecular Weight Polyethylene Composites Jiyun Feng, Chi-Ming Chan The Use of Conducting Polymer Composites in Thermoplastics for Tuning Surface Resistivity Sam J Dahman, Jamshid Avlyanov Monosandwich Injection Molding: Skin-Core-Structure and Properties of Sandwich-Molded Anti-electrostatic Components K Kuhmann, G W Ehrenstein Thermoformed Containers for Electrostatic Sensitive Devices Walter E Gately Electronic Packaging for the Next Century Steve Fowler Conducting Polymers as Alignment Layers and Patterned Electrodes for Twisted Nematic Liquid Crystal Displays Jerome B Lando, J Adin Mann, Jr., Andy Chang, Chin-Jen S Tseng, David Johnson Flexible Conductive Coatings on Thermoformed Films for EMl/RFl Shielding Bruce K Bachman Nylon in Thin-wall Housings for Portable Electronics James F Stevenson, Alan Dubin Finite Element Analysis Aided Engineering of Elastomeric EMI Shielding Gaskets Shu H Peng and Kai Zhang Index 209 219 225 231 239 245 253 259 267 275 281 Preface The introduction of the Electromagnetic Compatibility Directive and the burgeoning use of electronic components in a wide range of manufactured goods have created interest in plastic materials designed for EMI shielding, safe packaging, corrosion protection, and other applications Conductive plastics are positioned to play an increasingly important role in affairs of mankind, specifically in the area of electronic and electrical conductivity While general knowledge about conductive polymers and plastics has been available for many years, a true understanding of their application has only taken shape in the last to years This is attributable to advancements in materials and processing techniques Engineers have only begun to explore the design freedom and the economic benefits of specifying conductive polymers and plastics in industrial and business applications Shielding of electronic components and devices from effects of electrostatic discharge (ESD) and electromagnetic or radio frequency interference (EMI/RFI) is addressed frequently in various media ESD problems can damage or destroy sensitive electronic components, erase or alter magnetic media, or set off explosions or fires in flammable environments EMI can interfere with the operation of simple appliances, corrupt data in large-scale computer systems, cause inaccurate readings and output in aircraft guidance systems, and interrupt the functioning of medical devices such as pacemakers Liability to industry from these problems totals billions of dollars each year This book presents novel approaches and techniques in the area of electronic protection Beyond ESD and EMI problems lie very diverse application areas for conductive polymers and plastics Highlighted in this book are such uses as corrosion protection of metals; as resistors, capacitors, or detectors, and improved electrostatic painting processes This book is a collection of papers describing efforts of many individuals - both in industry and academia - in both pure research and application development of conductive polymers and plastics Numerous existing possibilities of material design are discussed, including intrinsically conductive polymers, polymers doped with conductive sites, ion implantation, polymers containing dispersed conductive fillers, and polymer blends technology in cost effective applications which are compared with metal plating viii Preface Conductive fillers discussed in the book include carbon black, hollow flexible carbon fibers, nickel coated carbon fibers, other conductive fibers, and multiphase thermoplastic composites containing several fillers In addition to existing technology, the book discusses improvements to current plastic processing methodology that provide enhanced conductive characteristics while improving economic benefits For instance, co-continuous phase technology in the preparation of conductive composite materials and co-injection molding techniques in forming finished articles are introduced Various methods of manufacture of polymer and final product are investigated, including electrohydrodynamic flow cells, transducers used as vapor-phase detectors, electrostatic paintable compounds, conductive polymer films, non-linear optical waveguides, conductive foams, thermoformed containers for electrostatic sensitive devices, disk-drive assemblies, and more This work is aimed at understanding the effect of processing parameters and formulation on material performance and uniform distribution of conductive components Although, conductive additives are incorporated to change electrical properties of materials, they also affect other performance characteristics of final products These effects are investigated and remedies proposed which allow production of defect-free finished products Larry Rupprecht Winona, May 1999 Electrical Conductivity in Conjugated Polymers Arthur J Epstein Department of Physics and Department of Chemistry, The Ohio State University, Columbus, Ohio, 43210-1106 INTRODUCTION In 1977, the first intrinsic electrically conducting organic polymer, doped polyacetylene, was reported,1 spurring interest in “conducting polymers.” These polymers are a different class of materials than conducting polymers, which are merely a physical mixture of a non-conductive polymer with a conducting material such as metal or carbon powder Initially these intrinsically conducting polymers were neither processable nor air stable However, later generations of these polymers were processable into powders, films, and fibers from a wide variety of solvents, and also air stable.2,3 Some forms of these intrinsically conducting polymers can be blended into traditional polymers to form electrically conductive blends The electrical conductivities of the intrinsically conducting polymer systems now range from that typical of insulators (