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HANDBOOK OF

Antistatics
Jürgen Pionteck & George Wypych, Editors

Toronto 2007
Published by ChemTec Publishing
38 Earswick Drive, Toronto, Ontario M1E 1C6, Canada

© ChemTec Publishing, 2007


ISBN 1-895198-34-8

Cover design: Anita Wypych


Photographs by: Darrell Coomes (USA) and Rodolfo Clix (Brasil)

All rights reserved. No part of this publication may be repro-


duced, stored or transmitted in any form or by any means with-
out written permission of copyright owner. No responsibility is
assumed by the Author and the Publisher for any injury or/and
damage to persons or properties as a matter of products liabil-
ity, negligence, use, or operation of any methods, product ideas,
or instructions published or suggested in this book.

Canadian Cataloguing in Publication Data

Pionteck, Jürgen
Handbook of antistatics / Jürgen Pionteck, George Wypych

(Encyclopedia of polymer additives)


Includes bibliographical references and index.

ISBN 1-895198-34-8

1. Polymers--Antistatic additives. 2. Polymers--Handbook, manuals, etc.


I. Wypych, George II. Title. III. Series.

TP1142.P516 2006 668.9 C2006-904558-5


Contents

1. Introduction ............................................................................. 1
1.1 Historical Developments in Studies on Static Electricity ............. 1
1.2 The Triboelectric Series and Electrostatic Charging ................... 4
1.3 Electrical Properties of Plastics ................................................... 5
1.3.1 Electrical Conductivity ................................................. 5
1.3.2 Dielectric Behavior of Plastics in Low Electric
Fields .......................................................................... 9
1.3.3 Electrostatic Charging of Dielectric Polymers ............. 10
1.3.4 Stability of Plastics in High Electric Fields .................. 11
1.4 Antistatic Agents .......................................................................... 11
1.4.1 Classification of Antistatics ......................................... 11
1.4.2 Expectations from Antistatics ...................................... 12
1.5 Definitions .................................................................................... 13
References ............................................................................................. 14

2. Types of Antistatic Agents .................................................... 17


2.1 Introduction .................................................................................. 17
2.2 Characteristic Properties of Industrial Antistatic Agents ............. 18
2.2.1 Amines (Quaternary and Others) ................................ 18
2.2.2 Carbon Black .............................................................. 20
2.2.3 Esters .......................................................................... 21
2.2.4 Fibers .......................................................................... 22
2.2.4.1 Metal ............................................................ 22
2.2.4.2 Carbon and Graphite Fibers ......................... 23
2.2.4.3 Others .......................................................... 24

This page has been reformatted by Knovel to provide easier navigation. v


vi Contents

2.2.5 Inorganic Materials ...................................................... 25


2.2.6 Masterbatches ............................................................ 26
2.2.7 Metal Powders and Nanopowders .............................. 27
2.2.8 Nanotubes ................................................................... 28
2.2.9 Polyethylene Glycol .................................................... 29
2.2.10 Polymers ..................................................................... 30
2.2.10.1 Inherently Conductive .................................. 30
2.2.10.2 Containing Antistatic .................................... 31

3. Typical Methods of Quality Control of Antistatics ............... 33


3.1 Abbreviations, Terminology, and Vocabulary ............................. 33
3.2 Acid Number ................................................................................ 33
3.3 Brookfield Viscosity ..................................................................... 34
3.4 Capacitance ................................................................................. 34
3.5 Chemical Resistance ................................................................... 34
3.6 Color ............................................................................................ 36
3.7 Compression Set ......................................................................... 36
3.8 Dielectric Breakdown Voltage ..................................................... 36
3.9 Dielectric Constant (Relative Permittivity) ................................... 37
3.10 Dielectric Strength ....................................................................... 38
3.11 Dissipation Factor ........................................................................ 38
3.12 Dry Arc Resistance ...................................................................... 39
3.13 Electrical Resistivity ..................................................................... 39
3.14 Erosion Resistance ...................................................................... 40
3.15 Flash and Fire Point .................................................................... 40
3.16 Hardness ..................................................................................... 41
3.17 Kinematic Viscosity ...................................................................... 41
3.18 Loss Index ................................................................................... 42
3.19 Marking (Classification) ............................................................... 42
3.20 Melt Rheology .............................................................................. 42
3.21 Refractive Index ........................................................................... 43
3.22 Residual Contamination .............................................................. 43
3.23 Saponification Value .................................................................... 43

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Contents vii

3.24 Specific Gravity ............................................................................ 43


3.25 Specifications for Commercial Products and Standard
Test Methods ............................................................................... 44
3.25.1 Adhesive Bonding ....................................................... 44
3.25.2 Aviation and Distillate Fuels ........................................ 44
3.25.3 Conductive Adhesives ................................................ 45
3.25.4 Conveyor Belting ......................................................... 45
3.25.5 Crosslinkable Ethylene Plastics .................................. 45
3.25.6 Electrical Insulating Materials ..................................... 45
3.25.7 Electrocoat Bath .......................................................... 46
3.25.8 Electronic Devices ...................................................... 46
3.25.9 Endless Belts .............................................................. 46
3.25.10 Extruded Film and Tape .............................................. 46
3.25.11 Flooring ....................................................................... 46
3.25.12 Footwear (Protective) .................................................. 47
3.25.13 Hoses .......................................................................... 47
3.25.14 Insulation Shielding Materials ..................................... 47
3.25.15 Liquid Paints ............................................................... 47
3.25.16 Medical Applications ................................................... 48
3.25.17 Polymer-based Microwave Circuit Substrates ............ 48
3.25.18 Protective Clothing ...................................................... 48
3.25.19 Rubber ........................................................................ 48
3.25.20 Textile Fabric .............................................................. 48
3.25.21 Ventilation Materials .................................................... 48
3.25.22 Writing Paper .............................................................. 48
3.26 Tensile Properties ........................................................................ 49
3.27 Thermal Expansion Coefficient ................................................... 49
3.28 Water Concentration .................................................................... 50
3.29 Weight Loss ................................................................................. 50
References ............................................................................................. 50

4. Electrostatic Hazards ............................................................. 57


4.1 Electrostatic Charge Generation ................................................. 57

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viii Contents

4.2 Electromagnetic Interference ...................................................... 61


References ............................................................................................. 63

5. Ignition Hazards and Preventive Measures .......................... 65


5.1 Conditions of Ignition ................................................................... 65
5.2 Types of Discharge and Discharge Energy ................................ 65
5.3 Minimum Ignition Energy ............................................................. 68
5.4 Preventive Measures ................................................................... 69
References ............................................................................................. 69

6. Mechanisms of Action of Antistatic Agents ......................... 71


6.1 Conductive Modification of Polymer Surfaces ............................ 71
6.2 Mechanism of Action of Antistatics Added into Bulk ................... 73
6.2.1 Internal Organic Antistatics ......................................... 73
6.2.2 Conductive Inorganic Fillers ........................................ 74
6.2.3 Conductive Inorganic Materials in Blends of
Insulating Polymers ..................................................... 79
6.2.4 Conductive Polymer/Insulating Polymer
Composites ................................................................. 81
6.3 Consideration of Mechanism in Selection of Antistatic
Agents for Application .................................................................. 83
References ............................................................................................. 85

7. Compatibility of Antistatic Agents with Matrix and


Their Performance .................................................................. 87
7.1 What Influences Compatibility of Antistatic Agents with
Matrix? ......................................................................................... 87
7.2 Methods of Antistatic Agent Selection Based on Principles
of Compatibility ............................................................................ 90
7.3 Influence of Compatibility on Permanence of Antistatic
Agent Incorporation ..................................................................... 91
References ............................................................................................. 91

8. Antistatic Agent Motion and Diffusion .................................. 93


8.1 Antistatic Agent Diffusion Rate and the Methods of Study ......... 93

This page has been reformatted by Knovel to provide easier navigation.


Contents ix

8.2 Antistatic Agent Motion and Distribution in Matrix ...................... 95


References ............................................................................................. 96

9. Structure and Distribution of Non-migrating


Antistatics ............................................................................... 97
9.1 Morphological Structure and Distribution of Non-migrating
Antistatics ..................................................................................... 97
9.2 Percolation Threshold .................................................................. 101
References ............................................................................................. 107

10. Antistatic Agent Incorporation Method and Its


Performance ............................................................................ 109
10.1 Grafting ........................................................................................ 109
10.2 Chemical Modification ................................................................. 110
10.3 Surface Coating ........................................................................... 111
10.4 UV and Electron Beam Curing .................................................... 113
10.5 Plasma Treatment ....................................................................... 113
10.6 Physical Vapor Deposition .......................................................... 114
10.7 Mixing/Dispersion ........................................................................ 114
10.8 Crystallization in Matrix ................................................................ 116
10.9 Nucleation of Inorganic Nanoparticles ........................................ 116
References ............................................................................................. 116

11. Antistatic Agents and Other Components of


Formulation ............................................................................. 119
11.1 Antistatic Agent Consumption by Fillers ..................................... 119
11.2 Absorption of Additives by Antistatic Agents ............................... 119
11.3 Molecular Mobility and Transport in the Presence of
Antistatic Agents .......................................................................... 120
11.4 Effect of Antistatic Agents on Polymerization and Curing
Reactions ..................................................................................... 121
11.5 Effect of Moisture and Humidity .................................................. 121
References ............................................................................................. 123

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x Contents

12. Effect of Antistatic Agents on Some Properties of


Compounded Materials .......................................................... 125
12.1 Mechanical Properties ................................................................. 125
12.2 Optical Properties ........................................................................ 130
12.3 Spectral Properties ...................................................................... 135
12.4 Rheological Properties ................................................................ 136
12.4.1 Effect of Low Molecular Weight Organic
Additives ..................................................................... 136
12.4.2 Effect of Conductive Inorganic Materials .................... 136
12.5 Electrical Properties ..................................................................... 139
12.6 Glass Transition Temperature ..................................................... 140
12.7 Thermal Stability .......................................................................... 142
12.8 Effect of UV and Ionized Radiation on Materials
Containing Antistatics .................................................................. 143
12.9 Morphology, Crystallization, Structure, and Orientation of
Macromolecules .......................................................................... 144
12.10 Hydrophilic Properties, Surface Free Energy .............................. 145
References ............................................................................................. 146

13. Antistatic Agent Selection for Specific Polymers ................ 149


13.1 ABS .............................................................................................. 149
13.1.1 Typical Antistatic Agents ............................................. 149
13.1.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 149
13.2 Acrylics ......................................................................................... 150
13.2.1 Typical Antistatic Agents ............................................. 150
13.2.2 Typical Formulations ................................................... 151
13.3 Cellulose Acetate ......................................................................... 151
13.3.1 Typical Antistatic Agents ............................................. 151
13.3.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 151
13.3.3 Typical Formulations ................................................... 152

This page has been reformatted by Knovel to provide easier navigation.


Contents xi

13.4 Cellulose Butyrate and Propionate .............................................. 152


13.4.1 Typical Antistatic Agents ............................................. 152
13.4.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 152
13.5 Cellulose Nitrate .......................................................................... 152
13.5.1 Typical Antistatic Agents ............................................. 152
13.6 Charge Transfer Polymers .......................................................... 153
13.6.1 Typical Antistatic Agents ............................................. 153
13.6.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 153
13.7 Chlorinated Polyvinylchloride ...................................................... 154
13.7.1 Typical Antistatic Agents ............................................. 154
13.8 Chlorosulfonated Polyethylene ................................................... 154
13.8.1 Typical Antistatic Agents ............................................. 154
13.9 Epoxy Resin ................................................................................. 155
13.9.1 Typical Antistatic Agents ............................................. 155
13.9.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 155
13.9.3 Typical Formulations ................................................... 156
13.10 Ethylene-propylene-diene Copolymer, EPDM ............................ 156
13.10.1 Typical Antistatic Agents ............................................. 156
13.11 Ethylene-vinyl Acetate Copolymer, EVA ..................................... 156
13.11.1 Typical Antistatic Agents ............................................. 156
13.11.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 156
13.11.3 Typical Formulations ................................................... 156
13.12 Ionomers ...................................................................................... 157
13.12.1 Typical Antistatic Agents ............................................. 157
13.12.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 157
13.13 Nitrile Rubber ............................................................................... 158
13.13.1 Typical Antistatic Agents ............................................. 158

This page has been reformatted by Knovel to provide easier navigation.


xii Contents

13.13.2 Effect of Antistatic Agents on Polymer and Other


Additives ..................................................................... 158
13.14 Polyacene .................................................................................... 158
13.15 Polyacetylene .............................................................................. 159
13.15.1 Typical Antistatic Agents ............................................. 160
13.16 Polyacrylonitrile ............................................................................ 160
13.16.1 Typical Antistatic Agents ............................................. 160
13.16.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 160
13.17 Polyamide .................................................................................... 161
13.17.1 Typical Antistatic Agents ............................................. 161
13.17.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 161
13.18 Polyaniline .................................................................................... 162
13.18.1 Typical Antistatic Agents ............................................. 163
13.18.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 163
13.19 Polybutadiene .............................................................................. 164
13.20 Polybutylmethacrylate ................................................................. 165
13.20.1 Typical Antistatic Agents ............................................. 165
13.21 Polycarbonate .............................................................................. 165
13.21.1 Typical Antistatic Agents ............................................. 166
13.21.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 167
13.22 Polyester ...................................................................................... 167
13.22.1 Typical Antistatic Agents ............................................. 167
13.22.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 168
13.23 Polyetheretherketone .................................................................. 169
13.23.1 Typical Antistatic Agents ............................................. 169
13.24 Polyetherimide ............................................................................. 169
13.24.1 Typical Antistatic Agents ............................................. 169

This page has been reformatted by Knovel to provide easier navigation.


Contents xiii

13.25 Polyethylene ................................................................................ 170


13.25.1 Typical Antistatic Agents ............................................. 170
13.25.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 170
13.26 Polyimide ..................................................................................... 171
13.26.1 Typical Antistatic Agents ............................................. 171
13.26.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 171
13.27 Polyisoprene ................................................................................ 172
13.27.1 Typical Antistatic Agents ............................................. 172
13.27.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 172
13.28 Polyisothionaphthene .................................................................. 172
13.28.1 Typical Antistatic Agents ............................................. 173
13.29 Polylactide .................................................................................... 173
13.29.1 Typical Antistatic Agents ............................................. 173
13.30 Polymethylmethacrylate .............................................................. 174
13.30.1 Typical Antistatic Agents ............................................. 174
13.30.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 174
13.31 Polyoxyethylene ........................................................................... 175
13.31.1 Typical Antistatic Agents ............................................. 175
13.31.2 Typical Formulations ................................................... 175
13.32 Polyoxymethylene ....................................................................... 175
13.32.1 Typical Antistatic Agents ............................................. 175
13.33 Poly(N-vinyl-2-pyrrolidone) .......................................................... 176
13.33.1 Typical Antistatic Agents ............................................. 176
13.34 Polyparaphenylene ...................................................................... 176
13.34.1 Typical Antistatic Agents ............................................. 177
13.35 Polyphenylene Ether ................................................................... 177
13.35.1 Typical Antistatic Agents ............................................. 177
13.35.2 Typical Formulations ................................................... 177

This page has been reformatted by Knovel to provide easier navigation.


xiv Contents

13.36 Polyphenylene Sulfide ................................................................. 178


13.36.1 Typical Antistatic Agents ............................................. 178
13.37 Polyphenylene Vinylene .............................................................. 178
13.37.1 Typical Antistatic Agents ............................................. 178
13.38 Polypropylene .............................................................................. 178
13.38.1 Typical Antistatic Agents ............................................. 179
13.38.2 Typical Formulations ................................................... 179
13.39 Polypyrrole ................................................................................... 180
13.39.1 Typical Antistatic Agents ............................................. 181
13.40 Polystyrene .................................................................................. 181
13.40.1 Typical Antistatic Agents ............................................. 182
13.41 Polysulfone .................................................................................. 183
13.41.1 Typical Antistatic Agents ............................................. 183
13.41.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 183
13.42 Polythiophene .............................................................................. 183
13.42.1 Typical Antistatic Agents ............................................. 185
13.43 Polyvinylacetate ........................................................................... 185
13.43.1 Typical Antistatic Agents ............................................. 185
13.44 Polyvinylalcohol ........................................................................... 185
13.44.1 Typical Antistatic Agents ............................................. 186
13.44.2 Typical Formulations ................................................... 186
13.45 Polyvinylbenzylalcohol ................................................................. 186
13.45.1 Typical Antistatic Agents ............................................. 186
13.46 Polyvinylbutyral ............................................................................ 186
13.46.1 Typical Antistatic Agents ............................................. 186
13.47 Polyvinylchloride .......................................................................... 187
13.47.1 Typical Antistatic Agents ............................................. 187
13.47.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 187
13.47.3 Typical Formulations ................................................... 187
13.48 Polyvinylene Sulfide .................................................................... 188
13.48.1 Typical Antistatic Agents ............................................. 189

This page has been reformatted by Knovel to provide easier navigation.


Contents xv

13.49 Polyvinylidenechloride ................................................................. 189


13.49.1 Typical Antistatic Agents ............................................. 189
13.50 Polyvinylidenefluoride .................................................................. 189
13.50.1 Typical Antistatic Agents ............................................. 189
13.51 Polyurethanes .............................................................................. 190
13.51.1 Typical Antistatic Agents ............................................. 190
13.51.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 190
13.51.3 Typical Formulations ................................................... 192
13.52 Proteins ........................................................................................ 192
13.52.1 Typical Antistatic Agents ............................................. 192
13.52.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 193
13.53 Rubber, Natural ........................................................................... 193
13.53.1 Typical Antistatic Agents ............................................. 194
13.53.2 Typical Formulations ................................................... 194
13.54 Silicone ........................................................................................ 195
13.54.1 Typical Antistatic Agents ............................................. 195
13.54.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 195
13.55 Styrene Butadiene Rubber .......................................................... 195
13.55.1 Typical Antistatic Agents ............................................. 195
13.56 Styrene Butadiene Styrene Copolymer ....................................... 196
13.56.1 Typical Antistatic Agents ............................................. 196
13.56.2 Effect of Antistatic Agents on Polymer and Other
Additives ..................................................................... 196
13.57 Starch ........................................................................................... 196
13.57.1 Typical Antistatic Agents ............................................. 196
References ............................................................................................. 197

14. Antistatic Agents in Polymer Blends .................................... 205


14.1 Antistatic Agent Partition between Blend Component
Polymers ...................................................................................... 205

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xvi Contents

14.2 Interaction of Antistatic Agents with Blend Components ............ 207


14.3 Blends of Conductive and Non-conductive Polymers ................. 207
References ............................................................................................. 211

15. Antistatic Agents in Various Industrial Products ................ 213


15.1 Adhesives and Sealants .............................................................. 213
15.1.1 Typical Antistatic Agents and Concentrations
Used ............................................................................ 213
15.1.2 Reasons for Antistatic Agent Use ............................... 214
15.1.3 Advantages and Disadvantages of Antistatic
Agent Use ................................................................... 214
15.1.4 Effect of Antistatic Agents on Product
Properties .................................................................... 215
15.1.5 Examples of Formulations .......................................... 215
15.2 Aerospace .................................................................................... 215
15.2.1 Typical Antistatic Agents and Concentrations
Used ............................................................................ 215
15.3 Agriculture .................................................................................... 215
15.3.1 Typical Antistatic Agents and Concentrations
Used ............................................................................ 215
15.4 Automotive Applications .............................................................. 216
15.4.1 Typical Antistatic Agents and Concentrations
Used ............................................................................ 216
15.4.2 Advantages and Disadvantages of Antistatic
Agent Use ................................................................... 216
15.5 Bottles and Plastic Containers .................................................... 217
15.5.1 Typical Antistatic Agents and Concentrations
Used ............................................................................ 217
15.6 Bulk Shipping Containers ............................................................ 217
15.6.1 Typical Antistatic Agents and Concentrations
Used ............................................................................ 217
15.6.2 Reasons for Antistatic Agent Use ............................... 217
15.7 Business Machines ...................................................................... 218

This page has been reformatted by Knovel to provide easier navigation.


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