Hbrubbond

The Handbook of Rubber Bonding
(Revised Edition)
Editor: Bryan Crowther
rapra
TECHNOLOGY
Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net
First Published 2001 by
Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
2001, Rapra Technology Limited Revised and Reprinted 2003
All rights reserved. Except as permitted under current legislation no part of this publication may be photocopied, reproduced or distributed in any form or by any means or stored in a database or retrieval system, without the prior permission from the copyright holder. A catalogue record for this book is available from the British Library. Cover photograph reproduced with permission from Rubber Chemistry and Technology, 1994, 67, 4582. Copyright 1994, Rubber Division, American Chemical Society, Inc.
ISBN: 1-85957-394-0
Typeset by Rapra Technology Limited Printed and bound by Rapra Technology Limited
Contents
Introduction .......................................................................................................... 1 1 Substrate Preparation Methods ....................................................................... 3 1.1 Metal Preparation - General Techniques ................................................ 3 1.1.1 1.1.2 1.1.3 1.1.4 1.2 Structure of Metal Substrates - Metallography .......................... 3 Bonding ..................................................................................... 5 Rubber Component with Metal Support ................................... 5 Metal Pre-treatments ................................................................. 6
Pre-treatments of Plastics and Rubbers ................................................ 12 1.2.1 1.2.2 1.2.3 1.2.4 1.2.5 1.2.6 1.2.7 1.2.8 Introduction ............................................................................. 12 Studies of Pre-treatments for Plastics ....................................... 13 Hydrocarbon Rubbers with Little or No Unsaturation ............ 19 Unsaturated Hydrocarbon Rubbers ......................................... 20 Halogenated Rubbers .............................................................. 25 Miscellaneous Rubbers ............................................................ 26 Discussion ................................................................................ 27 Summary ................................................................................. 29
1.3
Bonding Rubbers to Plastic Substrates ................................................. 29 1.3.1 1.3.2 1.3.3 1.3.4 Introduction ............................................................................. 29 Plastics Substrate Preparation .................................................. 31 Degreasing and Solvent Cleaning ............................................. 35 Adhesive/Bonding Agent Choice .............................................. 36
1.4
Substrate Preparation for Bonding Using the Wet Blast Process ........... 42 1.4.1 1.4.2 Summary ................................................................................. 42 The Wet Blast Phosphating Plant ............................................. 42
1.4.3 1.4.4 1.4.5 2
Comparison Between Conventional and Wet Blast Phosphating .. 45 The Wet Blast Phosphating Plant ............................................. 46 Advantages of the Wet Blast Phosphating Plant ....................... 47
Rubber to Metal Bonding ............................................................................. 57 2.1 2.2 History................................................................................................. 57 Bond System Characteristics ................................................................ 62 2.2.1 2.2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 Adhesive Characteristics .......................................................... 62 Compound Characteristics....................................................... 64
Adhesion .............................................................................................. 66 Effective Bond Formation .................................................................... 71 Post Vulcanisation Bonding ................................................................. 73 Factors Affecting Bond Integrity .......................................................... 73 Bond Failure Types .............................................................................. 74 Bond Test Procedures ........................................................................... 76 Summary .............................................................................................. 77
Rubber to Metal and Other Substrate Bonding ............................................. 81 3.1 Introduction ......................................................................................... 81 3.1.1 3.1.2 3.1.3 3.1.4 3.1.5 3.1.6 3.1.7 3.1.8 3.2 Foreword ................................................................................. 81 History .................................................................................... 81 Types of Bonding ..................................................................... 82 The Bonding Process - An Overview ........................................ 83 Development of Bonding ......................................................... 84 Bonding Agent Reliability ........................................................ 84 The Environment and Solvent Use ........................................... 86 Methods of Reduction in Solvent Emissions ............................ 87
Substrates and their Preparation .......................................................... 87 3.2.1 Mechanical Treatment of Metals ............................................. 88
ii
Contents
3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 3.3
The Abrasion Process ............................................................... 90 Levels of metal cleanliness ....................................................... 92 Time Window .......................................................................... 93 Chemical Preparation of Surfaces ............................................ 94 Future Developments ............................................................... 96
Bonding Agent Preparation .................................................................. 97 3.3.1 Solvent-borne Bonding Systems ............................................... 97
3.4
Bonding Agent Application and Use .................................................... 98 3.4.1 3.4.2 3.4.3 Application Methods ............................................................... 98 Waterborne Bonding Systems ................................................... 98 Bonding Agent Thickness......................................................... 99
3.5
Post Vulcanisation Bonding ............................................................... 100 3.5.1 3.5.2 3.5.3 3.5.4 3.5.5 Post Vulcanisation Bonding Applications ............................... 100 Choice of Bonding Agent for Post Vulcanisation Bonding ..... 100 Rubber Substrate Preparation for PV Bonding....................... 101 Metal Substrate Preparation .................................................. 101 Methods of Application ......................................................... 101
3.6
Waterborne Bonding Systems ............................................................. 103 3.6.1 3.6.2 3.6.3 3.6.4 3.6.5 3.6.6 3.6.7 History .................................................................................. 103 Differences Between Solvent and Waterborne Bonding Agents .. 103 Suggested Spraying Equipment and Conditions ..................... 105 Application and Substrate Temperatures ............................... 105 Film Thickness ....................................................................... 106 Layover .................................................................................. 106 Progress in Performance......................................................... 106
3.7
Health and Safety in the Workplace ................................................... 109 3.7.1 3.7.2 The Safety Data Sheet ............................................................ 109 Perspective ............................................................................. 110
3.8
Bonding Agent Testing ....................................................................... 110
iii
3.9
Shelf Life Considerations ................................................................... 112 3.9.1 3.9.2 Shelf Life Categories .............................................................. 113 Procedures for Re-certification of Bonding Agents ................ 113
3.10 Troubleshooting ................................................................................. 115 3.11 Summary ............................................................................................ 120 4 Bonding Rubber to Metals with Waterborne Adhesive Systems .................. 125 4.1 Introduction ....................................................................................... 125 4.1.1 4.1.2 4.2 Solvent Elimination by the Rubber Industry .......................... 126 Techniques Necessary in Bonding of Rubber to Meet Local Environmental Pollution Limits ................................... 127
Waterborne Bonding Systems ............................................................. 127 4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.2.6 4.2.7 4.2.8 4.2.9 Structure of Organic Solvent-based Bonding Systems ............ 127 Structure of Waterborne Bonding Systems ............................. 127 Fundamentals of Waterborne Bonding Agent Application ..... 128 Waterborne Bonding Systems in Factory Usage ..................... 128 Metal Preparation - For Waterborne Bonding Systems .......... 129 Waterborne Bonding Agent Application ................................ 129 Waterborne Bonding Agent Storage Stability ......................... 130 Non Bond Advantages of Waterborne Bonding Systems ........ 130 General Comments - Waterborne Bonding Agents ................. 130
4.3
Waterborne Bonding Agents - A Factory Experience ......................... 131 4.3.1 4.3.2 4.3.3 4.3.4 4.3.5 4.3.6 Thickness Effects ................................................................... 131 Pre-bake Resistance ............................................................... 133 Primers .................................................................................. 134 Polymer Range ....................................................................... 134 Product Range ....................................................................... 134 Current Disadvantages of Waterborne Bonding Agents ......... 134
Rubber to Rubber Bonding ......................................................................... 137 5.1 Bonding of Unvulcanised Rubbers ..................................................... 137
iv
Contents
5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6 5.1.7 5.1.8 5.1.9
Tack/Autohesion .................................................................... 137 Influence of Vulcanisation System .......................................... 139 Influence of Filler Type .......................................................... 140 Effects of Plasticisers/Process Oils .......................................... 141 Effects of Tackifiers ............................................................... 141 Effects of Other Ingredients ................................................... 142 Effects of Surface Modification .............................................. 142 Effects of Surface Roughness ................................................. 144 Influence of Contact Time/Pressure/Temperature ................... 144
5.1.10 Effects of Blooming ................................................................ 145 5.1.11 Effects of Ageing .................................................................... 146 5.1.12 Testing of Tack/Autohesion Levels ......................................... 147 5.1.13 Adhesion Theories ................................................................. 148 5.2 5.3 Bonding of Vulcanised Rubbers to Unvulcanised Rubbers ................. 150 Bonding of Vulcanised Rubbers ......................................................... 152 5.3.1 5.3.2 5.3.3 5.3.4 5.3.5 5.3.6 5.3.7 5.3.8 Strip Bonding of Tyre Retreading Components ...................... 152 Effects of Strip Thickness ....................................................... 155 Effects of Surface Roughness ................................................. 156 Effects of Temperature on Bonding ........................................ 156 Effects of the Chemical Nature of Polymers/ Polymeric Additives/Surface Roughness ................................. 156 Urethane Adhesive Systems .................................................... 158 Surface Treatments to Improve Bonding ................................ 158 Effects of Contact Time/Surface Bloom .................................. 159
5.4. The Mechanism of Adhesion of Fully Cured Rubbers........................ 159 6 Rubber-Brass Bonding ................................................................................. 163 6.1 6.2 Introduction ....................................................................................... 163 Mechanism of Rubber-Brass Bonding ................................................ 165 6.2.1 6.2.2 Reviews ................................................................................. 165 Recent Mechanistic Studies .................................................... 165
6.2.3 6.2.4 6.2.5 6.2.6 6.2.7 6.2.8 6.2.9
Updated Rubber-Brass Adhesion Model ................................ 170 New Evidence for Ageing of the Interfacial Sulphide Film ..... 177 Compounding for Brass Adhesion ......................................... 180 Additives to Compounds for Brass Adhesion ......................... 181 Developments in Metal Pre-treatments .................................. 184 Developments of Novel Alloys for Bonding to Rubber .......... 189 Miscellaneous ........................................................................ 190
6.2.10 Summary ............................................................................... 190 7 Review of Tyre Cord Adhesion ................................................................... 197 7.1 7.2 7.3 7.4 7.5 7.6 8 Introduction ....................................................................................... 197 Accepted Mechanisms of Rubber-Brass Bonding ............................... 198 Ageing of the Rubber-Brass Bond ...................................................... 200 Metal Organic Cobalt Salts ................................................................ 201 The Role of Resins and Silica/Resin Systems ...................................... 205 Summary ............................................................................................ 208
Rubber to Metal Bonding Using Metallic Coagents .................................... 213 8.1 8.2 Introduction ....................................................................................... 214 Metallic Coagents .............................................................................. 215 8.2.1 8.2.2 8.2.3 8.3 Scorch Safety ......................................................................... 217 Tensile Properties ................................................................... 219 Tear Strength ......................................................................... 220
Experimental ..................................................................................... 221 8.3.1 Materials ............................................................................... 221
8.4
Results and Discussion ....................................................................... 229 8.4.1 8.4.2 Adhesion to Metals ................................................................ 229 Adhesion to Fibres and Fabrics .............................................. 235
8.5
Summary ............................................................................................ 238
vi
Contents
Rubber to Fabric Bonding ........................................................................... 241 9.1 9.2 Introduction ....................................................................................... 241 Adhesive Systems ............................................................................... 241 9.2.1 9.2.2 9.2.3 9.3 Aqueous Fabric Treatments ................................................... 241 Solvent-Based Adhesive Systems ............................................ 248 In Situ Bonding Systems......................................................... 249
Mechanisms of Adhesion ................................................................... 250 9.3.1 9.3.2 Dip/rubber Interface .............................................................. 250 Dip/textile Interface ............................................................... 252
9.4
Other Factors Affecting Adhesion ...................................................... 253 9.4.1 9.4.2 Storage of Treated Textiles ..................................................... 253 Adhesion in Service ................................................................ 254
9.5
Environmental Aspects ...................................................................... 254 9.5.1 9.5.2 9.5.3 Storage and Handling ............................................................ 254 In Process ............................................................................... 255 Wastes and Disposal .............................................................. 255
10 Bonding Rubber with Cyanoacrylates ......................................................... 259 10.1 Introduction ....................................................................................... 259 10.2 Liquid Cyanoacrylates ....................................................................... 259 10.3 Curing of Cyanoacrylates .................................................................. 260 10.3.1 Factors Affecting Cure ........................................................... 261 10.3.2 Cure Speed ............................................................................. 263 10.4 Types of Cyanoacrylate ...................................................................... 263 10.4.1 Bonding to Acidic and Porous Substrates............................... 264 10.4.2 Toughened Cyanoacrylates .................................................... 265 10.4.3 Flexible Cyanoacrylates ......................................................... 266 10.4.4 UV Curing Systems ................................................................ 266 10.5 Design Considerations ....................................................................... 266
vii
10.5.1 10.5.2 10.5.3 10.5.4 10.5.5 10.6 10.7
Minimise Peel and Deavage Loads .................................... 267 Bond Line Thickness ......................................................... 268 Special Requirements for Bonding with Cyanoacrylates .... 269 Internal and External Mould Release Agents .................... 269 Successful Joint Design ...................................................... 269
Bonding to Silicone Rubber ............................................................. 270 Environmental Resistance ............................................................... 270 10.7.1 10.7.2 Glass Bonding ................................................................... 272 Hot Strength ..................................................................... 272
10.8 10.9
Activators ........................................................................................ 274 Application Methods for Cyanoacrylates ........................................ 275 10.9.1 10.9.2 Pressure/Time Systems ....................................................... 275 Syringe Systems ................................................................. 276
10.10 Health and Safety and Handling Precautions .................................. 276 10.11 Typical Applications........................................................................ 277 10.11.1 Bonding Nitrile, Polychloroprene and Natural Rubbers .... 277 10.11.2 Bonding EPDM ................................................................. 277 10.11.3 Bonding Santoprene and Silicone Rubbers ........................ 279 10.11.4 Bonding Medical Devices .................................................. 279 10.12 Troubleshooting .............................................................................. 280 10.12.1 Blooming of Cyanoacrylates ............................................. 280 11 Bonding Silicone Rubber to Various Substrate ............................................ 285 11.1 11.2 11.3 Introduction .................................................................................... 285 Why Bond Silicone Rubber? ............................................................ 286 Material Combinations of Interest - Examples ................................ 287 11.3.1 11.3.2 11.3.3 11.3.4
viii
Silicone to Silicone Bonding (Soft and Soft) ...................... 287 Silicone to Plastic Bonding (Soft and Hard) ...................... 288 Silicone to Metal Bonding (Soft and Hard) ....................... 288 Why Use Silicone Rubber for Such Composites? ............... 288
Contents
11.4 11.5
Some Applications of Silicone Rubber Composites ......................... 290 Bonding Concepts ........................................................................... 291 11.5.1 11.5.2 11.5.3 11.5.4 Undercuts .......................................................................... 291 Primers .............................................................................. 292 Self-adhesive Silicone Rubbers .......................................... 292 The Build-up of Adhesion ................................................. 292
11.6
Bonding of Liquid Rubber (LR) ...................................................... 293 11.6.1 11.6.2 Properties of Self-adhesive LR ........................................... 297 Limitations of Self-adhesive LR ......................................... 298
11.7
Bonding of Solid Rubber (HTV) ..................................................... 299 11.7.1 11.7.2 11.7.3 Self-adhesive HTV Silicone Rubber Applications .............. 299 Applications for Self-adhesive HTV .................................. 301 HTV Used in Other Bonding Applications ........................ 303
11.8
Processing Techniques ..................................................................... 303 11.8.1 11.8.2 Liquid Rubbers in Inserted Parts Technology .................... 303 LR in Two-component Injection Moulding Technology (Two Colour Mould) ......................................................... 306
11.9
Silicone to Silicone Bonding (Soft and Soft) .................................... 308
11.10 Cable Industry ................................................................................ 309 11.11 Duration of Bonding Properties ...................................................... 309 11.11.1 Duration of Bonding - Chemically Bonded Composites .... 311 11.12 Alternatives to Injection Moulding ................................................. 313 11.12.1 Adhesives .......................................................................... 313 11.12.2 Welding ............................................................................. 313 11.12.3 Mechanical Bonding Techniques After Moulding .............. 314 11.13 Summary ......................................................................................... 314 12 Failures in Rubber Bonding to Substrates ................................................... 319 12.1.1 12.1.2 Introduction ...................................................................... 319 Incorrect Moulding Procedures ......................................... 328
ix
12.1.3 12.1.4 12.1.5 12.1.6 12.1.7 12.1.8 12.1.9
Incorrect Production Quality Testing Procedures .............. 329 Corrosion in Service .......................................................... 330 Product Abuse ................................................................... 333 Other Failure Modes ......................................................... 333 Factors Affecting Adhesion of Rubbers ............................. 334 Topography of Substrate ................................................... 335 Surface Conditions of Adherend ....................................... 335
12.1.10 Classification of Rubber According to their Wettabilities .. 336 12.1.11 Bonding - Interphase or Interface Considerations ............. 337 12.1.12 Problems in Adhesion........................................................ 339 12.2 Rubber Bonding in Power Transmission Belting ............................. 339 12.2.1 12.2.2 12.2.3 12.2.4 12.3 Introduction ...................................................................... 339 Power Transmission Belt Failure Modes ............................ 340 Adhesion Systems in Power Transmission Belts ................. 346 Adhesion Testing in Power Transmission Belts .................. 347
Undesirable Adhesion Occuring Under Service Conditions (Fixing) .. 349 12.3.1 12.3.2 12.3.3 Factors Affecting Fixing .................................................. 349 Prevention of Fixing ........................................................ 351 Other Methods of Preventing Fixing Examined Experimentally ................................................. 351
Abbreviations and Acronyms............................................................................. 357 Author Index ..................................................................................................... 363 Company Index ................................................................................................. 371 Main Index ........................................................................................................ 373
Contributors
Derek Brewis Loughborough University, Institute of Surface Science and Technology, Department of Physics, Loughborough, Leicestershire, LE11 3TU, UK. Richard Costin The Sartomer Company, 502 Thomas Jones Way, Exton, PA 19341, USA. Bryan Crowther 49 The Avenue, Bengeo, Hertford, Hertfordshire, SG14 3DS, UK. Kenneth Dalgarno School of Mechanical Engineering, University of Leeds, Leeds, LS2 9JT, UK. Steve Fulton OMG Limited, Ashton New Road, Clayton, Manchester, M11 4AT, UK. Robert Goss Henkel Loctite Adhesives Limited, Watchmead, Welwyn Garden City, Hertfordshire, AL7 1JB, UK. Jim Halladay Lord Corporation, Chemical Products Division, 2000 West Grandview Boulevard, PO Box 10038, Erie, PA 16514-0038, USA. Richard Holcroft 5 Brooklands Drive, Birmingham, West Midlands, B14 6EJ, UK. Peter Jerschow Wacker-Chemie GmbH, Johannes-Hess Strasse 24, D-84489 Burghausen, Germany. Rani Joseph Department of Polymer Science and Rubber Technology, Cochin University of Science and Technology, Cochin 682022, Kerala, India. Mike Rooke Henkel Loctite Adhesives Limited, Watchmead, Welwyn Garden City, Hertfordshire, AL7 1JB, UK.
Commercial rubbers
Berndt Stadelmann Wacker-Chemie GmbH, Johannes-Hess Strasse 24, D-84489 Burghausen, Germany. Walter Strassberger Wacker-Chemie GmbH, Johannes-Hess Strasse 24, D-84489 Burghausen, Germany. Wim van Ooij Department of Chemical and Materials Engineering, University of Cincinnati, Cincinnati, OH 45221-0012, USA. Patrick Warren Lord Corporation, Chemical Products Division, 2000 West Grandview Boulevard, PO Box 10038, Erie, PA 16514-0038, USA. Ron Woodcock 5 Lower Leicester Road, Lutterworth, Leicester, LE17 4NF, UK. David Wootton 95 Greenhill Road, Bury, Lancashire, BL8 2LL, UK Keith Worthington Chemical Innovations Limited (CIL), 217 Walton Summit Centre, Bamber Bridge, Preston, PR5 8AL, UK.
Introduction
Although many volumes of information have been published about the subject of adhesion of materials in general, it is some forty years since a publication has been devoted solely to the subject of the bonding of rubbers to various substrates. Three very successful Rapra Technology, conferences on the subject of the bonding of rubber have shown that there is clearly a need for such a publication to be devoted to this topic of wide industrial significance. Although from time to time manufacturers of bonding agent systems publish papers in trade journals there is generally a dearth of available information for the factory practitioner to consult. The subject matter for this present volume has been selected to cover a wide range of interests, both in terms of products and applications. Rubbers in many applications need the support of, or reinforcement by, a variety of materials ranging from fibres to metals. To ensure optimisation of the properties from these composites it is necessary to ensure that the optimum adhesion levels are achieved, both initially and to be maintained throughout the service life of the products. Rubbers are bonded to a variety of substrates in many products, in numerous applications, to meet the needs of the modern world. The Rubber Bonding Handbook draws together the expertise of a number of world authorities engaged in improving the bonded product to meet the ever increasing demands placed on composites and components manufactured from rubbers bonded to metals, fabrics, fibres and plastic substrates. The papers included in this volume have been written by experts in their fields, many of whom have world-renowned reputations. Thus the information they include in their chapters can be considered to be the most up-to-date, state-of-the-art discussions of their respective areas of research and knowledge. The topics range from in depth discussions of such fundamental topics as the mechanisms of bonding of rubbers to brass, bonding techniques for adhesion to fabrics through to methods of preparation of substrates and the development of bonding agent systems for adhesion to metals and plastic substrates. Bonding with silicone rubbers and cyanoacrylate adhesives for post vulcanisation bonding are also included. A section dealing with information related to adhesion, failure and other adhesion related topics such as fixing and practical reasons for a variety of bond failures, either during production or service are also covered.
The Handbook of Rubber Bonding Although there is some discussion of relevant theory in various sections of text, the emphasis in this volume has been to concentrate on the practicalities of bonding of rubbers, to themselves and substrates. It is considered that this type of information is of immediate interest to the practising technologist dealing with shop floor problems on a daily basis. It is hoped that the publication of definitive papers on the subject of adhesion of rubbers will be of considerable value to the practitioner in factories engaged in the previously seldom discussed variety of bonding applications being carried out by the rubber industry. Because of the legislation now in progress of being implemented by the rubber industry to eliminate sources of environmentally hazardous chemicals, there is information on the development and applications of waterborne bonding systems.
Acknowledgements
I would like to express my appreciation of the help and assistance given to me in the editing of this publication. To Claire Griffiths (Editorial Assistant), Sandra Hall for typesetting, to Steve Barnfield for the cover design, Rebecca Dolbey for editorial advice and particularly to Frances Powers (Commissioning Editor), for her support, patience and guidance on general editorial matters. Bryan Crowther November 2000
Substrate Preparation Methods

B. Crowther (Section 1.1) D. Brewis (Section 1.2) K. Worthington (Section 1.3) R. Holcroft (Section 1.4)
1.1 Metal Preparation General Techniques
1.1.1 Structure of Metal Substrates Metallography

There is little written about the subject of metallography with respect to the bonding characteristics of the various metals used within the hot bonding process carried out by the general goods, rubber to metal bonding profession. Some work has been carried out in the field of adhesives for aeronautical applications [1]. In general only a few of the metals or adhesives described for this type of bonding have much application in the rubber to metal bonding factory, except perhaps if one is post vulcanisation bonding. The lack of fundamental metallography studies in the hot bonding of rubbers to metals is mainly due, no doubt, to the lack of influence which the bonding technologist has in these matters. He is usually told the grade of metal to be used and proceeds to find the best way, according to current factory processes, equipment, practices and experience, to deal with the problem. He can of course discuss the nature of his problem with his bonding agent supplier, who can in turn consult his research department if the problem is really abstruse. Perhaps a better understanding of metallography would enable the factory technologist to choose the best way to pre-treat his customer-dictated metal for his factory processes, or to discuss his customers real metal requirements. To understand some of the problems associated with the achievement of good rubber to metal bonds it is worth considering some of the scenarios involving the atomic structure of metals at their surfaces. A metal, or an alloy of metals, naturally assumes a crystalline structure and it is likely that it will have a regular shape and lattice structure, with some voids in the interstices. As with rubber compounds, metals are formed by mixing a number of components together which disperse relative to each other, but never, except maybe in the case of pure metals, become one totally uniform uninterrupted phase. Most metals are used as some type of alloy, i.e.,
Commercial rubbers
The Handbook of Rubber Bonding steel consists of iron mixed with carbon in varying proportions to produce the different grades of commercial product. Also minor proportions of other metals are added to give different processing and end use characteristics to the steel, e.g., chromium, manganese, molybdenum, nickel, tungsten. The finishing processes of steels can also seriously alter the ability of adhesive to bond to them, due to the altered surface microstructure. With a pure metal its strength will depend on the size of the crystals making up its structure. In general small crystals make strong metals, whilst metals with large crystals, such as zinc, are weaker. The strength of a metal is also affected by the amount of impurity which may be present, as the impurities tend to arrange themselves at the interfaces between the crystals, thus preventing perfect crystal contact. In most metal alloys, as with rubber alloys or blends, the individual metals remain in discrete, but dispersed domains within the metal alloy structure. In an alloy the metal crystals involved, during cooling, have different shrinkage values and thus tend to move apart, allowing either voids to occur or when chemically hardened, other metals to infiltrate into these voids or interstices, at or near the surface. The individual crystals of the metals during cooling and shrinkage can join together to form chain structures, giving interlocking of the various metallic crystals. In some metal mixtures there is a mutual solubility and in these cases all crystals of the metal are the same. Although as a rubber to metal bonder one is not very interested in the metals structure within the mass of the metal, one must consider what is happening in and on its surface layers. Most metals form oxide layers on their surfaces, some of which, like iron are porous and thus continual oxygen ingress enables the oxide layer continually to increase whilst in aerobic conditions. Other metals such as aluminium form a dense oxide film which does not permit oxygen ingress and thus protects the metal underneath from further oxidation. Both metals types are being oxidised, albeit at different rates and this oxidation can be termed as a form of corrosion. Although the rubber to metal bonder must take the precautions necessary to prevent this type of corrosion continuing under his processing conditions, once the bonding agent has been applied, the condition at the metal interface becomes anaerobic and thus further oxidative corrosion is prevented (see Sections 12.1.2.2 and 12.1.5). There are a great variety and complexity of steel microstructures available to the component specifier, which complicate any cleaning procedure carried out prior to bonding. Incorrect chemical cleaning of low carbon and stainless steels, for example, can result in iron oxide smutting of the surface leaving a deposit difficult to remove entirely [1] during metal cleaning. These deposits may subsequently give an extremely weak bonding surface and, as a result a bonded product which fails easily under low working stresses in service.
Substrate Preparation Methods However, as far the rubber to metal bonder is concerned he must avoid situations which can cause galvanic corrosion, a far more serious condition, which can propagate under the bonding system to cause eventual degradation of the bond and inevitable failure. Galvanic corrosion [2] is caused by the formation of an electrolytic cell between the different metal crystals within a structure in the presence of such agents as acids and salt water. Acids can be generated from degeneration of compounding materials or cleaning and degreasing fluids (see also Section 12.1.4). Certain metals are manufactured for their ability to prevent corrosion, e.g., stainless steel, and they contain chromium to enhance their corrosion resistance. If the level of chromium used in the metals makeup is high, then the very tough layer of chromium oxide, which forms on the metals surface as the anti-corrosion layer, is also exceedingly difficult to bond to rubbers. Wherever possible therefore stainless steels to be used in conjunction with bonding systems for rubbers should contain as low a chromium level as possible.
1.1.2 Bonding
The bonding mechanisms of the multiphase systems involved in making a rubber to metal component are complex and the chemistry of the reactions involved not totally disclosed or understood. In the region of the metal contact the interactions are deemed to be a combination of mechanical and chemisorption processes. From the patent literature and some of the more recent reviews of rubber to metal bonding [3, 4], it can be seen that the primers contain a variety of halogenated rubbers and resins, which are known to have a high ability to wet out metal surfaces, thus ensuring the greatest degree of interface contact. In addition these rubbers and resins act as barriers to the migration of external corrosion catalysts of the metal surface. The resins and rubbers probably form an interpenetrating network of polymer chains within the adhesive system, thus giving strength and structure to the primer and rubber bonding coats. Bond quality depends to a large extent on the ability of all interfaces to freely exchange chemical entities. Any contamination of surfaces will upset the surface chemistry at that point and will reduce the bond strength.
1.1.3 Rubber Component with Metal Support

Engineering products for a wide range of applications are made by the use of rubbers bonded to metals during the vulcanisation of the rubber. The quality of bond achieved during the manufacture of this type of component must be of sufficient integrity, not only to be stronger than the rubber itself, but also to outlast the active life of the rubber constituent of the components. To this end, the design of the component and
The Handbook of Rubber Bonding metal part must be carefully considered to ensure that no undue stress concentrations are created in the area of the bond between the rubber and the metal. Components consisting of moulded rubber bonded to metal, carried out during high temperature vulcanisation, can have inherent stresses simply due to shrinkage of the rubber when cooling from the vulcanisation temperature and the coefficient of thermal expansion relationship of the rubber/metal combination. The shrinkage of the rubber in the system will be different for each type of rubber being used and is dependent also upon the compound hardness, or degree of filler present. Allowances for the rubber shrinkage must be made in determining the shape of the mould cavity and hence the components final shape. The environment in which the component is to work will also affect the stresses to which the rubber-metal bond will be subjected. Some oil and solvent environments will penetrate a bond at the interface and thus may weaken or destroy the integrity of the bond until the stress becomes relieved by failure. Corrosion of the metal component of the bonded unit by salt environments can also be a major problem and thus due concern and allowance must be made for the service conditions in which the rubber to metal component will be resident. Corrosion of the bonded metal under the bonding system can also occur if the metal pre-preparation is carried out with acidic degreasing fluids. Care must be taken that degreasing fluids are and remain, neutral in pH throughout their use in the application. Recovery of used solvents and redistillation can significantly change the pH of a solvent. This can be a particular problem with chlorinated solvents, where after redistillation the distillate can be acidic in nature. To effect good long-lasting bonds between rubber and metals it is essential that both materials presented to the interface be clean and free from detritus. The presence of oils and the possibility that compounding ingredients can exude or bloom from the rubber surface, before or after moulding, or during the service life of the component must also be taken into consideration and remedied.
1.1.4 Metal Pre-treatments

Metals must be suitably pre-treated for satisfactory bonds to be achieved with rubbers. Two basic methods of preparation are used: Mechanical, Chemical.
1.1.4.1 Mechanical Methods

Metals, especially the more common iron and steel types, come from the foundry and metal plate stamping shop, coated with oil, grease and most often with a generous layer of oxide and rolling mill scale formed on the exposed surfaces. Oxide films can also develop further during storage prior to use by the bonding shop. All these materials must be removed from the surfaces and from the voids in the metal, to ensure that the oils and greases which otherwise may be trapped unseen cannot exude under the increased temperature of vulcanisation, when they become more mobile or volatile. Surface oxides must be removed for they are often only loosely structured in their attachment at the metal substrate and will rupture and detach themselves under duress, causing the metal/ adhesive bond to fail. Once the original oxide layer has been removed, the freshly exposed metal will immediately start to build a new oxide film which must be minimised by rapid degreasing and application of primer/adhesive coat.
Initial degreasing
Metals must be degreased as the first step in any metal preparation process, otherwise oil and grease contamination of blasting media, chemical treatments and machinery can result in severe factory quality problems and unreliable and variable bonding. Traditionally the most usual method of grease and oil removal from the metal surface has been by degreasing in the vapour of a chlorinated solvent such as trichloroethylene or 1,1,1-trichloroethane or perchloroethylene. The chlorinated solvent used must have a neutral pH, otherwise the acidic condition can cause the initiation of underbond corrosion. Re-distilled chlorinated solvents, especially if recovery is carried out in-house, must be adequately checked for neutrality. The metal parts must dwell in the solvent vapour until such time as the metal reaches the temperature of the vapour and condensation has ceased. The solvent will have had the best opportunity to work at its most efficient in grease removal under these conditions. Direct contact with the degreasing solvent is not an efficient way of removing greases from metal surfaces, always leaving a molecular layer at least, still lying on the cleaned surface. This cleaning method should not be used for metals to be used in bonding. All air lines in the bonding shop must have oil/water filters connected to them to remove the possibility of oil/water emulsion being sprayed onto the metal surfaces before, after or during bonding agent application. Air compressors are notorious for allowing oil seepage into the pressure vessel, together with an amount of water, which then usually causes an oil/water emulsion to be formed. This emulsion in contact with cleaned metal surfaces will give corrosion or reduce bond formation to a minimum level through the deposit of a film of oil.
The Handbook of Rubber Bonding The current legislation trend and environmental pressure for the industry is to move towards the use of alternative means of removal of contaminants from the metal surfaces (see Section 1.4). Equipment is available which uses water and detergents to remove these oils and thus present a more environmentally favourable working atmosphere. The action of the detergent can be supplemented by the use of ultrasonic agitation to remove oxide flakes. These systems being water-based require efficient drying of the metals, especially in the areas between contacting metals, otherwise further oxidation of the cleaned metal will rapidly take place. Careful choice of the detergent is also necessary otherwise its residues can detract from the bond strength achievable. The water quality being used in the degreasing system final wash process will have to be determined to prevent deposit of any salts or metallic ions. The ideal final wash is with de-ionised water. Alternative solvents, if used in a vapour degreasing system must have a similar evaporation rate to that of the presently used chlorinated solvents. Otherwise too rapid evaporation of the condensed solvent on withdrawal of the metals from the solvent vapour will result in rapid surface cooling of the metal, with resultant condensation of water, especially in conditions of high humidity.
Alkaline removal of oils and greases

An alternative method of removal of the metal preparation oils and greases is to use an alkaline cleaning method. The alkaline solution is used either in dip tanks or tumbler spray units (see Section 4.1). The strength of alkaline, the temperature used and the necessary dwell time in the solution to remove the amount of grease encountered will be determined in individual factories. The length of time required for oil and grease removal can be anything up to two hours. The alkaline tanks have to be followed by water rinse tanks to remove the alkaline dip from the metals, followed by drying.
Solvent dip methods for large scale removal of greases

Solvent dip methods are generally expensive to run and do not usually, unless a number of dip tanks are used, completely remove oils and greases from the metal surfaces. Contaminants are easily carried from tank to tank and it is difficult to ascertain whether the metal surface is completely cleaned after its passage through the tank series. This method would not normally be used for anything other than small scale operations. Fast drying solvents such as methylene chloride and acetone evaporate so quickly that they lower the temperature of the metal surface and water condenses.
Removal of surface oxides

Metals, after degreasing, have to be blasted with a sufficiently abrasive material to remove the surface oxidation layer. The usual medium used for ferrous substrates is steel or chilled-iron grit to BS EN ISO 11124-4 grades G12 to G24 [5] (see also Section 4.2.2). Alumina or other non-ferrous grits such as quartz sand and carborundum may be used on ferrous metals, but their use on non-ferrous metals is essential to prevent the possible formation of galvanic cells. Initially impingement of the metal surface with abrasive grit has the effect of gouging the surface of the steel to give a larger surface area for bonding, but with use the grit wears and its efficiency decreases. The type of grit used must be coupled to the type of metal being treated. Incorrect grit/ metal combinations can lead to formation of galvanic cells remaining on the surface of the blasted metals and the commencement of underbond corrosion. Grits larger than about 30-50 mesh diameter soon lose their irregularities and grittiness, effectively turning into shot at which stage they must be discarded. The hardness of the steel grits should be a Rockwell C hardness of 60 65. Iron or steel shot should not be used as these tend to give cavitation of the blasted metal surfaces, followed by peaning over of the sharp metal pinnacles, often trapping loose shot, blasted material, etc., in the peaned over cavities. These cavitations and their contents cause weaknesses and possible underbond corrosion sites, resulting in ultimate failure in service. The service life of the blasting media should be established for efficiency and quality of surface finish. Grit in use should be cleaned of dust resulting from removed oxide scale and its own degradation products and be downgraded or discarded if it becomes too worn. Revolving drum blast machines give the best production efficiency for metals which are stout enough to resist damage from the tumbling action involved. The metal parts are tumbled on a rubber belt inside a revolving drum whilst being bombarded with the abrasive medium. Once the metal surface has been adequately cleaned of oxide contamination, dusted off and once more degreased, it is vital that the application of a bonding agent primer coat be carried out as quickly as possible to ensure that the re-oxidation of the metal surface is kept to a minimum. Ambient temperature, humidity and dust must all be controlled if the optimum bond strength is to be achieved. To consistently ensure optimum bond quality, metal components, whether unprimed or primed, should be kept in enclosed cabinets. At no time should cleaned and degreased metals be handled with bare hands. Human skin, however clean it may appear, always carries a surface layer of oils and fats, which are bond killers. Neither should metals, whether in the just cleaned state, or
The Handbook of Rubber Bonding treated with bonding agent, be handled with press gloves. Press gloves are usually heavily contaminated with a variety of materials, from oil, to mould release agents and sweat. Clean, frequently discarded cotton gloves are the best protection for handling metals. They should not be allowed to become dirty and sweat ridden.
1.1.4.2 Chemical Methods

The alternative metal pre-treatment processes to grit blasting use a variety of different chemical routes. It is sufficient to say here that these can be very efficient, but do occupy rather large factory floor areas and can, if not controlled correctly give variable quality of prepared surface. The usual chemical pre-treatment systems consist of acid etching of the surface followed by several water dips and subsequent phosphate or in some circumstances cadmium plating and passivating (render inert). Many of these treatments will have been carried out by the metal processor and are not the rubber bonders processes.
Treatments for stainless steels (see also Section 3.3)

There are various systems for the pre-treatment of stainless steels which consist of treating the metal surface with strong acids to attack crystal grain boundaries in the alloys and chromium poor regions around chromium carbide particles. All the methods give surface roughness to the stainless steel which enhances the bond to the adhesive. Mixtures of nitric, hydrofluoric, sulphuric or chromic acid are suggested as most suitable. However, the nature of the substrate alloy and the heat treatment experienced all have a bearing on the bondability of the metal.
Phosphate coating (see also Sections 1.2, 3.3 and 4.2.5)

Steel is often phosphate coated for use within the engineering and decorative laminate industries to reduce corrosion. Iron or zinc phosphate can be used. However, although used for some years as a corrosion protection technique for rubber to steel bonding, it can be difficult to control the process, with a resultant variable thickness of phosphate deposit of varying crystalline structure. If too thick a phosphate layer is obtained it becomes too friable and lacking in the cohesive integrity required to maintain a rubber to metal bond under load during service. If only a moderate phosphate coat is produced it is often necessary to passivate the areas of steel, only minimally covered or lacking in a coating of phosphate, by treating with chromic acid to form chromium oxide to prevent corrosion. However, chromium oxide does not readily react with a bonding agent (see Section 3.1). Chromic acid is a restricted material and alternative materials can be recommended by bonding agent suppliers for the passivation or sealing of the phosphate coating.
10
Substrate Preparation Methods The nature of the phosphate deposited on the surface of the steel depends to a large extent upon the nature of the microstructure of the steels and the orientation of its underlying crystal lattice. Hardened steels having a martensite structured surface (consisting of interlacing rectilinear fibrous elements arranged in a triangular shape) support a fine flake phosphate structure. Cold-rolled steel can, having acquired a different surface orientation structure during the rolling process, acquire a lumpy large flake phosphate structure, which is easily broken apart under service stress. Any water going to drain from these processes is a potential pollution hazard and must be tested for zinc content, as this is a hazardous material. Any zinc present must be removed or limited to 1 2 parts per million.
Zinc coating or galvanising

To be effective the zinc coating must be hot dipped onto the freshly cleaned metal, to give a galvanised finish. Bonding to this finish is not easy, but sometimes demanded by the component specifier. The crystalline structure of the galvanised zinc and its dipped coating thickness, can result in the flaking off, under stress, of some of the coating, resulting in bond failure (see also Section 1.1.1). The recommended treatment [6] for cleaning a galvanised finish is a) degrease metal part b) abrade the galvanised surface with grit c) degrease then apply adhesive as soon as possible or a) immerse in a solution of 20 parts by weight concentrated hydrochloric acid with 80 parts by weight de-ionised water, for 2 4 minutes at 25 C b) rinse thoroughly in cold, running de-ionised water c) dry for 20 30 minutes in 70 C oven d) apply adhesive as soon as possible The second method of zinc coating is more widely used.
Zinc sheradising
A method used to give what is in effect a fused zinc surface to a steel component can be specified which gives very good environmental protection for the steel component.
11
The Handbook of Rubber Bonding The steel part to be bonded is baked whilst being tumbled in zinc dust. The process is not generally suitable for delicate metal parts and causes problems with zinc build-up in screw threaded components (the latter must be protected by a sleeve or require a die running down the thread to clear it). After treatment exposed zinc surfaces do of course oxidise if stored incorrectly, but this is not usually a problem. The oxide forms after both methods of zinc coating.
Aluminium - anodising
Aluminium is usually electrolytically anodised, in the presence of an acid, either sulphuric, chromic or phosphoric, to give a tough resistant oxide film, which usually forms good bonds with the usual bonding systems. The anodising must be carried out with care and with a mind to the type of crystalline structure being formed on the aluminium surface. A uniform reticulated structure is desired, not a microscopically fragmented rippled surface, sometimes called ice flows [7], which are unstable, easily fractured, and therefore too unstable to maintain good adhesive quality. If anodising is to be carried out by a custom plater he will need to be informed of the type of anodised structure desired. N.B. The final stages of any wet metal preparation process for metals to be bonded to rubber is to ensure that all chemicals used in the processes have been removed in the final water rinse tank, and then to ensure that all faces of the metal parts are fully dried prior to bonding agent application. All warehouse metal storage areas must be held at least 5 10 C above the dew-point and ideally as near to ambient temperature in the bonding agent application shop which should be in the region of 18 22 C minimum.
Metal preparation - for waterborne bonding systems

Although the general principles used for solvent-based adhesives apply, the cleaning of metals for the application of waterborne bonding systems becomes much more critical. Scrupulously clean metals are vital, to ensure maximum wettability of the prepared metal bonding surface. Lord Corporation [8] suggest that calcium modified phosphating of metals is preferable to conventional grit blasting with its potential for re-infecting the metal surface after initial degreasing by using contaminated grit. Proper housekeeping should eliminate such problems.
1.2 Pre-treatments of Plastics and Rubbers

1.2.1 Introduction
In many cases, rubbers are joined to other materials during the process of vulcanisation. However, in other cases, rubbers are joined to other materials after vulcanisation. With this
12
Substrate Preparation Methods second group, it is often necessary to pre-treat the rubbers before bonding. Pre-treatments range from physical methods such as a solvent wipe or abrasion to chemical methods such as treatment with trichloroisocyanuric acid (TCICA). Physical methods may remove cohesively weak layers from the polymer. This is essential to good bonding unless these layers can be absorbed by the adhesive. However, physical methods will only be effective if the underlying rubber possesses suitable groups which can interact strongly with the adhesive. Chemical methods may also remove weak layers or chemically modify them so that they are more compatible with the adhesive; in addition chemical methods may roughen a surface. However, an effective chemical method will also modify the chemistry of the rubber so that the interaction with the adhesive is increased. In general, rubbers contain a greater variety and quantity of additives than plastics; fifteen components in a particular formulation is quite common. These additives or compounding ingredients as they are often called, may well create a cohesively weak layer on the rubber surface. On the other hand, plastics usually contain a small number of additives and usually in relatively low concentration. Over the last 50 years many methods have been developed to pre-treat plastics and rubbers. Partly because of the much simpler formulations, pre-treatments for plastics have been the subject of much greater scientific interest. Our understanding of pretreatments for plastics is therefore much greater than that for rubbers. Some of the key studies on pre-treatments of plastics will therefore be outlined in Section 1.2.2. Pre-treatments for rubbers have been developed on an empirical basis but some scientific studies of successful pre-treatments have been undertaken. Methods for different rubbers will be reviewed in Section 1.2.3. Rubbers will be considered in groups, namely hydrocarbons that possess little unsaturation, unsaturated hydrocarbons, halogenated rubbers and miscellaneous materials.
1.2.2 Studies of Pre-treatments for Plastics

These studies may seem out of context in a book concerned with bonding of rubber but the great deal of work carried out with plastics can be used to understand the problems of rubbers. Some of the most important pre-treatments for plastics were developed in the 1950s. These include the corona and flame treatments for polyolefins [9, 10, 11, 12, 13] and the use of sodium complexes for fluorinated polymers [14 17]. The plasma treatment was developed somewhat later [18, 19], as was halogenation [20, 21]. It was suspected that these treatments were chemically modifying the surfaces of the plastics but there was little direct evidence as the analytical methods available at the time were not 13
The Handbook of Rubber Bonding sufficiently surface-sensitive. However, in the 1970s a new method for studying surface chemistry became available, namely X-ray photoelectron spectroscopy (XPS) which is also known as electron spectroscopy for chemical analysis (ESCA). This method is able to characterise and quantify the chemical changes caused by pre-treatments. XPS analyses the first few atomic layers of a material. This is important as some pre-treatments only modify a few nanometers of a polymer. Reflection infrared techniques in the 1970s were often unable to detect changes to the surface chemistry of polymers caused by the pre-treatments. Three of the earliest pre-treatment studies were by Dwight [15], Collins [22] and Briggs [23]. Dwight treated polytetrafluoroethylene (PTFE) and fluorinated ethylene-propylene copolymer (FEP) with sodium in liquid ammonia and sodium naphthalenide in tetrahydrofuran (THF). X-ray photoelectron spectroscopy showed extensive defluorination of the polymers together with formation of carboncarbon double bonds and various oxygen-containing groups. Collins treated PTFE with ammonia and air plasmas. Again, XPS showed extensive defluorination and in the case of the ammonia plasma, nitrogen containing groups were introduced. Briggs [23] was the first to quantify the chemical modification caused by a pre-treatment. Briggs studied the changes caused by chromic acid etching of low density polyethylene and polypropylene. Some of the results are given in Table 1.1. Angular variation studies, i.e., the angle of incidence of the X-ray beam was varied, showed that in the case of polypropylene, the depth of the chemically modified layer was only a few nanometers.
Table 1.1 XPS data for polyolefins treated with chromic acid [23]
Polymer LDPE Treatment None 1 min/20 C 6 h/70 C None 1 min/20 C 6 h/70 C Surface composition (atom %) C 99.8 94.4 85.8 99.8 93.4 94.0 O 0.2 5.2 13.1 0.2 6.3 5.7 S 0.4 1.1 0.3 0.3
PP
NB: The sulphur originates from the attack of the polyolefin by the sulphuric acid present in the chromic acid LDPE: low density polyethylene PP: polypropylene C: carbon O: oxygen S: sulphur Reproduced with permission from D. Briggs, D. M. Brewis and M. B. Konieczko, Journal of Materials Science, 1976, 11, 7, 1270. 1976, Kluwer Academic Publishers
14
Substrate Preparation Methods A given pre-treatment may result in the introduction of several different chemical groups. There are two methods by which these groups may be quantified and both involve XPS. The first method involves derivatisation reactions and the second method the use of high resolution spectra. The basic idea behind the derivatisation method is to use several reagents each of which will react with only one of the groups introduced by the pre-treatment. There are two other requirements. Each reagent should introduce an atom, e.g., fluorine, that is not already present in the surface and each reaction should proceed to 100% conversion. The method is illustrated by the work of Gerenser [24] where some corona treated polyethylene was derivatised. The reagents and derivatisation reactions are shown in Figure 1.1 and the results of the experiments are shown in Table 1.2.
Figure 1.1 Derivatisation reactions to identify functional groups introduced by pretreatments; a) peroxide groups reacting with sulphur dioxide, b) alcohol group reacting with hexafluoroacetic anhydride, c) carbonyl group reacting with hydrazine, d) epoxide group reacting with hydrogen chloride, e) carboxylic acid group reacting with tertiary amine. (Reprinted from L. J. Gerenser, J. F. Elman, M. G. Mason and J. M. Pochan, Polymer, 1985, 26, 8, 1162. 1985, with permission from Elsevier Science)
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Table 1.2 Quantification of surface functionalities after corona treatment using derivatisation
Functional group Group conc. X 102 * Initial 1.2 Washed 0.9
OOH
OH
1.7
1.1
1.8
0.9
O C C
2.3
1.1
O C OH
1.6 0.8 13.8 ~18
0.8 0.4 7.7 ~10
NO3 Total [O] tagged Actual [O] incorporated
Footnote: Allowing for the fact that some of the groups contain more than one oxygen atom, it can readily be calculated that the concentration of oxygen atoms involved in the derivatisation reactions was 13.8%; this is the amount of oxygen tagged. The actual amount of oxygen incorporated the corona treated surface was found by XPS to be 18%. This means that other oxygen-containing groups were present and/or the reactions with the above groups did not go to completion. *Moles of functional species per unreacted initial carbon atom Reprinted from L. J. Gerenser, J. F. Elman, M. G. Mason and J. M. Pochan, Polymer, 1985, 26, 8, 1162. 1985, with permission from Elsevier Science
The second method to quantify the chemical groups introduced by a pre-treatment involves obtaining a high resolution spectrum of the photoelectrons from the C1s core level and resolving this into the various contributions. This approach is illustrated by Beamson [25] who examined a rubber-modified polypropylene which had been subjected to a corona discharge treatment. The high resolution C1s spectrum is given in Figure 1.2 and
16
Corona treatment after derivatisation
the information on the groups introduced is given in Table 1.3. This method is much quicker than the derivatisation approach but requires an instrument with very good energy resolution and great care in attribution of the various peaks.
Figure 1.2 High resolution C1s spectrum of corona treated polypropylene [25]
Table 1.3 Assignment of peaks for corona treated polypropylene [25]

Peak no. 1 2 3 4 5 6 Position (eV) 285.0 286.5 287.1 288.1 288.9 289.5 Area (%) 91.7 1.2 2.3 2.3 1.2 1.3 Assignment C-C, C-H C-O C-O-O C=O COOH O=C-O-C=O *
* The assignment at 289.5 eV is tentative
17
The Handbook of Rubber Bonding Strobel [12] compared the effectiveness of various gas-phase reactions for polypropylene, by determining how much oxygen was introduced into the polymer surface (the O:C atomic ratio) in a given time. These results are summarised in Table 1.4. It can be seen that to achieve a given level of chemical modification, flame, corona and plasma require much shorter treatment times than ozone or UV or a combination of UV plus ozone. The pre-treatments described above represent just a few of the many studies relating to the mechanisms of pre-treatments for plastics. However, it is clear that much is known about pre-treatments of plastics relating to: Quantification of the chemical changes caused by pre-treatments, The depth of the chemical modification, Identification and quantification of chemical groups, The rate of chemical modification. In contrast, much less work has been done relating to the mechanisms of pre-treatments for rubbers.
Table 1.4 Surface analysis of treated polypropylene films [12]

Treatment None Corona (1.7 J/cm2) Corona (0.17 J/cm2) Flame Remote air plasma* Ozone UV/air UV/air plus ozone Exposure time (s) 0.5 0.05 0.04 0.1 1800 600 600 XPS O:C atomic ratio 0.0 0.12 0.07 0.12 0.12 0.13 0.08 0.14
*The plasma was produced by a microwave generator and passed 100 mm down a tube onto the polymer surface Reproduced with permission from M. Strobel, M. J. Walzak, J. M. Hill, A. Lin, E. Karbashewski and C. S. Lyons, in Polymer Surface Modification, Ed., K. L. Mittal, VSP, Utrecht, 1996, 233. 1996, VSP BV
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Surface analysis
1.2.3 Hydrocarbon Rubbers with Little or No Unsaturation 1.2.3.1 Ethylene-Propylene Rubbers

Ethylene-propylene rubbers (EP) have low total surface energies with small polar components. As would be expected, the adhesion of paints and adhesives to untreated EP is poor. To achieve good adhesion to EP, the introduction of suitable functional groups is necessary unless a diffusion mechanism can operate. Bragole [26] found that UV treatment of EPDM coated with a thin layer of benzophenone resulted in large increases in the adhesion of acrylic, epoxy and urethane paints to the polymer. Ellul [27] subjected EPDM/polypropylene and natural rubber/polypropylene blends to various halogenation treatments, namely fluorine/carbon dioxide, sodium hypochlorite/ acetic acid and bromine water. With the natural rubber blend, there was a substantial uptake of fluorine, chlorine and bromine in the surface regions as indicated by energy dispersive X-ray analysis and with all three pre-treatments the adhesion to an acrylic tape was greatly enhanced. In contrast, with the EPDM blend, fluorine was the only reagent which reacted with the rubbers and only this treatment resulted in a significant increase in adhesion to the acrylic tape. The above results can be explained in terms of the different concentrations of carboncarbon double bonds in the two blends. Substantial incorporation of chlorine and bromine could occur with the natural rubber-polypropylene blend but not with the EPDM blend. However, fluorine gas will react readily with saturated hydrocarbons [28, 29] and therefore the incorporation of fluorine into the EPDM blend is not surprising. Lawson [30] using X-ray photoelectron spectroscopy (XPS) found that trichloroisocyanuric acid (TCICA) in ethyl acetate did not chemically modify EPDM. Lawson [31] also found that a corona treatment improved the wettability of EPDM as indicated by glycerol contact angles and the use of a series of formamide/2-ethoxyethanol mixtures (ASTM D2578 [32]). However, the contact angles increased significantly over a period of one hour, indicating molecular rearrangement with the polar groups introduced by the pre-treatment tending to move to the bulk of the rubber. No improvement in a peel test involving a polyurethane coating was observed. Minagawa [33] treated an EP rubber with UV and sputter etching. Large increases in adhesion were reported. However, the treatment times were long, being 10 minutes for ion etching and one hour for the UV treatment. Scanning electron microscopy (SEM) indicated the two methods caused considerable roughening of the surface. XPS and Fourier transform infrared analysis (FTIR) indicated the introduction of substantial quantities of oxygen-containing functional groups. Kondyurin [34] noted only modest improvements, at best, after treating EPDM with UV, despite clear infrared evidence for the formation of hydroxyl and carbonyl groups after treatment.
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1.2.3.2 Butyl Rubber

Butyl rubber consists of 95% of isobutylene units with a small quantity of isoprene which permits crosslinking via sulphur vulcanisation. Butyl rubber has a low surface energy and in addition organic components with a low cohesive strength may exist on the surface. In one study [35] butyl rubber was subjected to several treatments which normally cause substantial chemical modification to polymer surfaces. The treatments included chromic acid etching, corona discharges, flames, bromination, UV radiation and potassium permanganate. Most of the treatments had little effect on the adhesion to an epoxide. It was concluded that much chain scission occurred with the result that suitable functional groups were not introduced in sufficient quantity into long polymer chains. Such chemical modification is necessary for good adhesion unless a diffusion mechanism is operating.
1.2.4 Unsaturated Hydrocarbon Rubbers 1.2.4.1 Natural Rubber

Natural rubber (NR), being essentially a hydrocarbon, has a low surface energy. Some of the components in a formulated rubber, such as zinc oxide and carbon black, may substantially increase the surface energy, whereas organic additives such as extender oil and antioxidants may migrate to the surface and create a potentially weak boundary layer. Pettit and Carter [36] found that chlorine gas, acidic sodium hypochlorite and an organic chlorine donor in a organic solvent all much improved the peel strengths of joints involving NR and a polyurethane adhesive. Oldfield and Symes [37, 38] found that aqueous or organic-based chlorination gave much higher joint strengths than a solvent-wipe, abrasion or cyclisation (see Table 1.5). Oldfield and Symes used X-ray fluorescence, infrared analysis and contact angle measurement to study the TCICA treatment. X-ray fluorescence showed the amount of chlorine introduced into the polymer increased with the TCICA concentration; with a 3% TCICA solution, they estimated the chlorine content in the treated NR was 16.7% w/w. Reflection infrared analysis indicated that chlorine substituted at the allylic position in the polymer backbone. Substantial improvements in wettability were achieved especially if the concentration of TCICA was at least 0.8%. Lawson [30] pre-treated various rubbers, including NR, with a 3% w/v solution of TCICA in ethyl acetate and used XPS to study the chemical changes caused by the pre-treatment. In agreement with Oldfield, they concluded that the chemical modification was mainly substitution rather than addition at the carboncarbon double bond.
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Table 1.5 Effect of pre-treatment on the peel strengths (N mm-1) of NR-epoxide-NR [37] Pre-treatment Toluene wipe Abrasion on grinding wheel Acidified hypochlorite Cyclisation TCICA in ethyl acetate Peel strength 0.1 1 10 1 18 Locus of failure I I R I R
I - apparent interfacial ; R - cohesive in rubber Reproduced with permission from D. Oldfield and T. E. F. Symes, Journal of Adhesion, 1983, 16, 2, 77. 1983, Gordon and Breach Publishers
Extrand [39] treated NR surfaces in an acidified sodium hypochlorite solution and used contact angle measurements and reflection FTIR to study the changes caused by the chlorination. They studied pure NR, a peroxide cured formulation and a conventionally cured formulation. Contact angles of glycerol on the rubber surfaces reduced after chlorination as shown in Table 1.6.
Table 1.6 Effect of chlorination on the contact angles between glycerol and various rubber surfaces [39] Substrate Contact angle () Before treatment Pure rubber Peroxide cured Conventionally cured 64 46 82 After treatment 11 30 30
Reproduced with permission from C. W. Extrand and A. N. Gent, Rubber Chemistry and Technology, 1988, 61, 4, 688. 1988, Rubber Division, American Chemical Society
Peel strengths 21
The Handbook of Rubber Bonding With regard to the infrared study, bands at 660, 750 and 1260 cm-1 were assigned to the effects of chlorination. In addition, bands at 780, 916 and 1410 cm-1 were almost certainly due to chlorination. Kusano [40] found that neither corona nor plasma treatments improved peel strength with a polyurethane adhesive despite improved wettability as indicated by water contact angles. FTIR indicated substantial oxidation after the corona treatment but only minor oxidation after the plasma treatment.
1.2.4.2 Styrene-Butadiene Copolymers

Styrene-butadiene rubber has a low surface energy, but this may be considerably increased by the incorporation of various components. Organic additives such as antioxidants will tend to migrate to the surface thus creating a potential weak boundary layer. Pettit [36] found that treatment of SBR with chlorine gas, acidified sodium hypochlorite or an organic chlorine donor in an organic solvent resulted in large increases in peel strength for SBR-polyurethane-SBR joints. Oldfield [37] found that physical treatments were inferior to three chemical pre-treatments (see Table 1.7).
Table 1.7 Effect of pre-treatments on the peel strengths (N mm-1) of SBR-epoxide-SBR joints [37]
Pre-treatment Toluene wipe Abrasion on grinding wheel Acidified hypochlorite Cyclisation TCICA in ethyl acetate Peel strength 0. 2 1 12 12 11 Locus of failure I I R R R
I - apparent interfacial; R - cohesive within rubber Reproduced with permission from D. Oldfield and T. E. F. Symes, Journal of Adhesion, 1983, 16, 2, 77. 1983, Gordon and Breach Publishers.
22
Substrate Preparation Methods Using X-ray fluorescence, they estimated the chlorine concentration in the first few microns of the SBR after treatment with TCICA at various concentrations. With a 3% solution, the resulting chlorine concentration was 16.1% w/w. Pastor-Blas [41] found that physical treatments such as abrasion did not result in significant increases in the peel strengths obtained with a polyurethane adhesive. On the other hand, treatment with TCICA in ethyl acetate resulted in large increases in peel strength. On the basis of the relative amounts of chlorine and nitrogen introduced into SBR, Lawson [30] concluded that both substitution and addition reactions were significant when this rubber was treated with TCICA in ethyl acetate. Similar results were obtained with polybutadiene. Pastor-Blas [42] studied the effect of TCICA concentration in ethyl acetate. For solutions up to 2% w/w mainly chlorinated hydrocarbon and CO species were reported. At between 2 and 5% w/w an excess of unreacted TCICA was indicated while above 5% w/w there was a detrimental effect on adhesion due to a weak boundary layer consisting of isocyanuric acid. Pastor-Blas [43] treated an SBR formulation with TCICA solutions in ethyl acetate having concentrations ranging from 0.5 7% by weight. The chemical changes caused by the pre-treatments are shown in Table 1.8. Rubber strips were bonded with a solvent-based polyurethane (PU) and the joint strengths determined in a T-peel test. After peeling, the test pieces were examined using a variety of techniques; XPS and FTIR confirmed that the treatment introduced various chemical groups. The peel strengths were obtained after treatments with 0.5, 2 and 7% w/w. The highest peel strength was obtained with the 2% solution.
Table 1.8 XPS studies of SBR treated with solutions of TCICA in ethyl acetate [43] Wt% concentration of TCICA 0 2 7 Surface analysis (atom %) C 92.27 92.7 91.5 O 2.8 4.3 4.6 Si 1.5 1.0 0.7 N 1.0 1.9 Cl 0.8 0.9 S 0.2 0.4
Reproduced with permission from M.M. Pastor-Blas, J.M. Martn-Martnez and J.G. Dillard, Journal of Adhesion, 1997, 62, 1/4, 23. 1997, Gordon and Breach Publishers.
Peel strengths
23
The Handbook of Rubber Bonding In a related publication, treatments with fumaric acid in a butan-2-ol/ethanol mixture and TCICA in butan-2-ol were compared [44]. In general, the TCICA was more effective at enhancing the peel strength achieved with a solvent-based PU adhesive. Infrared analysis indicated the treatments were probably effective by removing zinc stearate (reduction in peak at 1540 cm-1) and the introduction of carbon-oxide functionalities (1704 cm-1 and 1670 cm-1 for the TCICA and fumaric acid, respectively). With TCICA, CCl bonds were also observed. Pastor-Sempere [45] treated two styrene-butadiene rubbers with fumaric acid in a butan2-ol/ethanol mixture. This resulted in improved adhesion in both cases, but the improvement with one formulation was significantly greater than the other. The lower peel strength was attributed to the presence of paraffin wax and zinc stearate. Roughening prior to treatment with fumaric acid resulted in additional improvements with both rubbers. Infrared analysis indicated that the fumaric acid was effective by introducing C=O bonds and by reducing the concentration of zinc stearate. In addition, the fumaric acid caused a roughening of both rubbers. Later Pastor-Blas [46] demonstrated that high concentrations of TCICA could lead to the formation of weak boundary layers. Treatment of two SBR materials with a 7 wt% solution of TCICA in ethyl acetate resulted in poor peel strengths unless the treated surfaces were vacuum dried for one hour at 1.34 Pa. Other methods have been shown to considerably improve the bondability of SBR materials. Aqueous solutions of an organic chlorine donor or the use of an electrochemical method resulted in large increases in peel strength with a water-based PU adhesive [47]. Kusano [40] found that corona and plasma treatments resulted in large increases in peel strength with a PU adhesive. Lawson [31] reported that a 10 second corona treatment improved the water wettability of an SBR. He also reported cracking of the rubber which he ascribed to the ozone generated in the discharge. Styrene-butadiene block copolymers SBS thermoplastic rubbers have a low surface energy. Therefore, to achieve good adhesion to SBS a chemical pre-treatment may be necessary. A complicating factor is that migratory organic additives may lead to a weak layer. Pettit [36] found that treatment of SBS with chlorine gas, acidified sodium hypochlorite or an organic donor in an organic solvent resulted in large increases in peel strength with a polyurethane adhesive. As with SBR, aqueous solutions of an organic chlorine donor and an electrochemical method were also effective with SBS [47]. Pastor-Blas [48] treated SBS with TCICA solutions (0.5, 2 or 7 wt%) in ethyl acetate. The SBS was bonded with a PU and the joint strengths determined in a T-peel test. The failed surfaces, after peeling, were examined by a variety of techniques including XPS and FTIR.
24
Substrate Preparation Methods It was concluded that the highest strength (3.3 N mm-1) was obtained with the 0.5% solution. It was concluded that the stronger solutions weakened the surface regions. FTIR and XPS showed that the treatment introduced chlorine and oxygen functionalities.
1.2.5 Halogenated Rubbers

Introduction of bromine and chlorine atoms in hydrocarbon polymers will enhance adhesion. In the case of PE, introduction of bromine to a Br:C ratio of 0.05:1 resulted in high adhesion to an epoxide adhesive [49]. However, the quantity of halogen in bromoand chloro-butyl rubbers is low and poor adhesion to these polymers is not unexpected especially if organic additives are present on the surfaces. Oldfield [37] only obtained modest adhesion to untreated bromobutyl rubber (see Table 1.9). Of the treatments they investigated only TCICA in ethyl acetate resulted in very high peel strengths, although aqueous chlorination gave a substantial improvement. Using X-ray fluorescence, Oldfield and Symes found that the uptake of chlorine into bromobutyl rubber was very much less than that observed with NR, SBR and nitrile rubber, as would be expected from the relative number of carboncarbon double bonds using XPS. Lawson [30] found chlorobutyl rubber did not take up any measurable amount of chlorine in treatment with TCICA in ethyl acetate. The reason for the large improvement in bondability with bromobutyl observed by Oldfield is unclear. It may be that the TCICA was acting as an oxidising agent rather than a chlorinating agent. However, Lawson did not observe any introduction of oxygen-containing groups with chlorobutyl rubber.
Table 1.9 Effect of pre-treatments on the peel strengths (N mm-1) of bromobutyl rubberepoxidebromobutyl rubber joints [37] Pre-treatment Toluene wipe Abrasion on grinding wheel Acidified hypochlorite Cyclisation TCICA in ethyl acetate Peel strength 1 1 3 0.1 20 Locus of failure I I I I R
I - apparent interfacial; R - cohesive in rubber Reproduced with permission from D. Oldfield and T. E. F. Symes, Journal of Adhesion, 1983, 16, 2, 77. 1983, Gordon and Breach Publishers.
25
The Handbook of Rubber Bonding Polychloroprene (CR) has much more chlorine than the chlorobutyl rubber examined by Lawson and good adhesion to untreated CR would be expected provided there was no weak layer was on the surface. If such layers exist a suitable solvent treatment or abrasion should result in good adhesion. Cyclisation has been recommended as a pre-treatment [50, 51]. Lawson noted a large uptake of chlorine, nitrogen and oxygen on treatment of polychloroprene with TCICA, indicating addition across the carboncarbon double bond. Lawson [31] reported that a corona discharge treatment of CR increased its surface energy, but did not improve the peel strength with a polyurethane coating. Minagawa [32] reported large increases in adhesion with CR after UV irradiation or sputter ion etching. However, the treatment times were long, being 10 minutes with ion sputtering and one hour with the UV treatment. SEM indicates that the two methods caused considerable roughening of the surface. XPS and FTIR indicated the introduction of substantial quantities of oxygen-containing groups.
1.2.6 Miscellaneous Rubbers 1.2.6.1 Silicone Rubber (see also Chapter 12)
Adhesion to untreated silicone rubber is difficult. The poor adhesion may be due to a low surface energy (approximately 24 mJ m-2) or a layer of low cohesive strength or a combination of these two factors. Plasma treatment has been shown to substantially improve the wettability of silicone rubber [50-57]. Peel strengths were measured in one study and found to be much increased by plasma treatment [53]. Swanson [58] found that coating a silicone rubber with photoactive reagents and then exposing the surface to UV resulted in a large increase in joint strengths obtained with a cyanoacrylate adhesive. Combette [59] reported that microwave or radio frequency plasma treatment of silicone rubber with a gas rich in oxygen gave high peel strengths with an epoxide adhesive.
1.2.6.2 Nitrile Rubber

Nitrile rubber is moderately polar and good adhesion would be expected between a polar adhesive like an epoxide and the untreated polymer provided no weak boundary layers were present. This was found to be the case by Oldfield [37] as can be seen in Table 1.10. High adhesion values were obtained with a solvent wipe. Cyclisation and TCICA treatments resulted in large increases in adhesion. X-ray fluorescence indicated substantial uptake of chlorine in the latter case [37]. Peel strengths 26

Table 1.10 Effect of pre-treatments on the peel strengths (N mm-1) of nitrile rubber-epoxide-nitrile rubber joints [37] Pre-treatment Toluene wipe Abrasion on grinding wheel Acidified hypochlorite Cyclisation TCICA in ethyl acetate Initial strength 8 5 8 18 21 Locus of failure R I R R R
I - apparent interfacial; R - cohesive in rubber Reproduced with permission from D. Oldfield and T. E. F. Symes, Journal of Adhesion, 1983, 16, 2, 77. 1983, Gordon and Breach Publishers.
1.2.6.3 Polyurethanes
Polyurethanes (PU) have relatively high surface energies. Adhesion problems with PU substrates are, therefore, likely to be due to cohesively weak material, such as mould release agents on the surface. Abrasion is one of the main methods recommended as a pre-treatment [50]; such a pre-treatment can remove cohesively weak material and expose strong material of relatively high surface energy. Cryoblasting, in which carbon dioxide particles are fired at a substrate, has been shown to be capable of removing silicone release agents from PUs and thus giving large improvements in adhesion [47].
1.2.7 Discussion
As noted in Section 1.2.1, there have been many detailed studies relating to the pretreatment of plastics. Much is now known about these pre-treatments including the chemical groups introduced, their concentrations and the depth of chemical modification. In contrast, the number of studies involving rubbers is much lower and in general the studies have been much less informative. One of the reasons for this is that rubbers usually contain several additives, often in relatively high concentrations. These additives make an understanding of the pre-treatments much more difficult. Because of the wide range of formulations for a particular rubber, it is also more difficult to generalise about pre-treatments than it is with plastics. For example, it is known that some formulations of SBR are considerably easier to pre-treat than others.
27
Peel strengths The Handbook of Rubber Bonding The four groups of rubbers considered above will now be discussed. Conclusions about pre-treatments for rubbers will then be presented. Hydrocarbon materials with few carboncarbon double bonds will be considered first. The most important examples in this group are ethylene-propylene rubbers which may be crosslinked with peroxides or sulphur systems in which case small quantities of dimers are polymerised with ethylene and propylene (EPDM). As EP rubbers contain no polar groups it will normally be necessary to chemically modify the polymers to enable them to interact strongly with polar adhesives such as epoxides and polyurethanes. In the case of plastics such as polyethylene and polypropylene, large increases in adhesion can be achieved by treating with a flame [9, 10], corona [11, 13], plasma [18, 19], or etching solution [23]. It would be expected that EP rubbers would respond in the same way to these pre-treatments. However, this is not always the case. Thus, Lawson [31], found that a corona treatment of an EPDM did not improve the peel strength to a polyurethane coating. It is probable that the reason for the poor adhesion is a layer of low molecular weight material on the EPDM. During corona treatment this layer, rather than the underlying polymer, would be oxidised. Hence, the polyurethane coating would not be able to interact strongly with the EPDM. Even if the EPDM was oxidised by the corona treatment, there would still be a cohesively weak layer on its surface. Many rubbers possess carboncarbon double bonds. In such cases there is the possibility that pre-treatment may be effective by addition or substitution reactions. Thus some reagents may be effective with unsaturated hydrocarbons such as SBR and SBS but not with EP rubbers. This is demonstrated by the work of Lawson [30] who found that treatment with TCICA in ethyl acetate resulted in the introduction of substantial quantities of chlorine into SBR, polybutadiene and NR, but not into EPDM. Several methods have been shown to be effective at pre-treating unsaturated hydrocarbon rubbers. These include treatment with concentrated sulphuric acid, acidified sodium hypochlorite and TCICA in ethyl acetate. The last method is the most commonly used commercially but in many countries legislation is being introduced to reduce the use of organic solvents. Promising results have been obtained with new solvent-free methods, namely an electrochemical method involving a highly reactive complex ion, and a method involving a water-soluble organic chlorine donor [47]. Like hydrocarbon rubbers, silicones have low surface energies and interactions with polar adhesives will be low unless the surface chemistry is modified. Plasma treatments improve the wettability [52, 53, 54, 55, 56, 57] or bondability [58, 59] of silicones. It is generally accepted that the introduction of a wide range of functional groups makes a polymer much more bondable. The effect of introducing individual chemical groups into polyethylene was demonstrated by Chew [60]. Thus, bromine, carbonyl, hydroxyl
28
Substrate Preparation Methods and carboxylic acid groups were all shown to greatly increase the bondability of polyethylene to an epoxide adhesive. This is in line with the general experience that polymers possessing halogens or oxygen-containing groups are much easier to bond than polyolefins. Whether rubbers containing such groups are easy to bond depends very much on whether the bonding surface is covered by low molecular weight (MW) additives or contaminants. On the one hand, Oldfield [37] achieved high peel strengths with chemically unmodified nitrile rubber whereas Brewis [47] obtained low peel strengths with an as-received polyurethane. However, after the removal of a silicone release agent by cryoblasting, much higher peel strengths were obtained [47].
1.2.8 Summary
Methods are available to pre-treat all rubbers but additives or processing aids may make successful pre-treatment much more difficult. TCICA in various organic solvents is very effective with those rubbers possessing carbon-carbon double bonds. However, legislation restricting the use of organic solvents is being introduced in many countries. Promising new pre-treatments include the use of water-soluble organic chlorine donors and an electrochemical method in which a highly active complex ion is generated. With some polymers containing suitable chemical groups, e.g., PU, simply removing cohesively weak material from the surface may be all that is necessary to achieve good adhesion.
1.3 Bonding Rubbers to Plastic Substrates

1.3.1 Introduction
This section is based mainly on first hand personal experience and is not intended to be an overview of bonding. It covers the basic practical principles of bonding rubbers to a variety of plastics materials. It is typical to find that those who are skilled in the art of moulding and bonding rubbers have little affinity to plastics materials and vice versa. As for polyurethanes; these are something else altogether. This chapter will concentrate on those plastics and rubbers which are likely to have uses in the manufacture of composite materials (see Appendix 1.1).
29
1.3.1.1 Why Use Plastics?

Cost, Weight saving, Technically superior, Environmentally more acceptable, Fashion/style.
1.3.1.2 What Form Does the Plastics Material Come In?

Moulded components, Cast components, Sheet or film, Tube/pipe or rod. Fabric, fibres and filaments are obviously important forms and uses of plastics materials. Although the basic principles of bonding plastics apply to fibres and fabrics, the other factors involved in bonding them are a subject in themselves and will not be discussed further. In the bonding of rubbers it is assumed that the plastics component is an item which has been preformed and it is this which will be treated with a bonding agent. In most cases the rubber will be moulded onto the primed surface, by techniques including the following: Injection moulding, Reaction injection moulding (RIM), Compression moulding, Transfer moulding, Extrusion blow moulding, Lamination, which could involve post vulcanisation bonding, Autoclave vulcanisation - rollers, pipes, hoses, stators, Casting at zero or low pressure - casting of PU. The basic principles should apply to any form of plastics material and to any method of moulding.
30
Substrate Preparation Methods Of course there is always the potential to mould the plastics material onto the vulcanised rubber, but this is rare. In practice, this type of moulding is an example of post vulcanisation bonding.
1.3.2 Plastics Substrate Preparation

In preparing metals for bonding, steel in particular, the idea is to produce a surface which is free of contamination, is easy to wet, has a sharp irregular surface to promote a mechanical key and controlled oxidation (see Figure 1.3).
Figure 1.3 Metal surface sites for bond
Fortunately for the commonly used metals this controlled oxidation occurs naturally after grit blasting or acid etching. In the case of plastics, no such convenient oxidation process takes place. However, each material will have a unique surface layer containing potential sites for bonding:
Polyamides
The polar group NH-C=O is capable of hydrogen bonding through the activated C=O group and via the N-H group. The N-H leaves a reactive site for chemical reaction with silanes, epoxies, isocyanates and any chemical adducts, which can release such species or any other species, which can react with an active hydrogen. Of course the amide group needs to be on the surface to be able to undergo hydrogen bonding or chemical reaction and steric hindrance will reduce the capability of such groups to partake in bonding, which is especially so in the case of aromatic polyamides.
31
Polyesters
The C(=O)O, ester group will partake in hydrogen bonding through both oxygen atoms, especially the activated carbonyl group. Some polyesters will be less easy to bond if steric hindrance is likely. Even PBT proves difficult to bond and often requires further treatment.
Polyurethanes
In theory PU should be very active towards bonding, with an activated N-H and a carbonyl group, as described for polyamides. However PUs are never that easy to bond and could be due to surface oxidation and/or surface hydrolysis, it is normal to remove the surface, degrease and prime before the surface is too old.
Polyureas
The sites for hydrogen bonding and chemical reaction are significant and polyureas are generally easy to bond. Being more oxidation resistant and hydrolysis resistant than the urethane group is significant.
Polycarbonates
A regular repeating stable carbonyl group is available for polar attraction and hydrogen bonding.
PPS (and PPO)
32
Substrate Preparation Methods As for polycarbonates, a regular repeating stable polar sulphur (oxygen) atom allows for polar attraction and hydrogen bonding. However, in the case of the polyolefines, there are no obvious adhesion sites:
Polyethylene
Polypropylene
For the bonding of these an oxidation process is essential. When one looks at the surface of metals and plastics under an electron microscope the disruption in that surface explains why bonding is never straightforward. The surface is often described as a weak surface layer and in the case of plastics one can include the surface stresses, general contamination, the presence of abhesive ingredients, i.e., process aids which have migrated to the surface. Some high temperature moulding processes may lead to variable and unwanted oxidation and/or reversion (crosslink degradation) at the surface. Therefore, one can accept the general opinion that the surfaces of plastics do need some form of abrasive or chemical treatment to remove the weak surface layer, or at least reduce it to an adequate level, as shown by the number of publications on the subject [61-69]. Putting it in simple terms the level of surface preparation depends on the performance requirements of the bond. To apply a pressure sensitive decal, no surface treatment is a feasible option, but to make a suspension mount then the plastics surface will require controlled treatments. Most engineering plastics can be treated with alumina or steel grit as for metals. However, in the real world it is quite normal to find that grit blasting is impractical for many reasons, including: Loss of shape, especially in thin sections, The reduction in dimensions is not reproducible,
33
The Handbook of Rubber Bonding Surface damage, such as fibrillation and plastic flow, Trapped (embedded) grinding media and other contaminants. The harder and the thicker the surface to be bonded the better it is for grit blasting. Similarly, the more highly filled plastics respond much better to blasting than unfilled plastics, and thermosets, especially glass-filled thermosets, are usually very successfully prepared by blasting. If a standard grit blasting process gives problems then the use of a finer grit in any standard grit blasting machine should be thoroughly tested to determine if there is an effective optimum grit size. Abrasive and chemical techniques include the following: Treatment with abrasive belts, Hydrosonic/ultrasonic cleaning, High pressure water/detergent cleaning, Acid etching, but effluent control means that this is not feasible for anything other than high priced specialities and for long running applications, The satinisation process for POM is an example of acid etching and involves a slurry containing p-toluene sulphonic acid, Phenol treatments of polyamides. This includes RFL treatments, Alkali etching. As for acid etching, the action is mild surface hydrolysis and loosening of debris on the surface, Oxidation with relatively mild oxidising agents. Hydrogen peroxide and sodium hypochlorite are often cited, but a low hazard system worthy of testing out is ammonium persulphate, Powerful oxidising agents, such as sulphuric dichromate etching, Abrasion in an aqueous abrasive slurry. Since this involves effluent waste, it is seldom used on a large scale, but is an effective laboratory method, especially when combined with a mild acid, alkali or oxidising agent, Direct oxidation by flame, or hot air. Normally only applicable to simple shapes, like extruded film, tube and rod,
34
Substrate Preparation Methods UV treatments. Again this has restricted use, mainly films, Plasma treatments. Yet to become a mainstream treatment for rubber to plastics bonding, Corona discharge, Chlorination.
1.3.3 Degreasing and Solvent Cleaning

Degreasing has always been considered an integral part of ideal surface preparation, but under current environmental pressures, it is quite normal to find it has been partly eliminated or even totally eliminated. The need for thorough degreasing becomes more relevant where the environmental resistance of the bond is important and especially where an abrasive technique has left a contaminated surface. Degreasing of plastics with solvents can cause problems: Stress cracking of the surface, where the effect can remain undetected, Absorption and even adsorption of a solvent of a similar solubility parameter to the plastics material. This can be a very serious problem, since retained solvent within the bond line could well act as a release agent. If solvent degreasing/cleaning is going to be employed, then a fast drying solvent which has a relatively low solvating power towards the plastics being degreased needs to be used. Aqueous degreasing can be effective, especially when fully automated. However, any aqueous process can leave a surface which requires desorption of water, which adds another process. Unfortunately, for low pressure moulding and casting in particular, the ultimate bonds are often only achieved if desorption of the adsorbed water and gases is specified. This is most evident with polyamides, some polyesters, PU, melamine and urea resins and some epoxy resins. However, in the majority of high pressure moulding processes adsorbed water and gases do not appear to affect bonding, but long term environmental tests may show up a problem. A general guide to reduce the effects of water adsorption is to dry the plastics surface, prime with the bonding agent, dry the primed surface and give the component a prebake (the coated dried surface is heated, prior to the moulding process). Pre-bakes can
35
Table 1.11 A brief summary of the preferred treatments

Plastics group A1, A2 Degrease Yes Take care with acrylics if in doubt use alcohol Grit blasting Yes Check for optimum grit size Chemical treatments POM-satinisation polyesters difficult surfaces respond to alkali or ammonium persulphate treatments Yes Strong oxidising agents Other treatments Nylon 6 and 66 desorb at >100 C, especially for low pressure moulding and casting of PU other forms of abrasion work generally for these materials TPOs flame treat, UV, corona discharge treat. may be followed by chlorination
Yes
No
Yes Yes Avoid ketones Unless <50 alcohols are safer Shore D Yes No Solvent attack on Unless > 50 PVC and PVDC. Shore D Avoid aqueous degreasing of PU PTFE, PVF treat with sodium naphthalene PTFE, PVF prime with a thin coat of Cilbond 30/31, dry and fuse at >200 C
be as little as 10 minutes at 70 90 C, which could be part of the drying process, up to 30 minutes at 150 C, which would be an additional process (see Table 1.11). For plastics group definitions see Appendix 1.1
1.3.4 Adhesive/Bonding Agent Choice 1.3.4.1 Post Vulcanisation Bonding

This includes adhesive bonding and bonding with vulcanising bonding agents under the influence of heat and pressure, in those cases where the plastics component needs to be adhered to the preformed vulcanised rubber.
36
Degrease
Grit blasting
Chemical treatments Substrate Preparation Methods
This may be the only method of manufacture for some products and there is a host of adhesives available for plastics, some of which are described in the literature [63 69] for example. The main adhesives for bonding plastics to rubbers include cyanoacrylates, two-part urethanes, two-part epoxies, hot melt reactive urethane prepolymers, heat reactive contact cements and silane treatments. Many adhesive bonding applications require a unique answer and it is difficult to make generalised recommendations, as you can within limits, with vulcanisation bonding.
1.3.4.2 Vulcanisation Bonding

This is bonding the rubber during the vulcanisation process. The ideal situation is where no bonding agent is required, but in the real world it is rare to find situations where no bonding agent, whether an internal bonding agent (added to the rubber) or a conventional (external) agent is necessary.
Primers for the Plastics Substrate for Vulcanisation Bonding

In theory the primer should match the polarity of the plastics substrate, but this could infer the need for a range of primers depending on the polarity of the plastics to be bonded. In practice, bonding agent primers contain curable polar resins and less polar rubbery polymers, which may or may not be crosslinkable. This gives some versatility in the bonding of a range of polar plastics. An ideal primer would contain highly polar curable resins and speciality polymers. The speciality polymers would vary in their polarity along the polymer chains, giving it variable polarity, a positive attribute in the bonding of a range of plastics. The polymer could be produced by grafting a polar monomer (or monomers) onto an unsaturated polymer such as NR, IR, BR or even NBR, which leads to a polymer which has certain properties: 1. It still contains unsaturation and segments of the original main chain polymer. This means it can crosslink and intermix with the rubber being moulded. 2. Any polar groups on the ungrafted polymer (for example CN groups in NBR) take part in polar bonding to the plastics substrate. 3. The grafted monomer(s), being polar, can also partake in polar bonding.
37
The Handbook of Rubber Bonding 4. If the grafted monomer retains reactivity it can take part in chemical bonding. Such reactivity could include isocyanates, silanes, epoxides, or even heat reactive adducts, such as blocked isocyanates. 5. If the grafted monomer results in a large and highly polar site, it is possible for this moiety to behave in a way which appears similar to solvent welding (surface softening), but in this case the solvent is the polar moiety. This phenomenon is a particular feature of one type of speciality one coat technology, because this welding not only applies to the plastics surface, but also to the rubber surface, whether the rubber is in an uncured state or cured state. Though it has been compared to solvent welding the phenomenon described above shows no thermoplasticity, in fact heat and solvent resistance are the big features of this type of technology, along with the capability of post vulcanisation bonding. 6. The ability of the polymer and resin in the primer to react with each other generally improves the environmental resistance of both the bond and the bonding agent. 7. For improved heat resistance, aliphatic chlorine should be avoided in the polymers. For general purpose vulcanisation bonding, conventional primers are available from the established suppliers of bonding agents and all such suppliers can cite many examples of rubber to plastics bonding (see Table 1.12). For improved adhesion and improved environmental resistance the more reactive primers can exhibit advantages, such that in some tough applications, they are the only choice.
Cover coat/top coat

If one is required it should be chosen only with regard to the rubber/rubber being moulded, just as for rubber to metal bonding. (See Table 1.12.)
Summary
With attention to detail, most plastics can be bonded to rubbers, provided one accepts the limitations of the rubbers, the plastics and the adhesive system chosen to bond them. It is the aim of those who recommend the adhesives/bonding agents to ensure the bonds are fit for purpose, but it is normal to find that the component manufacturer wants to see no failure attributable to the adhesive.
38
Table 1.12 Rubbers, vulcanisation bonded to plastics - systems and techniques

Plastics Materials PPO Rubber VAMAC (Dupont) Environmental Resistance of the Bonds Heat to 180 C Bonding System Cilbond 22 Cilbond 60W Special Treatments Grit blast PPO (200 400 m grit) and degrease with acetone or use alcohol for large or awkward shapes As above Satinse POM with p-TSA Abrade or grit blast with fine grit. Degrease with MEK Prebake first thin coat of primer at 100 C use Cilbond 22 for PV bonding Sodium treat PTFE and prime as soon as possible Oxidise/flame treat PP. Prebake a first thin coat of primer Belt abrade and water or hydrocarbon degrease. Allow first coat to dry >2 h and second coat for >4 h, but <30 h Alkali or ammonium persulphate etch PET
PPS POM
NR SBR VMQ
Glycol resistant to 160 C Heat to >>160 C
Cilbond 21T Cilbond 22 Cilbond 65W Cilbond 89 Cilbond 22
ARAMID XNBR HNBR Heat and fluids to
>170 C
PTFE
FKM
Hot oils to >>160 C Cilbond 65W
PP FILLED GRP
EPDM
Water to 100 C
Cilbond 89
PU rotation cast
Bonds outperforms the PU for roller and pipe coatings
Cilbond 41+B Cilbond 49SF+B
PET
TPU
Heat to 140 C
Cilbond 49SF
p-TSA: para-toluene sulphonic acid
39
APPENDIX 1.1
Plastics are divided into groups, loosely based on factors such as surface preparation and bonding characteristics:
Group A1 Plastics
Engineering Thermoplastics
Acrylics POM - Acetals Polyesters - PET, PBT Polycarbonate, PC PES PPO PPS Polyamides - Nylon 6, 66, 11, 12 Aramids PEEK
Group A2 Plastics - Thermosets

Epoxies Unsaturated polyesters, FRP/GRP Phenolics, including RF resins Polyamides
Group B Plastics - Other Thermoplastics

TPOs
Group C Plastics - Miscellaneous

ABS SEBS
40
Substrate Preparation Methods Polystyrene Cellulosics UF, MF
Group D Plastics - Miscellaneous

PU PVC, PVDC PTFE, PVF Rubbers
Conventional Rubbers
NR SBR IR BR CR CSM ACM, VAMAC NBR, XNBR, HNBR EPDM IIR ECO EVM CPE Millable PU
Others
PUs - TPU and castable PU Thermoplastic rubbers VMQ FKM Polyolefins
41
1.4 Substrate Preparation for Bonding Using the Wet Blast Process
1.4.1 Summary
Abrasive Developments have, in conjunction with their Japanese licensee, developed a wet blast phosphating plant that raises the quality standard within the industry. The solution achieved delivers high quality components from an automatic machine that combines both the cleaning and phosphating processes. The cleaning section benefits from the unique degreasing and surface treatment properties of the VAQUA process. Wet blast phosphating was first developed some 15 years ago in co-operation with the Yamashita Rubber Company, who make anti-vibration rubber and bond it to supporting metal parts exclusively for the Honda Motor Company. Yamashita had two main objectives to achieve from the development of a wet blast phosphating plant: To increase the strength of adhesive bonding between the anti-vibration rubber and the metal parts, To improve the corrosion resistance of the metal parts and hence their useful life under any weather conditions. In addition to these objectives, the demand from the automotive industry as a whole for this type of component was increasing, and the requirement was for it to be phosphated prior to bonding whilst still keeping the cost at an acceptable level. To achieve the improved quality and reduced cost requirements the wet blast phosphating plant had to operate continuously and automatically process the metal parts for phosphating.
1.4.2 The Wet Blast Phosphating Plant

The plant has two major processing sections, the wet blast section and the phosphate treatment section.
1.4.2.1 The Wet Blast Process

The wet blast process is one of the worlds most versatile, efficient and economical processes for metal cleaning and finishing, replacing costly chemicals and the need to sandblast. It saves hours of messy cleaning and eliminates health and environmental hazards associated with strong chemicals and dust from conventional blasting methods. 42
1.4.2.2 How is Wet Blasting Done?

The component surfaces are bombarded by a recirculating high volume flow of water borne particles (normally abrasive or glass beads) contained within the cabinet. The specially developed VAQUA pump pulls the concentrated slurry of media and water, inhibitors and degreasing agents, from the cabinet sump and pushes it at constant high volume to the process gun. The VAQUA pumps have been developed to minimise the friction wear from the blast media as it is accelerated round the system by the blast pump itself. Before reaching the process gun a proportion of the water and media is diverted down the bypass to provide agitation in the sump, this ensures a stable concentration of media and water. To accelerate the flow of media particles onto the surface of the work piece and therefore achieve the cleaning and surface finishing effects, a controlled flow of compressed air is introduced into the blast gun. The water within the system lubricates, washes, carries mild inhibitors/degreasers and eliminates dust formation. At the rinse stage, elements of the blasting media will be carried over and need to be removed and recirculated, this is done by cyclones. There is a two-stage cyclone system, with the first stage separating the media and water by centrifugation which removes high concentration slurry, returning it to blast tank from the pipe arrangements located at the bottom of the cyclone. Low concentration slurry is transferred to the second cyclone where the process is repeated and the media further separated from the water. The water separated here is used for subsequent rinse stages and the separated broken down media is transferred to the klarti separator. This is a form of oil and grease settling tank where the broken down abrasive is separated from the water to allow for subsequent removal of the used media.
1.4.2.3 The Wet Blast Section

It is important that a certain type of surface finish is produced on the metal components to enable effective phosphating and bonding. The optimal surface roughness for bonding is 5 10 m, this can be best achieved by wet blasting. The machine is equipped with a specially designed barrel in which the components are held, and large capacity process guns, through which the media, water and air combination is delivered. This set up allows metal parts with complicated shapes to be effectively and thoroughly processed giving a uniform and fine satin finish on all of the metal parts. By adding a degreasing agent to the blasting slurry, any oil and grease on the metal parts surface is completely removed thus providing a clean component for presentation to the phosphating section.
43
Figure 1.4 The VAQUA pump
Wet blasting removes the oxide film covering the metal parts and exposes the pure metal under the film offering an ideal condition for the phosphate treatment which follows. The process is so efficient that even cast components, if wet blasted, can be treated with phosphate which was impossible using traditional methods.
44
1.4.2.4 The Phosphate Treatment Section

In the phosphate treatment section, metal parts go through multiple vessels containing phosphate, rinse water, and a specially designed barrel in each vessel oscillates to keep the metal parts in continuous motion thus preventing bubbles forming or liquid staying inside the parts that have openings within them. The barrel oscillation also ensures that the metal parts are always exposed to fresh phosphate which is essential for a uniform and stable phosphate film to be created. To avoid cross contamination of the phosphating chemicals, the barrel containing the metal parts does not travel through the individual vessels but stays in a particular vessel. When the processing of the metal parts in the barrel is complete they are automatically dumped into the next barrel for the subsequent process. During their transfer from one vessel to the next, the metal parts are only exposed to the air for a short time which avoids the possibility of them rusting in the future. By automatically transferring products from one vessel to another this also minimises the contamination of chemicals from one vessel to the next.
1.4.3 Comparison Between Conventional and Wet Blast Phosphating

The conventional process stages are: 1. Dip in trichloroethane for degreasing, 2. Dry shot blasting, 3. Treat with triethane vapour for degreasing, 4. Water rinse, 5. Phosphate treatment, 6. Water rinse, 7. Hot water rinse, 8. Drying. By comparison the wet blast phosphating stages are: 1. Wet blast, 2. Degrease detergent system, 3. Water rinse,
45
The Handbook of Rubber Bonding 4. Phosphate treatment, 5. Water rinse, 6. Hot water rinse, 7. Drying.
1.4.4 The Wet Blast Phosphating Plant

Typical processing time and performance at each process stage:
Process Wet blasting 1st rinsing Degreasing (non-solvent type) 2nd rinsing 3rd rinsing 1st phosphating 2nd phosphating Dipping for rinse Dipping for hot rinse Drying Total process time
Time (s) 300 30 300 60 60 180 180 60 60 120 1350
Performance Wet blasting with satin finish and degreasing Rinsing work to remove remaining media Degreasing areas of the work piece that could not be degreased by wet blasting Removing degrease chemicals Removing degrease chemicals Phosphate coating Phosphate coating Removing phosphate Removing phosphate and warming up work for drying Drying work completely
46
1.4.5 Advantages of the Wet Blast Phosphating Plant 1.4.5.1 Product Quality
High quality phosphate film. The plant produces high quality phosphate film for a number of reasons as listed below: The quality of the phosphating achieved is very dependent upon the surface finish of the component prior to phosphating. The surface finish achieved through wet blasting is ideal for the phosphating process, hence the high quality film. The wet blast section connects with the phosphate treatment plant and therefore the metal work pieces are treated with phosphate immediately after blasting. During transit from the wet blast section to the phosphating plant the work pieces are covered with water so eliminating the possibility of oxidation of the components. A rust inhibitor in the blast system also prevents the oxidation of the components.
1.4.5.2 Clean Components Prior to Phosphating

The powerful wash available from the wet blast process removes any kind of oil and grease without any adjustment of the system. The wet blast media physically removes oil and grease from the surface of the components and prevents it from sticking to the surface. This is achieved through the repeated blasting of the water media slurry, in a 7:1 ratio, against the work piece. The media particles in a slurry can reach speeds in excess of sonic speeds so imparting large energy to the component and assisting in the cleaning.
1.4.5.3 High and Uniform Quality Products Made Continuously

The wet blast phosphating plant is fully automated which means that once the initial set up is complete, the repeatability of the process ensures a consistent quality of component after phosphating. In an alternative system where a barrel transfers components from one process to the next the inconsistency of time in each stage means that there could be some inconsistency in the end result, which is not the case with the wet blast phosphating plant. In chemical processes involving pre-treatment and processing, the concentration of chemicals may alter depending upon the condition of the work pieces such as the type of oil or grease on them. With wet blast phosphating the type of oil or grease is irrelevant, the process continues to give the same high quality cleaning and phosphating of the work pieces regardless of the type of oil and grease.
47
1.4.5.4 The Wet Blast Phosphating Plant Can Process Any Type of Material
The wet blast process physically removes the surface oxide film and does not rely on a chemical reaction, therefore the range of materials that can be processed can be anything from common steel and steel alloy to special steels. This physical scraping off of the oxide layer means the process is consistent for each work piece and also does not require change of chemicals between different types of component metals. The universal nature of the wet blast process can significantly reduce process times if alternative processes require chemical or other changes between different types of components.
1.4.5.5 Ease of Machine Operation

Two factors assist in the efficient operation of this machine, these are: Automatic operation, Footprint of the machine. The automatic nature of the wet blast phosphating plant means that once loaded the machine will complete the process automatically allowing the operator to carry out other tasks at the same time. This may even be operating more than one wet blast phosphating plant because the small footprint of this machine will allow two of these machines to be located in the area normally allocated to a conventional process. The reason it is possible to obtain such a small footprint is that there is no requirement for conveyors between the cleaning and phosphating plants as they are incorporated in the same machine. In addition to these operational benefits, the plant is of a single floor type, thus making it simple to install and easy to locate related machinery nearby. It is worth noting that only three days are required for installation before the plant is ready for operation. There is also no ancillary pipe work required for the machine apart from the primary supply piping. The ability to locate related machinery nearby has enabled some users to incorporate automatic load and unload facilities to their plants thus increasing the automation of the machine and hence reducing the labour costs further.
1.4.5.6 Work Pieces of Any Shape Can be Processed

Any shape of component can be processed through the wet blast phosphating plant without the possibility of any liquid remaining inside the component. The barrel in the machine has
48
Substrate Preparation Methods been designed to prevent the components slipping inside the barrel whilst the barrel oscillates. Components such as tubes, struts and flat washers are all being successfully processed with the wet blast phosphating plant.
1.4.5.7 Environmental Issues

Each country or region has its own laws relating to the safe and environmentally friendly use of chemicals. Cleaning and degreasing is possible without using chemicals which damage the environment. Wet blasting is a physical cleaning method that does not rely upon chemicals. The reduction in the use of chemicals can also reduce the taxes or disposal charges required for some chemicals.
1.4.5.8 The Work Environment

Traditional blasting processes have in some cases been associated with high dust levels and therefore a poor work environment, this is not true for the wet blast process. Dust generated by the physical cleaning is absorbed into the liquid supporting the cleaning media and subsequently extracted through the filtration and/or the oil separation system. The wet blast process is a completely dust free cleaning system. As the equipment is essentially self-contained, the clean work environment also benefits from the absence of piping on the floor thus making it easy to clean the area around the machine.
1.4.5.9 Enclosed Phosphate Treatment Plant

The design of the phosphating plant is such that any vapour generated is not allowed to escape. The specially designed transfer system allows the phosphate treatment section to be fully enclosed. The transfer system of a conventional machine is such that the barrels themselves have to travel through each process, meaning the enclosure has to be large enough to enclose the whole machine. On the contrary with the wet blast phosphating plant, just each vessel is enclosed and the mechanical devices are outside the enclosure.
1.4.5.10 Additional Benefits

With the wet blast phosphating plant, only the work pieces and not the barrels transfer, thus reducing the amount of rinse water consumed. The volume of the rinse water consumed is proportional to the amount of chemical liquid brought into the rinse water vessel. For the same reason, that only the work pieces are transferred, the amount of chemical liquid consumed is relatively small.
49
1.4.5.11 Maintenance
Maintenance is significantly reduced, with the wet blast phosphating machine not requiring all barrels to be regularly maintained but only the phosphating vessels and the following water rinse vessel. If the maintenance is not sufficient in conventional machines, sludge can be transported into the drying section giving poor quality components with sludge sticking to them.
1.4.5.12 The Wet Blast Phosphating Process

Stage 1 Stage 2 Hoist loader Blast inlet hopper This hoist raises the components to the hopper located at the upper side of the blast section This works as a transfer accumulator and shortens the transfer time for loading components into the blast barrel Simultaneous degreasing and matt surface finishing through barrel processing Water collected within the components is removed here before transfer into the next stage The degreasing process is completed here
Stage 3 Stage 4 Stage 5 Stage 6 Stage 7 Stage 8 Stage 9
Wet blast section Blast unload bucket Remove tank
2nd and 3rd rinse tanks Removed grease and media are rinsed off with water Surface adjustment tank Pre-processing is done so that a stable phosphate film can be made in the phosphating process Phosphate tanks Water rinse Two tanks are used to form the phosphate film Two water rinse tanks are used to remove residual chemicals from the components Two water rinse tanks are used to remove residual chemicals from the components Water is cut off and the components dried by hot air Processed components are unloaded
Stage 10 Hot water rinse tanks Stage 11 Dryer Stage 12 Unload conveyor
50
References
1. H. M. Clearfield, J. Thomas, D. K. McNamarra and G. D. Davis in Adhesive Bonding, Ed., L-H. Lee, Plenum Press, New York, 1991. J. S. Thornton, R. E. Montgomery and J. F. Cartier, Presented at the ACS Division of Polymeric Materials: Science and Engineering, Chicago, IL, Fall 1985, 53, 465. T. Symes and D. Oldfield, in Treatise on Adhesion and Adhesives, Volume 7, Ed., J. D. Minford, Marcel Dekker, Inc., New York, 1991, Chapter 2. F. H. Sexsmith, in Rubber Products Manufacturing Technology, Eds., A. K. Bhowmick, M. M. Hall and H. A. Benarey, Marcel Dekker, Inc., New York, 1994, Chapter 11. BS EN ISO 11124-4 Preparation of steel substrates before application of paints and related products specifications for metallic blast-cleaning abrasives - low-carbon cast-steel shot, 1997. C. L. Mahoney, in Handbook of Adhesives, 3rd Edition, Ed., I. Skeist, Van Nostrand Rheinhold, New York, 1990, p.74-93. L. Setiawan, D. Schoenherr and J. Weihe, International Polymer Science and Technology, 1993, 20, 9, T13. K. M. Bond and D. H. Mowrey, Presented at the 141st ACS Rubber Division Meeting, Louisville, KY, Spring 1992, Paper No.57. R. L. Ayres and D. L. Shofner, SPE Journal, 1972, 28, 51.
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10. D. Briggs, D. M. Brewis and M. B. Konieczko, Journal of Materials Science, 1979, 14, 6 ,1344. 11. D. Briggs, C. R. Kendall, A. R. Blythe and A. B. Wootton, Polymer, 1983, 24, 1, 47. 12. M. Strobel, M. J. Walzak, J. M. Hill, A. Lin, E. Karbashewski and C. S. Lyons, in Polymer Surface Modification, Ed., K. L. Mittal, VSP, Utrecht, 1996, 233. 13. R. Krger and H. Potente, Journal of Adhesion, 1980, 11, 2, 113. 14. H. Brecht, F. Mayer and H. Binder, Die Angewandte Makromolekulare Chemie, 1973, 33, 89. 51
The Handbook of Rubber Bonding 15. D. W. Dwight and W. M. Riggs, Journal of Colloid Interface and Science, 1974, 47, 3, 650. 16. I. Mathieson, D. M. Brewis, I. Sutherland and R. A. Cayless, Journal of Adhesion, 1994, 46, 1/4, 49. 17. E. R. Nelson, T. J. Kilduff and A. A. Benderly, Industrial Engineering Chemistry 1958, 6, 221. 18. H. Schonhorn and R. H. Hansen, Journal of Applied Polymer Science, 1967, 11, 8, 1461. 19. C. A. L. Westerdahl, J. R. Hall, E. C. Schramm and D. W. Levi, Journal of Colloid and Interface and Science, 1974, 47, 3, 610. 20. H. Schonhorn and R. H. Hansen, Journal of Applied Polymer Science, 1968, 12, 5, 1231. 21. A. Chew, R. H. Dahm, D. M. Brewis, D. Briggs and D. G. Rance, Journal of Colloid and Interface Science, 1986, 110, 88. 22. G. C. S. Collins, A. C. Lowe and D. Nicholas, European Polymer Journal, 1973, 9, 11, 1173. 23. D. Briggs, D. M. Brewis and M. B. Konieczko, Journal of Materials Science, 1976, 11, 7, 1270. 24. L. J. Gerenser, J. F. Elman, M. G. Mason and J. M. Pochan, Polymer, 1985, 26, 8, 1162. 25. G. Beamson, D. M. Brewis and J. F. Watts, unpublished work. 26. R. A. Bragole, The Journal of Rubbers and Plastics, 1974, 6, 3, 213. 27. M. D. Ellul and D. R. Hazleton, Rubber Chemistry and Technology, 1994, 67, 4, 582. 28. I. Brass, D. M. Brewis, I. Sutherland and R. Wiktorowicz, International Journal of Adhesion and Adhesives, 1991, 11, 5, 150. 29. G. Kranz, R. Lschen, T. Gesang, V. Schlett, O. D. Hennemann and W. D. Stohrer, International Journal of Adhesion and Adhesives, 1994, 14, 4, 243. 30. D. F. Lawson, K. J. Kim and T. L. Fritz, Rubber Chemistry and Technology, 1996, 69, 2, 245.
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Substrate Preparation Methods 31. D. F. Lawson, Rubber Chemistry and Technology, 1987, 60, 1, 102. 32. ASTM D2578-99a Standard Test Method for Wetting Tension of Polyethylene and Polypropylene Films 33. M. Minagawa, T. Saito, Y. Fujikura, T. Watanabe, H. Iwabuchi, F. Yoshi and T. Sasaki, Journal of Applied Polymer Science, 1997, 63, 12, 1625. 34. A. Kondyurin and Y. Klyachtin, Journal of Applied Polymer Science, 1996, 62, 1, 1. 35. B. C. Cope, D. M. Brewis, J. Comyn, K. R. Nangreave and R. J. P. Carne, Adhesion 10, Ed., K. W. Allen, Elsevier Applied Science Publishers, London, 1986, 178. 36. D. Pettit and A. R. Carter, Journal of Adhesion, 1973, 5, 4, 333. 37. D. Oldfield and T. E. F. Symes, Journal of Adhesion, 1983, 16, 2, 77. 38. D. Oldfield and T. E. F. Symes, Journal of Adhesion, 1992, 39, 2-3, 91. 39. C. W. Extrand and A. N. Gent, Rubber Chemistry and Technology, 1988, 61, 4, 688. 40. Y. Kusano, T. Noguchi, M. Yoshikawa, N. Kato and K. Naito, Presented at Kobe International Rubber Conference (IRC 95), 1995, Kobe, Japan, 432. 41. M. M. Pastor-Blas, M. S. Snchez-Adsuar and J. M. Martn-Martnez in Polymer Surface Modification Ed., K. L. Mittal, VSP, Utrecht, 1996, 379. 42. M. M. Pastor-Blas, J. M. Martn-Martnez and J. G. Dillard, Journal of Adhesion, 1997, 63, 1/3, 121. 43. M. M. Pastor-Blas, J. M. Martn-Martnez and J. G. Dillard, Journal of Adhesion, 1997, 62, 1/4, 23. 44. A. Torr-Palau, J. C. Fernndez-Garca, A. C. Orgils-Barcel and J. M. MartnMartnez, Journal of Adhesion, 1996, 57, 1/4, 203. 45. N. Pastor-Sempere, J. C. Fernndez-Garca, A. C. Orgils-Barcel, R. TorregrosaMaci and J. M. Martn-Martnez, Journal of Adhesion, 1995, 50, 1, 25. 46. M. M. Pastor-Blas, J. M. Martn-Martnez and J. G. Dillard, Journal of Adhesion Science and Technology, 1997, 11, 4, 447.
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The Handbook of Rubber Bonding 47. D. M. Brewis and I. Mathieson, Presented at the 22nd Annual Meeting of the Adhesion Society, Panama City Beach, USA, 1999, 4. 48. M. M. Pastor-Blas, R. Torregrosa-Maci, J. M. Martn-Martnez and J. G. Dillard, International Journal of Adhesion and Adhesives, 1997, 17, 2, 133. 49. A. Chew, R. H. Dahm, D. M. Brewis, D. Briggs and D. G. Rance, Journal of Colloid and Interface Science, 1986, 110, 1, 88. 50. J. Shields, Adhesives Handbook, 3rd Edition, Butterworth, London, 1984, 87. 51. R. F. Wegman, Surface Preparation Techniques for Adhesive Bonding, Noyes Publications, New Jersey, 1989, 127. 52. R. R. Sowell, N. J. DeLollis, H. J. Gregory and O. Montoya, Journal of Adhesion, 1972, 4, 1, 15. 53. J. Y. Lai, Y. Y. Lin, Y. L. Denq, S. S. Shyu and J. K. Chen, Journal of Adhesion Science and Technology, 1996, 10, 3, 231. 54. E. P. Everaert, H. C. van der Mei, J. de Vries and H. J. Busscher, Polymer Surface Modification, Ed., K. L. Mittal, VSP, Utrecht, 1996, 33. 55. M. Hudis and L. E. Prescott, Journal of Applied Polymer Science, 1975, 19, 2, 451. 56. J. R. Hollahan and G. L. Carlson, Journal of Applied Polymer Science, 1970, 14, 10, 2499. 57. J. L. Fritz and M. J. Owen, Journal of Adhesion, 1995, 54, 1/4, 33. 58. M. J. Swanson and G. W. Opperman, Journal of Adhesion Science and Technology, 1995, 9, 3, 385. 59. C. Combette, D. Hivert, J. Maucourt, W. Brunat, T. M. Duc, G. Michel, P. Le Prince and G. Legeay, Presented at Euradh 94, Mulhouse, France, 1994, 416. 60. A. Chew, D. M. Brewis, D. Briggs and R. H. Dahm in Adhesion 8, Ed., K. W. Allen, Elsevier Applied Science Publishers, London, 1984, 97. 61. Handbook of Plastics Joining, A Practical Guide, Plastics Design Library, Norwich, NY, 1997. 62. K. W. Allen, Joining of Plastics, Rapra Review Report No.57, Rapra, Shrewsbury, UK, 1992.
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Substrate Preparation Methods 63. D. G. Brandon and W. D. Kaplan, Joining Processes, An Introduction, Wiley, Chichester, 1997. 64. F. Garbassi, M. Morra and E. Occhiello, Polymer Surfaces from Physics to Technology, Wiley, Chichester, 1998. 65. J. Shields, Adhesives Handbook, 3rd Edition (Revised), Butterworths, London, 1985. 66. Handbook of Adhesives, 3rd Edition, Ed., I. Skeist, Van Nostrand Reinhold, New York, 1990. 67. Treatise on Adhesion and Adhesives, Volume 5, Ed., R. L. Patrick, Marcel Dekker Inc., New York, 1981. 68. A. H. Landrock, Adhesives Technology Handbook, Noyes Publications, Parkridge, NJ, 1985. 69. R. C. Snogren, Handbook of Surface Preparation, Palmerton, New York, 1974.
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The Handbook of Rubber Bonding

Editor: Bryan Crowther

Rapra Technology Limited

First Published 2001 by

Rapra Technology Limited

2001, Rapra Technology Limited Revised and Reprinted 2003

The Handbook of Rubber Bonding

1.4.3 1.4.4 1.4.5 2

3.2.2 3.2.3 3.2.4 3.2.5 3.2.6 3.3

Bonding Agent Preparation .................................................................. 97 3.3.1 Solvent-borne Bonding Systems ............................................... 97

Bonding Agent Testing ....................................................................... 110

The Handbook of Rubber Bonding

5.1.1 5.1.2 5.1.3 5.1.4 5.1.5 5.1.6 5.1.7 5.1.8 5.1.9

The Handbook of Rubber Bonding

6.2.3 6.2.4 6.2.5 6.2.6 6.2.7 6.2.8 6.2.9

Experimental ..................................................................................... 221 8.3.1 Materials ............................................................................... 221

Summary ............................................................................................ 238

The Handbook of Rubber Bonding

10.5.1 10.5.2 10.5.3 10.5.4 10.5.5 10.6 10.7

Silicone to Silicone Bonding (Soft and Soft) .................................... 308

The Handbook of Rubber Bonding

12.1.3 12.1.4 12.1.5 12.1.6 12.1.7 12.1.8 12.1.9

The Handbook of Rubber Bonding

Substrate Preparation Methods

1.1 Metal Preparation General Techniques

1.1.1 Structure of Metal Substrates Metallography

1.1.3 Rubber Component with Metal Support

1.1.4 Metal Pre-treatments

Substrate Preparation Methods

1.1.4.1 Mechanical Methods

Alkaline removal of oils and greases

Solvent dip methods for large scale removal of greases

Substrate Preparation Methods

Removal of surface oxides

1.1.4.2 Chemical Methods

Treatments for stainless steels (see also Section 3.3)

Phosphate coating (see also Sections 1.2, 3.3 and 4.2.5)

Zinc coating or galvanising

Metal preparation - for waterborne bonding systems

1.2 Pre-treatments of Plastics and Rubbers

1.2.2 Studies of Pre-treatments for Plastics

The Handbook of Rubber Bonding

1.6 0.8 13.8 ~18

0.8 0.4 7.7 ~10

NO3 Total [O] tagged Actual [O] incorporated

Corona treatment after derivatisation

Substrate Preparation Methods

Table 1.3 Assignment of peaks for corona treated polypropylene [25]

* The assignment at 289.5 eV is tentative

Table 1.4 Surface analysis of treated polypropylene films [12]

Substrate Preparation Methods

1.2.3 Hydrocarbon Rubbers with Little or No Unsaturation 1.2.3.1 Ethylene-Propylene Rubbers

The Handbook of Rubber Bonding

1.2.3.2 Butyl Rubber

1.2.4 Unsaturated Hydrocarbon Rubbers 1.2.4.1 Natural Rubber

Substrate Preparation Methods

1.2.4.2 Styrene-Butadiene Copolymers

1.2.5 Halogenated Rubbers

1.2.6.2 Nitrile Rubber

Substrate Preparation Methods

1.3 Bonding Rubbers to Plastic Substrates

The Handbook of Rubber Bonding

1.3.1.1 Why Use Plastics?