Handbook of Rubber Bonding

Handbook
of Rubber
Bonding
Bryan Crowther (Editor)

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 Structure of Metal Substrates - Metallography .......................... 3
1.1.2 Bonding ..................................................................................... 5
1.1.3 Rubber Component with Metal Support ................................... 5
1.1.4 Metal Pre-treatments ................................................................. 6
1.2 Pre-treatments of Plastics and Rubbers ................................................ 12
1.2.1 Introduction ............................................................................. 12
1.2.2 Studies of Pre-treatments for Plastics ....................................... 13
1.2.3 Hydrocarbon Rubbers with Little or No Unsaturation ............ 19
1.2.4 Unsaturated Hydrocarbon Rubbers ......................................... 20
1.2.5 Halogenated Rubbers .............................................................. 25
1.2.6 Miscellaneous Rubbers ............................................................ 26
1.2.7 Discussion ................................................................................ 27
1.2.8 Summary ................................................................................. 29
1.3 Bonding Rubbers to Plastic Substrates ................................................. 29
1.3.1 Introduction ............................................................................. 29
1.3.2 Plastics Substrate Preparation .................................................. 31
1.3.3 Degreasing and Solvent Cleaning ............................................. 35
1.3.4 Adhesive/Bonding Agent Choice .............................................. 36
1.4 Substrate Preparation for Bonding Using the Wet Blast Process ........... 42
1.4.1 Summary ................................................................................. 42
1.4.2 The Wet Blast Phosphating Plant ............................................. 42
i
The Handbook of Rubber Bonding
1.4.3 Comparison Between Conventional and Wet Blast Phosphating .. 45

1.4.4 The Wet Blast Phosphating Plant ............................................. 46
1.4.5 Advantages of the Wet Blast Phosphating Plant ....................... 47
2 Rubber to Metal Bonding ............................................................................. 57

2.1 History................................................................................................. 57
2.2 Bond System Characteristics ................................................................ 62
2.2.1 Adhesive Characteristics .......................................................... 62
2.2.2 Compound Characteristics....................................................... 64
2.3 Adhesion .............................................................................................. 66
2.4 Effective Bond Formation .................................................................... 71
2.5 Post Vulcanisation Bonding ................................................................. 73
2.6 Factors Affecting Bond Integrity .......................................................... 73
2.7 Bond Failure Types .............................................................................. 74
2.8 Bond Test Procedures ........................................................................... 76
2.9 Summary .............................................................................................. 77
3 Rubber to Metal and Other Substrate Bonding ............................................. 81

3.1 Introduction ......................................................................................... 81
3.1.1 Foreword ................................................................................. 81
3.1.2 History .................................................................................... 81
3.1.3 Types of Bonding ..................................................................... 82
3.1.4 The Bonding Process - An Overview ........................................ 83
3.1.5 Development of Bonding ......................................................... 84
3.1.6 Bonding Agent Reliability ........................................................ 84
3.1.7 The Environment and Solvent Use ........................................... 86
3.1.8 Methods of Reduction in Solvent Emissions ............................ 87
3.2 Substrates and their Preparation .......................................................... 87
3.2.1 Mechanical Treatment of Metals ............................................. 88
ii
Contents
3.2.2 The Abrasion Process ............................................................... 90

3.2.3 Levels of metal cleanliness ....................................................... 92
3.2.4 Time Window .......................................................................... 93
3.2.5 Chemical Preparation of Surfaces ............................................ 94
3.2.6 Future Developments ............................................................... 96
3.3 Bonding Agent Preparation .................................................................. 97
3.3.1 Solvent-borne Bonding Systems ............................................... 97
3.4 Bonding Agent Application and Use .................................................... 98
3.4.1 Application Methods ............................................................... 98
3.4.2 Waterborne Bonding Systems ................................................... 98
3.4.3 Bonding Agent Thickness......................................................... 99
3.5 Post Vulcanisation Bonding ............................................................... 100
3.5.1 Post Vulcanisation Bonding Applications............................... 100
3.5.2 Choice of Bonding Agent for Post Vulcanisation Bonding ..... 100
3.5.3 Rubber Substrate Preparation for PV Bonding....................... 101
3.5.4 Metal Substrate Preparation .................................................. 101
3.5.5 Methods of Application ......................................................... 101
3.6 Waterborne Bonding Systems ............................................................. 103
3.6.1 History .................................................................................. 103
3.6.2 Differences Between Solvent and Waterborne Bonding Agents .. 103
3.6.3 Suggested Spraying Equipment and Conditions ..................... 105
3.6.4 Application and Substrate Temperatures ............................... 105
3.6.5 Film Thickness ....................................................................... 106
3.6.6 Layover .................................................................................. 106
3.6.7 Progress in Performance......................................................... 106
3.7 Health and Safety in the Workplace ................................................... 109
3.7.1 The Safety Data Sheet ............................................................ 109
3.7.2 Perspective ............................................................................. 110
3.8 Bonding Agent Testing ....................................................................... 110
iii
3.9 Shelf Life Considerations ................................................................... 112

3.9.1 Shelf Life Categories .............................................................. 113
3.9.2 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 Solvent Elimination by the Rubber Industry .......................... 126
4.1.2 Techniques Necessary in Bonding of Rubber to Meet
Local Environmental Pollution Limits ................................... 127
4.2 Waterborne Bonding Systems ............................................................. 127
4.2.1 Structure of Organic Solvent-based Bonding Systems ............ 127
4.2.2 Structure of Waterborne Bonding Systems ............................. 127
4.2.3 Fundamentals of Waterborne Bonding Agent Application ..... 128
4.2.4 Waterborne Bonding Systems in Factory Usage ..................... 128
4.2.5 Metal Preparation - For Waterborne Bonding Systems .......... 129
4.2.6 Waterborne Bonding Agent Application ................................ 129
4.2.7 Waterborne Bonding Agent Storage Stability ......................... 130
4.2.8 Non Bond Advantages of Waterborne Bonding Systems ........ 130
4.2.9 General Comments - Waterborne Bonding Agents ................. 130
4.3 Waterborne Bonding Agents - A Factory Experience ......................... 131
4.3.1 Thickness Effects ................................................................... 131
4.3.2 Pre-bake Resistance ............................................................... 133
4.3.3 Primers .................................................................................. 134
4.3.4 Polymer Range ....................................................................... 134
4.3.5 Product Range ....................................................................... 134
4.3.6 Current Disadvantages of Waterborne Bonding Agents ......... 134
5 Rubber to Rubber Bonding ......................................................................... 137

5.1 Bonding of Unvulcanised Rubbers ..................................................... 137
iv
Contents
5.1.1 Tack/Autohesion .................................................................... 137

5.1.2 Influence of Vulcanisation System .......................................... 139
5.1.3 Influence of Filler Type .......................................................... 140
5.1.4 Effects of Plasticisers/Process Oils .......................................... 141
5.1.5 Effects of Tackifiers ............................................................... 141
5.1.6 Effects of Other Ingredients ................................................... 142
5.1.7 Effects of Surface Modification .............................................. 142
5.1.8 Effects of Surface Roughness ................................................. 144
5.1.9 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 Bonding of Vulcanised Rubbers to Unvulcanised Rubbers ................. 150
5.3 Bonding of Vulcanised Rubbers ......................................................... 152
5.3.1 Strip Bonding of Tyre Retreading Components ...................... 152
5.3.2 Effects of Strip Thickness ....................................................... 155
5.3.3 Effects of Surface Roughness ................................................. 156
5.3.4 Effects of Temperature on Bonding ........................................ 156
5.3.5 Effects of the Chemical Nature of Polymers/
Polymeric Additives/Surface Roughness ................................. 156
5.3.6 Urethane Adhesive Systems .................................................... 158
5.3.7 Surface Treatments to Improve Bonding ................................ 158
5.3.8 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 Introduction ....................................................................................... 163
6.2 Mechanism of Rubber-Brass Bonding ................................................ 165
6.2.1 Reviews ................................................................................. 165
6.2.2 Recent Mechanistic Studies .................................................... 165
v
6.2.3 Updated Rubber-Brass Adhesion Model ................................ 170

6.2.4 New Evidence for Ageing of the Interfacial Sulphide Film ..... 177
6.2.5 Compounding for Brass Adhesion ......................................... 180
6.2.6 Additives to Compounds for Brass Adhesion ......................... 181
6.2.7 Developments in Metal Pre-treatments .................................. 184
6.2.8 Developments of Novel Alloys for Bonding to Rubber .......... 189
6.2.9 Miscellaneous ........................................................................ 190
6.2.10 Summary ............................................................................... 190
7 Review of Tyre Cord Adhesion ................................................................... 197

7.1 Introduction ....................................................................................... 197
7.2 Accepted Mechanisms of Rubber-Brass Bonding ............................... 198
7.3 Ageing of the Rubber-Brass Bond ...................................................... 200
7.4 Metal Organic Cobalt Salts ................................................................ 201
7.5 The Role of Resins and Silica/Resin Systems ...................................... 205
7.6 Summary ............................................................................................ 208
8 Rubber to Metal Bonding Using Metallic Coagents .................................... 213

8.1 Introduction ....................................................................................... 214
8.2 Metallic Coagents .............................................................................. 215
8.2.1 Scorch Safety ......................................................................... 217
8.2.2 Tensile Properties ................................................................... 219
8.2.3 Tear Strength ......................................................................... 220
8.3 Experimental ..................................................................................... 221
8.3.1 Materials ............................................................................... 221
8.4 Results and Discussion ....................................................................... 229
8.4.1 Adhesion to Metals ................................................................ 229
8.4.2 Adhesion to Fibres and Fabrics .............................................. 235
8.5 Summary ............................................................................................ 238
vi
Contents
9 Rubber to Fabric Bonding ........................................................................... 241

9.1 Introduction ....................................................................................... 241
9.2 Adhesive Systems ............................................................................... 241
9.2.1 Aqueous Fabric Treatments ................................................... 241
9.2.2 Solvent-Based Adhesive Systems ............................................ 248
9.2.3 In Situ Bonding Systems......................................................... 249
9.3 Mechanisms of Adhesion ................................................................... 250
9.3.1 Dip/rubber Interface .............................................................. 250
9.3.2 Dip/textile Interface ............................................................... 252
9.4 Other Factors Affecting Adhesion ...................................................... 253
9.4.1 Storage of Treated Textiles ..................................................... 253
9.4.2 Adhesion in Service ................................................................ 254
9.5 Environmental Aspects ...................................................................... 254
9.5.1 Storage and Handling ............................................................ 254
9.5.2 In Process ............................................................................... 255
9.5.3 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 Minimise Peel and Deavage Loads .................................... 267

10.5.2 Bond Line Thickness ......................................................... 268
10.5.3 Special Requirements for Bonding with Cyanoacrylates .... 269
10.5.4 Internal and External Mould Release Agents .................... 269
10.5.5 Successful Joint Design ...................................................... 269
10.6 Bonding to Silicone Rubber ............................................................. 270
10.7 Environmental Resistance ............................................................... 270
10.7.1 Glass Bonding ................................................................... 272
10.7.2 Hot Strength ..................................................................... 272
10.8 Activators ........................................................................................ 274
10.9 Application Methods for Cyanoacrylates ........................................ 275
10.9.1 Pressure/Time Systems ....................................................... 275
10.9.2 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 Introduction .................................................................................... 285
11.2 Why Bond Silicone Rubber? ............................................................ 286
11.3 Material Combinations of Interest - Examples ................................ 287
11.3.1 Silicone to Silicone Bonding (Soft and Soft) ...................... 287
11.3.2 Silicone to Plastic Bonding (Soft and Hard) ...................... 288
11.3.3 Silicone to Metal Bonding (Soft and Hard) ....................... 288
11.3.4 Why Use Silicone Rubber for Such Composites? ............... 288
viii
Contents
11.4 Some Applications of Silicone Rubber Composites ......................... 290

11.5 Bonding Concepts ........................................................................... 291
11.5.1 Undercuts .......................................................................... 291
11.5.2 Primers .............................................................................. 292
11.5.3 Self-adhesive Silicone Rubbers .......................................... 292
11.5.4 The Build-up of Adhesion ................................................. 292
11.6 Bonding of Liquid Rubber (LR) ...................................................... 293
11.6.1 Properties of Self-adhesive LR ........................................... 297
11.6.2 Limitations of Self-adhesive LR ......................................... 298
11.7 Bonding of Solid Rubber (HTV) ..................................................... 299
11.7.1 Self-adhesive HTV Silicone Rubber Applications .............. 299
11.7.2 Applications for Self-adhesive HTV .................................. 301
11.7.3 HTV Used in Other Bonding Applications ........................ 303
11.8 Processing Techniques ..................................................................... 303
11.8.1 Liquid Rubbers in Inserted Parts Technology .................... 303
11.8.2 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 Introduction ...................................................................... 319
12.1.2 Incorrect Moulding Procedures ......................................... 328
ix
12.1.3 Incorrect Production Quality Testing Procedures .............. 329

12.1.4 Corrosion in Service .......................................................... 330
12.1.5 Product Abuse ................................................................... 333
12.1.6 Other Failure Modes ......................................................... 333
12.1.7 Factors Affecting Adhesion of Rubbers ............................. 334
12.1.8 Topography of Substrate ................................................... 335
12.1.9 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 Introduction ...................................................................... 339
12.2.2 Power Transmission Belt Failure Modes ............................ 340
12.2.3 Adhesion Systems in Power Transmission Belts ................. 346
12.2.4 Adhesion Testing in Power Transmission Belts .................. 347
12.3 Undesirable Adhesion Occuring Under Service Conditions (Fixing) .. 349
12.3.1 Factors Affecting Fixing .................................................. 349
12.3.2 Prevention of Fixing ........................................................ 351
12.3.3 Other Methods of Preventing Fixing -
Examined Experimentally ................................................. 351
Abbreviations and Acronyms............................................................................. 357
Author Index ..................................................................................................... 363
Company Index ................................................................................................. 371
Main Index ........................................................................................................ 373
x
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
Walter Strassberger
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.
1
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
2
1
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.,
3
Commercial rubbers
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.
4
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
5
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.
6
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.
7
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.
8
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
9
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
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 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
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 pre-
treatments 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
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]
Surface composition (atom %)
Polymer Treatment
C O S
LDPE None 99.8 0.2 -
1 min/20 C 94.4 5.2 0.4
6 h/70 C 85.8 13.1 1.1
PP None 99.8 0.2 -
1 min/20 C 93.4 6.3 0.3
6 h/70 C 94.0 5.7 0.3
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
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 pre-

treatments; 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)
15
Table 1.2 Quantification of surface functionalities after corona treatment

using derivatisation
Group conc. X 102 *
Functional group
Initial Washed
C OOH 1.2 0.9
C OH 1.7 1.1
C O 1.8 0.9
O
C C 2.3 1.1
O
1.6 0.8
C OH
NO3 0.8 0.4

Total [O] tagged 13.8 7.7
Actual [O] incorporated ~18 ~10
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. Position (eV) Area (%) Assignment
1 285.0 91.7 C-C, C-H
2 286.5 1.2 C-O
3 287.1 2. 3 C-O-O
4 288.1 2.3 C=O
5 288.9 1.2 COOH
6 289.5 1.3 O=C-O-C=O *
* The assignment at 289.5 eV is tentative
17
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 Exposure time (s) XPS O:C atomic ratio
None 0.0
Corona (1.7 J/cm2) 0.5 0.1 2
Corona (0.17 J/cm2) 0.05 0.0 7
Flame 0.04 0.1 2
Remote air plasma* 0.1 0.1 2
Ozone 1800 0.1 3
UV/air 600 0.0 8
UV/air plus ozone 600 0.1 4
*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
18
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.
19
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.
20
Table 1.5 Effect of pre-treatment on the peel strengths (N mm-1) of

NR-epoxide-NR [37]
Pre-treatment Peel strength Locus of failure
Toluene wipe 0.1 I
Abrasion on grinding wheel 1 I
Acidified hypochlorite 10 R
Cyclisation 1 I
TCICA in ethyl acetate 18 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 After treatment
Pure rubber 64 11
Peroxide cured 46 30
Conventionally cured 82 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
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]
Toluene wipe 0.2 I
Cyclisation 12 R
I - apparent interfacial; R - cohesive within rubber
1983, 16, 2, 77. 1983, Gordon and Breach Publishers.
22
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 Surface analysis (atom %)
of TCICA C O Si N Cl S
0 92.27 2.8 1.5 - - -
2 92.7 4.3 1. 0 1.0 0.8 0.2
7 91.5 4.6 0.7 1.9 0.9 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
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 butan-
2-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
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 bromo-
and 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]
Toluene wipe 1 I
Acidified hypochlorite 3 I
Cyclisation 0.1 I
I - apparent interfacial; R - cohesive in rubber
25
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 Initial strength Locus of failure
Toluene wipe 8 R
Cyclisation 18 R
I - apparent interfacial; R - cohesive in rubber
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 pre-
treatment 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 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
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
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
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
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
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 pre-
bake (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 Chemical
Degrease Grit blasting Other treatments
group treatments
A1, A2 Yes Yes POM-satinisation Nylon 6 and 66
Take care with Check for polyesters - desorb at >100 C,
acrylics if in optimum grit difficult surfaces especially for low
doubt use size respond to alkali pressure moulding and
alcohol or ammonium casting of PU other
persulphate forms of abrasion
treatments work generally for
these materials
B Yes No Yes TPOs flame treat, UV,
Strong oxidising corona discharge treat.
agents may be followed by
chlorination
C Yes Yes
Avoid ketones Unless <50
alcohols are safer Shore D
D Yes No PTFE, PVF treat PTFE, PVF prime with
Solvent attack on Unless > 50 with sodium a thin coat of Cilbond
PVC and PVDC. Shore D naphthalene 30/31, dry and fuse at
Avoid aqueous >200 C
degreasing of PU
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
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
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
Environmental
Plastics Bonding
Rubber Resistance of the Special Treatments
Materials System
Bonds
PPO VAMAC Heat to 180 C Cilbond 22 Grit blast PPO (200
(Dupont) Cilbond 60W 400 m grit) and
degrease with
acetone or use
alcohol for large or
awkward shapes
PPS NR SBR Glycol resistant to Cilbond 21T As above
160 C Cilbond 22
POM VMQ Heat to >>160 C Cilbond 65W Satinse POM with
p-TSA
ARAMID XNBR HNBR Heat and fluids to Cilbond 89 Abrade or grit blast
>170 C Cilbond 22 with fine grit.
Degrease with MEK
Prebake first thin
coat of primer at
100 C use
Cilbond 22 for PV
bonding
PTFE FKM Hot oils to >>160 C Cilbond 65W Sodium treat PTFE
and prime as soon
as possible
PP EPDM Water to 100 C Cilbond 89 Oxidise/flame treat
FILLED PP. Prebake a first
thin coat of primer
GRP PU rotation Bonds outperforms Cilbond 41+B Belt abrade and
cast the PU for roller and Cilbond water or
pipe coatings 49SF+B hydrocarbon
degrease. Allow first
coat to dry >2 h and
second coat for >4
h, but <30 h
PET TPU Heat to 140 C Cilbond 49SF Alkali or ammonium
persulphate etch
PET
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
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
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:
Time
Process Performance
(s)
Wet blasting 30 0 Wet blasting with satin finish and degreasing
1st rinsing 30 Rinsing work to remove remaining media
Degreasing (non-solvent Degreasing areas of the work piece that could
300
type) not be degreased by wet blasting
2nd rinsing 60 Removing degrease chemicals
3rd rinsing 60 Removing degrease chemicals
1st phosphating 18 0 Phosphate coating
2nd phosphating 18 0 Phosphate coating
Dipping for rinse 60 Removing phosphate
Removing phosphate and warming up work for
Dipping for hot rinse 60
drying
Drying 120 Drying work completely
Total process time 1350
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
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 Hoist loader This hoist raises the components to the hopper
located at the upper side of the blast section
Stage 2 Blast inlet hopper This works as a transfer accumulator and shortens
the transfer time for loading components into the
blast barrel
Stage 3 Wet blast section Simultaneous degreasing and matt surface finishing
through barrel processing
Stage 4 Blast unload bucket Water collected within the components is removed
here before transfer into the next stage
Stage 5 Remove tank The degreasing process is completed here
Stage 6 2nd and 3rd rinse tanks Removed grease and media are rinsed off with water
Stage 7 Surface adjustment tank Pre-processing is done so that a stable phosphate
film can be made in the phosphating process
Stage 8 Phosphate tanks Two tanks are used to form the phosphate film
Stage 9 Water rinse Two water rinse tanks are used to remove residual
chemicals from the components
Stage 10 Hot water rinse tanks Two water rinse tanks are used to remove residual
chemicals from the components
Stage 11 Dryer Water is cut off and the components dried by hot air
Stage 12 Unload conveyor Processed components are unloaded
50
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56
2
Rubber to Metal Bonding
J. R. Halladay and P. A. Warren
2.1 History
Rubber finds use in many applications as a means of isolating vibration and reducing shock
or as a way to seal in solids, liquids and gases. For many of these applications, it is desirable
or even imperative that the rubber be attached to a metal substrate in a reliable manner.
There is a fundamental difference between bonding of rubber to metal involving crosslinking
mechanisms and the physical sticking of rubber to metal using a non-vulcanising adhesive.
The former involves a chemical reaction (generally during cure) while the latter generally
relates to a physical surface tension phenomenon. Bonded rubber parts have found use in a
myriad of dynamic applications such as engine mounts, suspension bushings, body mounts,
torsional dampers, helicopter rotor bearings, seismic bearings, transmission and axle seals,
and as flexible couplings. These parts are usually made by vulcanising the rubber and bonding
it to the metal component in a single-stage press operation.
Fluid engine mounts (Figure 2.1) for the aerospace industry and automotive hydromounts
require the bonded rubber to act as both a seal for the fluid and as a spring component
Figure 2.1 Cross section of a typical Fluidlastic mount
Courtesy of Lord Corporation
57
in the isolation system. Many of the applications such as a helicopter rotor bearing
(Figure 2.2) comprised of alternating layers of rubber and metal in special geometric
configurations, would be impractical or even impossible without the ability to obtain a
rubber to metal bond with a high degree of integrity and reliability.
Other rubber parts may be bonded to metal simply for ease of assembly or to provide a
tolerance for misalignment. Just within an automobile, bonded rubber to metal assemblies
are used for engine mounts, oil seals, couplings and bushings for the engine, transmission
and drive train, fan hub couplings, body mounts, exhaust hangers, weather strips and
window channelling, and tuned vibration absorbers within the frame and suspension. This
illustrates just how important bonded rubber to metal assemblies are to everyday life.
The increased use of rubber in automotive, aerospace, and industrial applications has
driven the requirement for strong and robust bonds between rubber and metal. Much
literature has been published on the history and technology of bonding rubber to metal
[1, 2, 3, 4, 5, 6, 7, 8]. The earliest historical methods of attaching rubber to metal involved
attaching the rubber by mechanical means or by the use of ebonite. Mechanical
Figure 2.2 Cross section of a helicopter rotor bearing

(Photograph by James Halladay. Courtesy of Lord Corporation)
58
attachment, which is still used today in some cases, creates an insecure union. Ebonite is
made by mixing approximately 30 to 40 phr (parts per hundred rubber) of elemental
sulphur with natural rubber (NR). It forms a true bond to the softer sulphur curable
rubbers. It also adheres rather strongly to metal. Soft rubber compounds normally contain
less than 4 phr sulphur which creates sulphur crosslinks between the rubber molecules.
At sulphur levels between 25 and 45 phr, hard rubber or ebonite is formed. In ebonite, a
large proportion of the sulphur is believed to be in the form of intramolecular addition
since it is noticeably thermoplastic [9]. Bonding with ebonite has several disadvantages.
One significant drawback is that the ebonite is thermoplastic and becomes quite weak
with moderate temperature exposure. Depending on the amount of sulphur, ebonite
based on NR shows a thermoplastic transition temperature, i.e., softening, between 70 and
80 C. At sulphur levels between 4 phr and 25 phr, NR goes through a transition where
it becomes rather leathery and is of little use. Because there will be a gradient of sulphur
between the ebonite adhesive and the soft rubber compound, at some point, the sulphur
content of the compound must pass through this transition zone. This transition zone
weakens the softer rubber in the interfacial region and it reduces the flexibility in that
region. As a further drawback, bonding with ebonite limits the chemistry of rubber
formulations that can be successfully bonded using this technique.
Another method of bonding involved the use of special metal alloys which were capable
of reacting with and combining with sulphur. The earliest patent for the use of alloys
was in Germany in 1904 [10]. Daft patented alloys containing antimony in the US between
1912 and 1913 [11, 12, 13, 14]. He also claimed the use of alloys of copper and zinc
with bismuth and arsenic. These alloys were electrically deposited on the metal and the
bonds to rubber were formed during the vulcanisation process.
In 1862, Sanderson submitted a British patent application for the use of electrodeposited
brass as an intermediary for bonding rubber to iron or steel [15]. It was not until between
1920 and 1930 that the process of bonding to a galvanic layer of brass (brass plating)
was commercialised. The bond is obtained by virtue of the chemical reaction that occurs
between the brass and the sulphur curative in the rubber and it has the advantage over
the ebonite process of not being heat sensitive. This process requires a large investment
in processing machinery and it is difficult to keep all the variables in the galvanic bath
constant. It is somewhat unpredictable and shows a high sensitivity to processing
conditions. As with bonding to ebonite, it limits the chemistry of the formulations that
can be successfully bonded to only those compounds with a high sulphur cure (2 to
4 phr). As a further complication, not all types of brass will bond to rubber and it appears
that the best ratio of copper to zinc is somewhat compound dependent. In a production
environment, consistent results are often hard to obtain without considerable experience
and the factors which must be carefully controlled include bath and anode composition,
temperature, voltage, current density, time of deposition and hydrogen-ion concentration.
59
However, the brass plating process has proven quite successful for certain applications
such as steel cords for automotive tyres.
Another method of rubber to metal bonding was discovered in Germany around the
end of World War II and involves the use of isocyanates, in particular triphenylmethane
triisocyanate [16, 17]. Polyisocyanates applied to a clean metal surface give good primary
adhesion between many types of NR and synthetic rubber formulations and a wide
variety of metal substrates without the brass layer. Isocyanates are very sensitive to
moisture and steam and because they are extremely reactive, there is the potential for
undesirable side reactions with the compounding ingredients in the rubber formulation.
Because of their extreme reactivity with moisture, exposure to even moderately humid
conditions during the time between application to the metal and the moulding process
results in loss of much of the adhesive strength of the bond.
During the 1950s, another area of research was based around self-bonding compounds.
Patents issued in the late 1950s and early 1960s covered the addition of cobalt salts to
the rubber formulation [15]. The use of resorcinol and a formaldehyde donor (RFL
system) had been developed in 1935 as a dip for rubber to textile adhesion (see also
Chapter 9). In the 1960s, these components were added directly into the rubber along
with a reinforcing silica filler by Bayer and Degussa independently to make self-bonding
compounds (RFK system). Hexamethylolmelamine ethyl ethers or hexamethylene
tetramine were used as the formaldehyde donors to form an in situ curable resin capable
of bonding the rubber to textiles or metal, particularly steel tyre cord.
More recently, techniques for making self-bonding compounds by incorporating

metallic coagents have been proposed [18] (see also Chapter 11). The coagents most
often used are zinc diacrylate (ZDA) and zinc dimethacrylate (ZDMA) although other
metals such as calcium and magnesium have been noted as somewhat less effective.
These metallic monomers derive some unique physical and mechanical properties
from the ionic bonds that are formed between the metal cation and the carboxylate
anion. The same ionic crosslink mechanism is believed to occur with rubbers that are
cured with ZDA or ZDMA. These coagents are only effective with peroxide (or free
radical) cure systems.
There are several drawbacks to the use of self-bonding compounds which are worthy
of mention. To make a self-bonding compound, one must modify the properties of the
bulk rubber compound in order to affect the chemistry of the reactions which are
required to take place only at the rubber to metal interface. Processing is adversely
affected since the compounds want to bond to the mould and metals alike, and the
environmental resistance of the rubber to metal bond is generally poor compared to
that which is obtained with the use of a conventional rubber to metal adhesive system.
60
The dearth of versatile and highly satisfactory bonding approaches prompted the Lord
Corporation to investigate improvements in the rubber to metal bonding process shortly
after World War II. The efforts led to the development of general purpose chemical
adhesives containing polymers and crossbridging agents in solution. The first general
purpose adhesive system was introduced in 1956 and comprised a primer and an
adhesive top coat or cover-coat which produced rubber tearing bonds over a spectrum
of different rubbers which were commercially available at that time [2]. Rubber tearing
bonds refers to bonds which show cohesive failure (failure within the rubber) when
subjected to destructive testing. Migration of crosslinking agents from the adhesive
layer into the rubber compound produce a tougher layer adjacent to the metal and
increase the tendency to have cohesive failure in the rubber during destructive testing.
The primer/cover-coat system gave bonds with better environmental resistance than
any other system available at the time and rapidly became the standard for rubber to
metal bonding practice. Perhaps more importantly, the new adhesives were broadly
compatible with all the important high diene rubbers over a broad range of curing
conditions. They paved the way for bonding newer rubbers such as the polychloroprenes
and for compounds containing a wider range of compounding ingredients than was
previously possible. They also helped to eliminate the restrictions on the design engineers
choice of metal for the substrate.
The last four decades have seen the introduction of many new rubber to metal adhesives
designed to cover the ever increasing range of synthetic rubbers currently available for
use in dynamic applications. These include one coat adhesives, adhesives for post-
vulcanisation bonding, specialty rubber adhesives for silicones, fluorosilicones,
fluororubbers, acrylics, and hydrogenated nitrile rubbers, along with the recent
introductions of water-based adhesives.
Today, many companies make adhesives for chemically bonding rubber to metal. The
following companies supply general purpose primers and adhesives:
Company Tradename
Lord Chemical Products Division of Lord Corporation Chemlok

Henkel KGaA (Lord licensee) Chemosil
Rohm and Haas Thixon; Megum
Par Chemie Parlok
Chemical Innovations Limited Cilbond
Metalok Metalok
Proquitec Adetec
61
2.2 Bond System Characteristics
2.2.1 Adhesive Characteristics
General purpose primers and adhesives used for bonding rubber to metal are highly
proprietary, specially formulated products. They usually contain a mixture of polymers,
resins, curatives, pigments, extenders, and other ingredients, e.g., corrosion inhibitors or
viscosity stabilisers. These materials are either dissolved or suspended in a liquid media.
Up until the early 1990s, rubber to metal adhesives were almost exclusively formulated in
organic solvents. Due to the need to reduce emissions of volatile organic compounds (VOCs),
a growing number of aqueous rubber to metal adhesives are being commercialised.
Rubber to metal primers contain organic resins which react with most metal (steel,
aluminum, stainless steel, copper, brass) surfaces during the vulcanisation process to
form a chemical bond to the metal. They also contain polymers which allow for better
film formation and act as an anchor for the subsequent application of the adhesive.
Rubber to metal adhesives contain polymeric materials that are compatible with the
ingredients in the primer, as well as the rubber compound to be bonded. Many are based
on halogenated polymers. Halogenated polymers or resins are known to wet metals
efficiently and can be used in both the primer and adhesive formulation. They provide
effective barriers to chemicals that can undermine the adhesive bond. The adhesive also
contains very powerful curatives that react with both the polymers in the rubber and the
polymers in the adhesive [19]. Difunctional and polyfunctional chemicals are capable of
making the film forming polymer a thermoset as well as reacting across the interface of
the film to link into the rubber.
The rubber to metal bonding mechanism is very complex as there are several reactions
occurring simultaneously. All these reactions must take place in a very short period of
time (i.e., during the press cure time of the rubber) in order for a strong bond to form.
The different reactions taking place are shown in Figure 2.3.
Each of the three organic layers in a rubber to metal bond (primer, adhesive, rubber) crosslink
or cure during the moulding step. The source of this crosslinking is the presence of either a
heat reactive resin or externally added crosslinking agents. This internal curing increases the
molecular weight and cohesive strength of each layer. In addition, each layer undergoes
reactions with the layers immediately above and below it. These interlayer reactions are
caused by the same chemical ingredients that allow for internal crosslinking to occur.
The first link in a rubber to metal bond is the primer to metal interface. As mentioned
previously, in addition to the internal crosslinking that takes place in the primer, organic
62
Figure 2.3 Schematic of vulcanisation bonding process

(Courtesy of Lord Corporation)
resins in the primer react with metal oxides on the surface of the metal part to form very
strong covalent chemical bonds. This type of reaction is called chemisorption [8]. It is
differentiated from normal adsorption or physical bonding in that bonds formed by
chemisorption are very resistant to attack from water, heat, and chemicals. In contrast,
bonds formed by adsorption are easily destroyed by the application of environmental
forces such as heat or chemical exposure.
The next link in the rubber to metal bond is between the primer and adhesive interface.
The curative present in the adhesive layer migrates or diffuses into the primer layer
during vulcanisation and forms a chemical bond between the primer and adhesive. The
polymeric film former present in the primer diffuses and knits with the adhesive layer
and further strengthens the bond between primer and adhesive because of its compatibility
with polymers present in the adhesive layer. The final link in the rubber to metal bond is
the adhesive to rubber interface. The curative present in the adhesive layer also diffuses
into the rubber during vulcanisation and forms a chemical bond between the adhesive
and the rubber. These bonds which span across the layers in the assembly are called
crossbridges to differentiate them from the crosslinks which occur within the rubber
itself. In addition, sulphur from the rubber compound diffuses into the adhesive layer
and helps to form additional crossbridges between the rubber and the adhesive.
Rubber to metal adhesive systems generally occur in two broad classes. These are primer/
cover-coat systems and one coat (or single coat) systems. In the primer/cover-coat systems,
63
the primer primarily contains materials which will form strong and enduring bonds with the
metal surface. The modulus of the cured primer is intermediate between that of the rubber
and that of the metal, but it is closer to that of the metal. The cover coat, on the other hand,
primarily contains materials that form bonds with the rubber and the resulting modulus of
the cured adhesive is closer to that of the cured rubber. The complete system provides a
gradation in the modulus between the rubber and metal and creates a better stress distribution.
One coat adhesives, by necessity, contain both materials which react with the metal surface
and materials which react with the rubber. These materials, in many cases, are not stable
together, so long term shelf stability of one coat adhesives is more difficult to achieve.
Each system has its advantages and disadvantages. Typically, primer/cover-coat systems
are more resistant to extreme environmental conditions such as hot oil or extended salt
spray exposure. However, primer/cover coat systems are more expensive to apply because
of the need to have two sets of application equipment, one for primer and another for
cover-coat. One coat systems only require one set of application equipment and require
only one application step instead of two, and hence, are less costly to process. Inventory
issues are significantly simplified with the use of one coat adhesives.
2.2.2 Compound Characteristics
Although the development and successful commercialisation of organic adhesives for

bonding rubber to metal has freed rubber chemists to use a wider variety of materials
while still achieving excellent bonds to metal, there are some general rules of thumb that
should be followed where possible to improve the probability of bonding to the rubber.
The first rule is to use the easiest-to-bond type of rubber that will provide the required
service performance of the part. In general, there is a hierarchy among rubber types
which ranks them according to their ability to be bonded with adhesives. This hierarchy
is called the bondability index [4]. What causes differences in bondability is still a
matter of debate. It has been attributed to differences in polarity, chemical reactivity,
solubility and molecular symmetry between the different available classes of rubbers [4].
Regardless of the cause, the bondability of general purpose rubbers is ranked as follows:
Easiest to bond Nitrile (acrylonitrile-butadiene) rubber (NBR)

Polychloroprene (CR)
Styrene butadiene rubber (SBR)
Natural rubber or polyisoprene (NR or IR)
Ethylene propylene diene rubber (EPDM)
Most difficult to bond Isobutylene-isoprene (butyl) rubber (IIR)
64
Many times, the choice of rubber is dictated by the service requirements of the part.
Even within classes of rubbers, there are different degrees of bondability based on the
specific polymer chosen and depending on the rest of the ingredients in the formulation.
Nevertheless, the bondability index shows the relative ease of bonding certain classes
of rubbers.
The choice of vulcanisation system for the rubber can have a dramatic effect on adhesion.
Typically sulphur cured rubbers are easier to bond to than sulphur-free or peroxide
cured rubbers. This is believed to be due to the interaction of sulphur with key curative
materials in the adhesive. The more sulphur that is present, the more interactions that
are available, and hence the better the chance of getting good adhesion. SEV (semi-
efficient vulcanisation) and EV (efficient vulcanisation) cure packages are typically more
difficult to bond because of their lower free sulphur contents. EV refers to cure systems
which give predominantly monosulphidic or disulphidic crosslinks whereas conventional
sulphur cure systems produce mostly polysulphidic crosslinks. SEV systems fall somewhere
between EV and conventional systems in the type of crosslinks produced. Vulcanisation
proceeds at different rates and with different efficiencies in different types of polymers,
so the amount of sulphur needed to produce an EV cure system will also vary. For example,
in NR, an EV system will generally contain between 0.4 and 0.8 phr of sulphur, while in
NBR the sulphur level will generally be less than 0.3 phr of free elemental sulphur.
In sulphur cured rubbers, accelerators are generally used to reduce the dependency on
sulphur in order to achieve more efficient vulcanisation, to improve heat and flex resistance
due to the presence of more monosulphidic crosslinks, and to increase the cure rate of
the rubber and improve production capacity. Two accelerators which have been shown
to enhance bondability of rubbers are 2-mercaptobenzothiazole (MBT) and
mercaptobenzothiazole disulphide (MBTS). An accelerator which is known to negatively
impact on adhesion is tetramethyl thiuram disulphide (TMTD).
Peroxide cured rubbers are the most difficult to bond to metal with conventional adhesives.
This is because the free radical peroxide cure mechanism competes with the curative in
the adhesive for reactive sites on the rubber backbone.
Fillers in the rubber play an important part in adhesion. When used in normal amounts
(20 50 phr), the more highly filled the rubber, the easier it is to bond. This is because
increasing the filler loading of the rubber increases the modulus of the rubber to more
closely resemble the modulus of the adhesive, thus reducing differential stress at the
interface. Of course, at excessive filler loadings, a point is reached where the adhesive
film contacts more filler than rubber. At this point adhesion drops off significantly. Carbon
black and silica are the preferred fillers for improved adhesion and channel blacks are
preferred over thermal or furnace blacks [4].
65
Processing oils are often necessary to ensure good flow and proper filling of moulds.
Unfortunately, the use of these oils can seriously hamper adhesion due to their ability to
migrate to the adhesive/rubber interface during vulcanisation and interfere with
crossbridging reactions. Lower levels of processing oils are always preferred for best
adhesion. Naphthenic oils have the least deleterious effect on adhesion, while aromatic
and ester based oils should be avoided if at all possible.
Antidegradants including waxes, antiozonants, antioxidants, and prevulcanisation

inhibitors are also necessary for good processability and performance of rubbery parts.
Unfortunately, these materials are also bad for adhesion because they can also migrate to
the rubber surface and interfere with crossbridging reactions. The lowest possible amount
of these materials necessary to get acceptable part performance without causing blooming
to the surface of the rubber is preferred.
2.3 Adhesion
The selection of the best adhesive to use in a particular bonding situation depends on
several factors. They include:
The rubber being bonded,

Government regulations in force in a particular area,
The moulding process employed (compression, injection or transfer),
Level of environmental resistance required,
Adaptability to existing adhesive application equipment,
Cost.
Of course, one needs to use an adhesive that is designed for use with the particular
rubber being bonded. Some adhesives are designed for bonding a broad range of NR and
general purpose synthetic rubbers. Others are designed to bond specific hard-to-bond
general purpose rubbers such as EPDM or IIR. Some adhesive systems are designed
specifically for bonding specialty rubbers such as urethanes, hydrogenated nitrile rubber
(HNBR), silicones and fluororubbers. It should be obvious that these are not
interchangeable simply from a chemistry standpoint. Adhesives for specialty rubbers are
often based on organofunctional silanes or on reactive phenolic resins. Silane-based
adhesives chemisorb strongly onto clean glass or metals such as aluminum, brass, iron,
steel, titanium, and other alloys.
Government regulations regarding solvent emissions in the users locality are also of
importance. In the US, some customers must use aqueous adhesives or adhesives containing
66
certain permissible solvent systems in order to stay in compliance with government

regulations on volatile solvent emissions.
The type of moulding process being employed is important to consider. Some adhesives
perform better at low cure temperatures (less than 155 C) with long cure times, e.g.,
compression moulding. Some adhesives are designed to work in high temperature (greater
than 170 C) and short cure time applications, such as injection moulding.
The level of environmental resistance required and equipment available may determine
whether to evaluate primer/cover coat systems versus one coat adhesive systems. And last,
but not least, cost of both the adhesive and the application process is an important factor
to consider in any industrial application, rubber to metal bonding being no exception.
An important requirement for good bonds is proper preparation of the metal substrate.
Untreated metal surfaces are generally subject to corrosion and other changes over time.
Corrosion is often described as destruction of metal by chemical or electrochemical
reaction. Most environments are corrosive, but by no means to the same degree. Simply
bonding a rubber layer over the top of the metal surface does not stop corrosion from
occurring underneath the bond. While a strong primary (initial) bond may sometimes be
obtained with poorly prepared substrates, the bond will degrade over time, especially
with exposure to harsh environments, leading to premature failure or a shortened
operating life. Environments which foster corrosion include: air and moisture, fresh or
salt water, steam, chlorine, ammonia, hydrogen sulphide, sulphur dioxide, mineral acids,
organic acids, alkalis, solvents and fuel gases. Often, the underbond corrosion is
aggravated by bonding to surfaces where corrosion has already begun. The substrate
and type of contaminant dictate the proper cleaning procedure. In most cases, metal
preparation involves two main steps. The first is a cleaning step to remove dirt, oil, and
other surface contaminants. The cleaning step can be accomplished by either solvent
degreasing (typically with perchloroethylene) or by alkaline cleaning (aqueous).
Next comes a step designed to activate the metal. The functions of the metal activation
step are:
1. to remove any contaminants such as rust, scale, and pre-existing corrosion byproducts
which are bound to the metal surface,
2. to increase the surface area of the metal,
3. to provide an active surface for bonding.
The metal activation step can be accomplished by use of mechanical or chemical means.
Mechanical methods for steel include blasting with 40 mesh steel grit, sand or aluminium
oxide grit. Other metals may be blasted using clean sharp aluminium oxide grit or sand.
67
Steel grit should not be used on non-ferrous metals as it will leave a ferrous smudge that
can later oxidise and degrade the bond. After blasting, it is recommended to use either
solvent degreasing or alkaline cleaning on the metal a second time to remove dust and
any other particulate byproducts from the blasting process.
While it is possible to bond to a freshly abraded or cleaned metal surface, chemical

treatments are preferred for rendering the metal surface inactive to corrosion over time.
For low carbon steel, phosphatising is the recommended pre-bond surface preparation
treatment. Stainless steel should be passivated or acid etched, while titanium is usually
treated with a hydrofluoric acid pickle. Aluminium or magnesium are best treated with
a chromate conversion coating. Zinc and cadmium are generally prepared mechanically
but a phosphate or chromic acid treatment may be used. Brass and copper may be treated
with an ammonium persulphate etch or an acid-ferric chloride etch.
The type of surface preparation employed depends on several factors. Cost is one
important factor. Chemical pretreatments are usually less expensive than mechanical
treatments, especially from the standpoint of labour efficiency. But versatility of the
process is also important. Mechanical treatments can be useful for many different metal
surfaces. However, chemical treatments are usually metal specific. So several chemical
treatments may be necessary if different metals are to be bonded in the same plant or
operation. It is important to use metal treatments that can be adapted to the users
manufacturing environment. Available floor space, ventilation, and equipment capacities
must be taken into account. The environmental resistance requirements of the bonded
part are the key to determining what type of metal treatment may be used. For parts
which have very demanding corrosion resistance requirements, i.e., automotive or
aerospace applications, chemical treatments are highly recommended. For parts being
used in non-demanding environments, for example, indoor applications, mechanical
pretreatments may suffice. Finally, local government regulations regarding hazardous
waste disposal must be considered. Chemical treatments, such as zinc phosphatising,
usually involve the generation of hazardous sludge as a byproduct of the process. If local
regulations in force for a given area make disposing of this sludge expensive or
inconvenient, then mechanical treatment methods may be a less troublesome option.
Regardless of the metal pretreatment used, it is important to maintain as much control

over the process as possible in order to assure consistently good results. Lubricants and
anticorrosive oils that contain chlorinated paraffins or silicone should be avoided, as
they can interfere with adhesion. All degreasing solvents and cleaning solutions must be
kept clean and free of contamination. Grits and abrasives must be kept clean and
periodically changed. Rinse water and drying air must be checked frequently for purity
and kept free from oils. A simple test to measure the effectiveness of the metal pretreatment
is called the water-break test. In this test, the prepared metal part is dipped briefly in
68
de-ionised water and then removed. The surface of the dipped part is examined for signs
of poor wetting. If the part can be wet by water with no breaks or fisheyes, then the
metal is considered to be clean. The water break test is described in ASTM (American
Society for Testing and Materials) test method F22 [20].
A typical metal pretreatment process for steel might involve the following steps: alkaline
cleaning, water rinse, phosphoric acid pickle, water rinse, zinc phosphate treatment, rust
inhibitive treatment (seal), water rinse, followed by drying. The zinc phosphate coating
must be controlled for maximum effectiveness. While a thin coating of zinc phosphate
crystals reduces underbond corrosion and improves environmental resistance, a thick
coating will reduce the bond strength. This is because the cohesive strength of the zinc
phosphate crystal is less than the adhesive strength of the crystal to the adhesive or to the
metal substrate. As a result, too thick a coating will simply fracture within the zinc
phosphate crystal causing lower than expected bond values.
A typical treatment for stainless steel is a vapour degrease or alkaline clean followed
by immersion for 15 to 20 minutes at 50 to 55 C in a solution consisting of 20 25%
nitric acid (by weight), 2 4% sodium dichromate (by weight), and 71 78% water
(by weight).
There is increasing use of rigid plastics as substrates in place of metals. Plastic surfaces
may be prepared by chemical cleaning and/or surface roughening with a mechanical
blast. Flame treatment and corona treatment are also viable options.
Once an optimum surface condition has been obtained, care must be taken to preserve it
until the primer or adhesive has been applied. It is important to prevent exposure to
dust, moisture, mould sprays, or oils from handling. Even exposure to air over a period
of time can create an oxide layer so thin it cannot be seen, but one which can cause
adhesion problems later. One of the best methods of preserving the surface is to apply
primer as soon as possible.
Primer and adhesive application are generally accomplished by spraying, brushing,

tumbling or dipping. Each different application method has its own strengths and
weaknesses. The choice of the application method is dependent on the size and shape of
the parts, the number of parts to be coated, and whether the part is to be wholly or only
partially coated.
Spraying assures excellent application where selective or spot coating is required and
may be easily automated. Spraying can be accomplished by several methods (conventional
air assisted, airless spray or electrostatic spray). Sprayed films usually give the best aesthetic
appearance to a coated part (no runs, sags or tears). Dry film thickness is easier to
control with spraying because adjustments can be made in adhesive dilution, fluid flow,
69
and air pressure to give different levels of film buildup. In applications where only specific
areas of the part are to be coated with adhesive, spraying allows the best chance to coat
only certain areas of the part by the use of spray masks. The weakness of spraying is that
adhesive is lost due to the need for overspray to ensure proper coverage of the part. The
use of high volume low pressure (HVLP) and electrostatic spray options has improved
the efficiency of spraying as an application process.
There are many manufacturers of spray equipment who can recommend the proper spray
guns for a particular application. The air pressure to the gun should be adjustable, as
should the atomisation pressure and the tip opening. Adjustment of these variables will
allow for proper wetting and coverage of the metal. Liquid lines should have a 100 mesh
screen to prevent dried or agglomerated material from getting to the gun and clogging it.
Liquid lines should be short with diameters of 13 mm or less. This will provide good
mixing of the product in the line from turbulent flow. Short liquid lines will prevent
settling of dispersed particles in the line. Air lines should have water traps to prevent oil
or water from contaminating the adhesive and causing bond problems. The adhesive
being sprayed should be under continuous agitation to keep the product homogeneous
and to prevent settling of active solid materials.
Proper maintenance of spray equipment is important to ensure continuous problem-free

operation. Gun tips should be checked periodically for adhesive build up. If any is found,
it should be removed to keep the spray pattern consistent. Fluid lines should be flushed
periodically. Fluid pressure regulators should be cleaned periodically to keep them working
properly. Spray guns should be flushed and rebuilt periodically to replace worn parts
and to remove any adhesive build up.
Dipping is a convenient and economical method for adhesive application for small runs
and it can be automated for larger runs using a conveyor belt. Dip application of rubber-
to-metal adhesives allows for better transfer efficiency because once the metal part comes
out of the dip tank, much of the adhesive which drains off the part goes back into the
bath thus conserving adhesive. The transfer efficiency of dipping is better than that of
spraying and because dipping is a simpler process than spraying, there are less variables
to control. However, there are not many things one can do to control dry film thickness
in dipping due to its lack of control variables, e.g., adhesive solids and viscosity are fixed
unless dilution can be used. Also, in dip applications, the dry film thickness of adhesive
increases going from the top to the bottom of the part. This is due to gravity pulling the
wet adhesive down the part surface as it dries. Dipped parts are susceptible to formation
of tears and drips on the parts. These tears can cause problems with mould fouling
during the moulding step. Also, dipping is useful only for those parts where no masking
is necessary, since the whole metal part is dipped. Adhesive is applied even to areas
where there will be no rubber present for bonding, so some adhesive is wasted.
70
Adhesive used in dip applications should be kept under continuous agitation. If a dip
tank is used, double diaphragm type circulating pumps are recommended and impeller
type agitators should be used.
Brushing is useful for prototypes and small or discontinuous production runs. However,
brush application of rubber to metal adhesives, while being the simplest method, is not
recommended. This is because control of dry film thickness is very difficult to achieve
over the part surface. Also, imperfections, such as brush marks or loose bristles in the
adhesive film can interfere with performance.
Both primers and adhesives should be kept well agitated prior to, and during, application
and the coatings should be uniform in thickness across the part. Primers are required
for maximum environmental resistance and the primer should be completely dry before
the adhesive cover coat is applied. When more than one coat of adhesive is applied,
adequate time and temperature must be allowed to ensure complete solvent evaporation
between coats.
Primers are usually applied to a dry film thickness of 5 to 10 m. Cover coat adhesives
are applied at dry film thicknesses of 10 to 15 m. One coat adhesives work best at
applied dry film thicknesses of 20 to 25 m. Measuring instruments to check dry film
thickness should be used to insure adequate adhesive application and as a quality control
check. Beta backscatter machines work well for all types of inorganic surfaces. However,
they are not suitable for adhesives that contain radiation absorbers such as lead.
Magnetic induction current instruments work well on steel, but not on non-magnetic
substrates such as aluminum or glass.
2.4 Effective Bond Formation
Even after the metal parts are coated with adhesive, care must be taken to ensure that the
surface of the adhesive film does not become contaminated prior to moulding. Any
material (dirt, oil, etc.) which can get in between the adhesive and the rubber will prevent
the formation of a robust chemical bond and failure will be likely to result. Operators
who handle coated parts should wear clean cotton gloves to prevent oils from their
hands from contaminating the adhesive. Coated parts should not be stored in areas
where they can be exposed to mould releases (either splashed or airborne droplets), dust,
and moisture. If coated parts are to be stored for any extended period of time, the container
should be covered with either cardboard or untreated Kraft paper. Coated parts should
also be kept in areas where they will not be exposed to sunlight or UV radiation for
extended periods of time.
71
The moulding step is arguably the most important step in the process of making rubber
to metal bonded parts. It is during this step, with heat and pressure applied for a prescribed
amount of time, that the rubber is vulcanised and the actual bond between the rubber
and the adhesive-coated part is formed. Each step of the moulding process must be carefully
controlled to maintain consistently good quality in the bonded parts. Three of the most
important factors are moulding pressure, moulding temperature, and mould design. For
the best adhesion, it is important to maintain maximum mould pressure while the rubber
is at minimum viscosity. This ensures the best wetting of the rubber over the adhesive
surface. Adequate pressure must be maintained throughout the rubber cure cycle. If the
pressure is insufficient, the rubber may become porous during the cure and the bond to
the adhesive will be poor. The temperature throughout the mould must be maintained at
a consistent level. Low temperature zones in the mould can cause undercure of the rubber
and this will lead to poor adhesion. High temperature areas in the mould can cause
overcure or reversion (crosslink degradation) of the rubber and possible pre-cure of the
adhesive before rubber can come into intimate contact with it.
When designing moulds, loading of coated metals and removal of bonded parts should be
made as easy as possible. The time required to load the mould with adhesive coated metals
should be kept to a minimum. The longer the coated metals sit in the hot mould without
being exposed to rubber, the greater the chance that premature curing of the adhesive will
take place, with a subsequent loss of adhesion. Effort should be made when designing both
the part and the mould to place areas of high stress concentration as far away from the
rubber/metal interface as possible. Mould parting lines should be avoided in critical bond
areas. Sprues and gates into the cavity should be placed if possible in such a manner that
the flow of rubber does not cause sweeping of the adhesive from the metal surface.
Moulds can create problems for the bonding process if they are either too tight or too
loose. If they are too tight, volatile gases cannot escape, but if they are too loose, the
rubber compound can continue to seep out under pressure before and during the
vulcanisation stage. This continued seepage can cause the adhesive to be swept from the
metal surface, reducing the integrity of the bond. It can also cause a loss of pressure
inside the cavity, and adequate pressure is one of the factors necessary for good bonding.
Moulds should be vented if possible to allow for escape of volatile components from
both the adhesive film and from the rubber during the moulding process. If the volatile
components from the adhesive are not allowed to escape, they may react with the rubber
being introduced into the mould cavity and cause pre-cure of the rubber before it has a
chance to fill the cavity. When this happens, bonded parts have small knit lines or
splits formed in the body of the rubber. These knit lines often dramatically shorten the
useful service life of a bonded part by developing into premature fatigue cracks during
service. If volatile compounds from the rapidly heating rubber are not vented, they may
contaminate the adhesive surface, thus reducing the quality of the bond.
72
2.5 Post Vulcanisation Bonding
Post vulcanisation bonding (also referred to as PV bonding) is a specialised variation of

the rubber to metal bonding process. For PV bonding, adhesive is applied to metal, just
as for vulcanisation bonding. However, in this process, the rubber has already been
moulded and is fully vulcanised. Not all adhesives give good results in PV bonding and
the selection of satisfactory adhesives for a given application will be more limited than
for vulcanisation bonding. Usually the surface of the vulcanised rubber to be bonded is
given a treatment to remove any materials which can interfere with bonding (i.e., surface
bloom, mould release agents) and to provide a fresh surface to bond to. Chemical or
mechanical methods can be used. Chemical methods involve applying a chlorination
treatment to the rubber surface. The chlorination treatment creates reactive sites on the
surface of the rubber where the adhesive can interact. It also changes the surface energy
and makes it easier for the adhesive to wet the rubber surface completely. A common
mechanical method is buffing the rubber surface with an abrasive material, such as
sandpaper. The treated rubber is then put in contact with the adhesive coated metal
using moulds or tooling fixtures to position the rubber and hold it in place. A compressive
deflection of 5 10% is maintained to keep the two surfaces in intimate contact while
heat is applied until a bond is formed. An oven, autoclave, or induction heating unit can
be used, depending on the size and number of parts to be bonded.
PV bonding has both advantages and disadvantages. Advantages include the elimination
of the need for expensive moulds to make parts and the ability to make bonded parts at
lower temperatures (125 150 C). One disadvantage is that extra steps are needed in
the process of making the parts (separately moulding the rubber sections followed by
treatment of rubber surface and finally bringing the rubber and metal parts into intimate
contact at elevated temperatures). Another disadvantage is that since the rubber is already
cured, limited interfacial mixing between the rubber and the adhesive may lessen the
quality of the final bond.
2.6 Factors Affecting Bond Integrity
After bonding, subsequent manufacturing procedures are generally required to finish the
part and prepare it for shipment. These procedures can have an effect on the integrity of
the bond if caution is not exercised. First, care must be taken during demoulding to
avoid over-stressing the bond while the part is at curing temperature. Deflashing
procedures such as wire brushing and grinding as well as post-bond machining operations
must be controlled to avoid exposing the part to excessive heat and stress. Electroplating
can reduce the bond strength if the current densities are not controlled or if the plating
solution attacks the adhesive. Applying rust preventatives or high solvent paints to the
73
exposed metal surfaces can lead to attack at the bond line if the adhesive is not resistant
to the chemicals in these materials. Finally, galvanic corrosion can result from contact of
dissimilar metals in a part with multiple metals.
2.7 Bond Failure Types
A rubber to metal bonded part can be thought of as a chain which holds rubber and
metal together. Any chain is only as strong as its weakest link. So it follows that when a
rubber to metal part fails, it will fail in the weakest section of the part. A test method
exists which specifically covers adhesion of rubber to metal, ASTM D429-2002 [21].
The vast majority of bond failures can be attributed to one or a combination of the
following ASTM designations:
R - Rubber failure: failure in the body of the rubber.

RC - Rubber/Cement failure: failure at the rubber to cement (adhesive) interface.
CP - Cement/Primer failure: failure at the cement (adhesive) to primer interface.
CM - Cement/Metal failure: failure at the primer to metal interface. For one coat
adhesives, this is failure at the adhesive to metal interface.
Rubber failure (R) is the type of failure to strive for. It indicates cohesive failure of the
rubber. This means that the bond between the rubber and the adhesive is stronger than
the tear strength of the rubber.
Rubber/cement (RC) failures indicate that the weakest point in the bonded part is at the
interface between the rubber and adhesive. These failures are characterised by a relatively
glossy and hard bonded surface with little or no rubber present. Common causes of RC
failure are the incorrect choice of adhesive, insufficient dry film thickness of adhesive,
failure to properly agitate the adhesive to achieve a uniform dispersion prior to application,
pre-cure of adhesive caused by excessive dwell time in the mould cavity before introducing
rubber, low mould pressure, undercure of the part, migration of plasticisers and other
ingredients from the body of the rubber to the rubber/adhesive interface or contamination
of the surface of the adhesive coated part.
Cement/metal (CM) failures usually indicate a problem with metal preparation or

application of adhesive. They are characterised by the appearance of bare metal in the
bonded area of the part. Common causes of CM failure include poor metal preparation,
i.e., the presence of contamination on the metal before application of adhesive, insufficient
dry film thickness of primer, failure to properly agitate the adhesive to achieve a uniform
dispersion prior to application, environmental attack (salt, water) on the primer/metal
interface, dry spray of primer on to the metal (which does not allow the primer to
74
adequately wet out the metal surface), or sweepage (when the flow of rubber strips some
or all of the adhesive or primer film from the metal surface) of the primer and adhesive
off the metal during injection or transfer moulding.
Cement/primer (CP) failures are characterised by the appearance of the primer on the
bonded surface. Usually the adhesive and primer are different colours to allow for easier
identification of both layers. CP failure is usually caused by contamination of the primer
surface before application of adhesive, migration of plasticiser from the rubber into the
adhesive/primer interface, insufficient drying of the primer film before application of the
adhesive or by incompatibility between primer and adhesive.
In many cases, combinations of the above failure modes appear on the same part.
For instance, a failed part may show some R failure, as well as RC and CM failure.
Steps must be taken to increase the proportion of R failure while reducing the other,
unwanted failure modes. Bond failures are usually given in terms of the percent of
the bonded area that contains a certain failure mode. For example, a failed part with
the designation 65R, 15RC, 20CM means that in the bonded area, 65% of the
bond surface shows failure in the rubber, 15% shows rubber/cement failure, and
20% shows cement/metal failure.
Whatever the particular failure mode seen in a part, the goal of the process engineer is
generally to work towards maximising the amount of rubber failure and minimise the
amount of failure at the other interfaces.
Often questions are raised by engineers and/or quality control personnel about how to
best evaluate the strength or quality of a rubber-to-metal bond. Discussions and occasional
conflicts occur in connection with the writing, enforcing, and interpreting specifications
for such bonds. Differing points of view may be held even within groups of engineers,
rubber technologists, and quality professionals, and a variety of types and levels of
specification requirements can be found scattered throughout industry.
From an engineering point of view the best known and perhaps simplest criterion for
good bonding is readily demonstrated in welding practice. As long as any forced breaks
of a welded assembly always occur away from the weld and in one of the parent
substrates, the weld can be considered fully acceptable. Clearly the resistance of any
assembly to applied stress cannot exceed that of the principal materials in the load
path, so failure in the parent metal is the best that can be expected. This demonstrates
the weld itself is stronger than the main mass of metal; and although the true strength
of the weld itself is not readily determined, neither is it of particular importance to the
engineer. This same criterion has often been applied to rubber-to-metal bonding starting
in the early part of this century.
75
This means that for many years it was reasonably valid to judge rubber bonds by their
appearance. A totally rubber covered metal piece after bond rupture confirmed the original
bond quality, and a clean metal surface strongly implied a serious problem with the
bonding process. The practice of writing specifications calling for destructive bond testing
with 100% rubber coverage of the metal surface became common.
However, bond appearance after destructive testing is not the only element of a bond
specification. Nondestructive proof testing of bonded parts and minimum failure loads
are also used routinely.
2.8 Bond Test Procedures
ASTM D429-99 [21] evolved as an official bond testing methodology over the years.
Method A uses simple flat bond surface geometry to put the bond into tensile stress,
and Method B was developed as a peel type test in order to better serve in those instances
where rubber-metal bonds were more likely to fail in that mode rather than due to
simple tension. After some years of use, D429-99 had Method C added to it, which
uses a conical specimen shape precisely in order to create maximum stress along the
rubber-metal bond line when a tensile force is exerted on the assembly. More recently
Method D was added for testing PV bonds and the part configuration resembles Method
A except that the rubber has been vulcanised prior to bonding. Method E is a special
test used exclusively to measure adhesion in rubber tank lining applications. Method F
is the newest bond test method for vulcanised bonds and it uses a smaller, convex
specimen sometimes referred to as the buffer specimen (see Figure 2.4). The part
configuration gives a better representation of typical force distributions encountered
in actual mount applications.
The different bond test methods yield results that do not always correlate closely in
terms of bond strength or mode of failure [22]. Some of these contrasts in results
reflect substantial differences in the manner in which the rubber to metal bond is stressed.
This is likely to be more meaningful for some actual applications of bonded parts and
less for others, depending on how the bond is stressed in such applications, e.g., shearing,
tension or peeling.
The test specimen geometry impacts the ability to discriminate between the bond strength
of different formulation and adhesive systems. Of the methods used, Method A seems
to be the least discriminating and the other tests should probably be used preferentially,
depending on what kind of application is being evaluated. Method F appears to have
the most consistent ability to discriminate differences in response [22].
76
test procedures
Figure 2.4 Cross section of adhesion test specimens

(Courtesy of Lord Corporation)
2.9 Summary
Bonding rubber to metal is a complex and multifaceted combination of metallurgy, surface

science, adhesion science, rubber chemistry, and process engineering, with a multitude of
interactions. In all aspects of bonding, scrupulous cleanliness, adherence to process
controls and meticulous attention to detail are essential if good adhesion is to be attained
on a consistent production basis.
In general, there are a number of factors that should be considered when selecting an
adhesive system. The adhesive system should wet the substrate and spread evenly over
the surface under varying conditions. The adhesive system must be compatible with both
the polymer type and the vulcanisation chemicals used in the rubber formulation. It
should have sufficient cohesive strength to avoid sweeping at moulding temperatures. It
should be capable of interfacial mixing with the rubber without destroying the integrity
of the adhesive film. It should maintain bond integrity both through all post-bond finishing
operations and when exposed to the environmental conditions which the part will see
during service. Finally, the adhesive system should accommodate variations in cure and
processing conditions used in making the parts.
77
References
1. D. M. Alstadt, Rubber World, 1955, 133, 2, 221.
2. D. M. Alstadt and E. W. Coleman, Jr., inventors; Lord Corporation, assignee; US

Patent 2,905,585, 1959.
3. S. Buchan, Rubber to Metal Bonding, Palmerton, New York, 1959.
4. W. M. DeCrease, Rubber Age, 1960, 87, 1013.
5. P. J. Jazenski and L. G. Manino, inventors; Lord Corporation, assignee; US

Patent 4,119,587, 1978.
6. D. J. Elliot in Developments in Rubber Technology -1, Eds., A. Whelan and K. S.

Lee, Applied Science Publishers, London, 1979, p.1-44.
7. M. A. Weih, C. E. Siverling and F. H. Sexsmith, Rubber World, 1986, 195, 5, 29.
8. A. K. Bhowmick, M. M. Hall and H. A. Benarey, Rubber Products

Manufacturing Technology, Marcel Dekker, New York, 1994, p.776-778.
9. Vulcanisation of Rubbers, Eds., G. Alliger and I. J. Sjothun, Reinhold Publishing

Corporation, New York, 1964, p.117-118.
10. German Patent 170361.
11. L. Daft, inventor; Electro-Chemical Rubber & Manufacturing Company,

assignee; US Patent 1036576, 1912.



15. Rubber Technology and Manufacture, Ed., C. M. Blow, Newnes-Butterworth,

London, 1977, p.296-298.
16. Rubber Technology and Manufacture, Ed., C. M. Blow, Newnes-Butterworth,

London, 1977, p.480.
78
17. DT 928.252, 1942, Bayer.
18. R. Costin and W. Nagel, Rubber World, 1998, 219, 2, 18.
19. W. Hofmann, Rubber Technology Handbook, Hanser Publishers, New York,

1980, p.315.
20. ASTM F22

Standard Test Method for Hydrophobic Surface Films by the Water-Break
Test, 2002.
21. ASTM D429

Standard Test Methods for Rubber Property - Adhesion to Rigid Substrates, 2002.
22. R. J. Del Vecchio and J. R. Halladay, Presented at the 152nd ACS Rubber
Division Meeting, Cleveland, Ohio, Fall 1997, Paper No.25.
79
80
3
Rubber to Metal and Other Substrate Bonding
M. Rooke
3.1 Introduction
3.1.1 Foreword
This chapter on bonding describes the use of modern bonding agents and some of the
requirements necessary to produce a reliable bond. It is intended to serve as an introduction
and perspective for students in the field of bonding technology as well as providing a
reference for plant engineers and others who are concerned with the implementation of
processes related to bonding.
3.1.2 History
Rubber to metal bonding was invented, perhaps by accident, in the middle of the 19th
century [1] when natural rubber was bonded to brass during the vulcanisation of the
rubber. This process of bonding rubber to metals and other substrates during the
vulcanisation of the rubber is still the basis of most rubber bonding today. Applications for
bonded items such as antivibration components quickly became established in the growing
automotive industry of the 20th century particularly from the late 1930s, using brass plated
steel as the substrate. The restrictions of using high sulphur compounds that were necessary
for bonding to brass, but had inherently poor dynamic properties, were overcome by use
of multiple tie layers of rubber with decreasing sulphur levels in each layer to create a
modulus bridge between the ebonite bonding layer and the rubber used in the component
for antivibration. The layers of rubber were applied from a solvent solution. Other
approaches for bonding included using polyisocyanates in the 1940s and bonding proceeded
in this way until the 1950s. The breakthrough was made in the middle of the 1950s at the
laboratories of Hughson Chemicals (which later became the Chemical Products Division
of Lord Corporation, Erie, PA, USA) when the first of the modern bonding agents, Chemlok
220, was invented. Chemlok 220 was introduced into the United States market place in
1956, and into the European market in 1959. It was marketed and subsequently
manufactured by Henkel KGaA, Dsseldorf Germany under the Chemosil trade name.
The trade name Chemosil was chosen at that time because the lok of Chemlok was not
81
Commercial rubbers
perceived as having any meaning in French or German, the main European markets at that
time and the sil of Chemosil was derived from the detergent Persil, a Henkel invention in
1905. The irony of this however was that while sil had no meaning in connection with
bonding, Persil was actually a scientific derivation as Per was from perborate and sil
from silicate the main ingredients of the worlds first synthetic detergent.
This new technology used heat activated polymers applied from a solvent solution. These
bonding agents dried to a non-tacky surface, and reacted chemically with the rubber and
the metal during the vulcanisation process. They were designed to be stable in the can and
had a long chemical shelf life (of years in many cases) when stored at ambient temperatures.
Unlike isocyanate bonding systems they were not susceptible to humidity. In the eastern
bloc countries where isocyanate systems lingered towards the end of the 20th century,
bonding could only be reliably carried out in the winter because of summer humidity.
Brass plating as a means of bonding continued in Europe and America into the mid 1960s
when it was replaced by modern bonding agents. The process of replacing tie layers with
modern bonding agents was often a slow process and there was an element of disbelief that
many thick and viscous layers of tie cement could be replaced by a few microns of bonding
agent and primer. Around 1970, in one instance, it was found that 7 layers of tie cement
were being covercoated with Chemosil 220 making 8 coats for bonding.
3.1.3 Types of Bonding
Types of bonding can be divided into three categories and the principles outlined in this
section apply in each case.
Rubber to substrate bonding is used for three main applications. Antivibration, the
chemical or physical properties of the rubber, and a combination of antivibration with
the chemical physical properties of the rubber. This is shown in Table 3.1.
Table 3.1 Types of bonding

Purpose Example
Antivibration mounts, seismic mounts,
Antivibration
shock absorbers, rollers, solid tyres
Physical and/or chemical properties of Chemical tank lining, abrasion resistant
the rubber linings
Both antivibration and sealing properties Dynamic seals, hydromounts
82
3.1.4 The Bonding Process - An Overview
Bonding to substrates requires that a clean stable substrate is prepared for the bonding
agent. In the case of metals the surface preparation can be chemical or mechanical.
Chemical preparation involves the removal of oxide and usually the deposition of a
stable chemical layer, typically phosphate, on to the metal surface. Mechanical
preparation involves the abrasion of the metal usually by grit blasting to remove oxide
layers from the metal. The bonding agent or bonding agent primer should be applied
to the grit blasted surface within a time window for the particular metal so that the
surface is not re-oxidised to such an extent that the surface will again be an unstable
substrate for bonding. Some metals such as stainless steel re-oxidise fairly rapidly despite
the fact that they may have a deceptive glossy lustre and a time window of just 30
minutes is recommended. As stainless steels have many different chemical compositions
it is better to err on the side of caution until it is established that other periods between
metal preparation and application of bonding agent primer can be used. Polymeric
substrates may have surfaces contaminated with mould release agent or lubricants and
so may have to be degreased or cleaned in some way. Most grades of bonding agents
contain solids that must be fully homogenised and brought into suspension. More
bond failures have occurred due to inadequate mixing than almost any other cause.
Technologists should always believe in the consistency of science and always look for
scientific explanations. The author was called to a problem with a bonding agent that
was thick at the bottom of the container but thin at the top despite vigorous stirring
with an electric stirrer. Investigation revealed that the blade had dropped off the bottom
of the stirrer shaft and only the shaft was rotating. Components coated with bonding
agent should be kept free of contamination during the period prior to bonding (layover
period). Components should be loaded into the mould and moulded quickly to avoid
pre-crosslinking of the bonding agent before rubber contact. The bonding agent during
the vulcanisation process reacts chemically with both the rubber and the substrate. A
properly made component will have a bond that will endure and not fail in service.
These points may be summarised as follows:
Produce a clean substrate and keep it clean and avoid contamination,
Stir the bonding agent and keep it fully homogenous,
Work within the time window for the substrate,
Apply an even coat of bonding agent,
Avoid prebake of bonding agent.
A schematic picture of a bonding agent mechanism is shown in Figure 3.1.
83
Henkel
Elastomer
Adsorptio n &/or
interdiffusion &
chemical reaction Bonding Agent Crossbridging,
interdiffusion &
chemical reaction
Primer
Adsorption &
chemical reactio n
with metal
Metal
Figure 3.1 Two coat rubber bonding
3.1.5 Development of Bonding
Almost from the very beginning there were changing demands upon rubber bonding
agents where the variables were technology, quality and the environment. The demands
from technological progress were in the form of newer more difficult to bond to polymers,
and this led to the creation in the 1970s of improved bonding agents, the so called
Supercovers typified by Chemosil 411. The quality revolution, improved reliability from
failure mode and effect analysis (FMEA) [2], and finally the social audit of the
environment, first questioning what products ought to be used, and then legislating on
substances that produced or depleted ozone in the atmosphere, have all had an impact
on bonding agent development.
3.1.6 Bonding Agent Reliability
Reliability of the bond was a key feature in bonding agent design from the very beginning.
In order to produce reliable components the chemical composition of the bonding agents
were and are tailored to meet the in-service requirements of the component. This is
achieved during the development of the bonding agent through a process described as
controlled product design (CPD). The CPD methodology has similar objectives to design
FMEA (FMEA is an important concept used in the engineering industries to predict
what may go wrong in a controlled system) in that it seeks to eliminate the possibility of
future failures by product design. To give one example, layover (time between the
84
application of a bonding agent and the actual bonding) experiments up to two years
were carried out in the late 1950s. The use of CPD in the evaluation of how a product
could fail enables products made according to this design philosophy (a corollary of this
is that equivalent products can only really be equivalent if they have the same CPD
background) to have some or all of these physical characteristics:
Stable in can chemistry,

Good layover,
Prebake resistance,
Bond strengths greater than the polymer,
Brake fluid resistance,
Dynamic fatigue resistance,
Gasoline resistance,
Heat resistance of bond,
Hot glycol resistance,
Hot water resistance,
Oil resistance,
Salt spray resistance.
Engineers are rightly much concerned about process FMEA. In the case of bonding agents
using a liquid as a carrier for bonding agents the reactive constituents function as a
single phase or single component system. This is due to Brownian movement (Robert
Brown, 1827), first explained by Wiener in 1863. Kinetic theory proof was developed by
Perrin (1906) using Maxwell-Boltzmann distribution and the chemical diffusion - diffusion
theory developed by Einstein in 1905 and 1908. The reliability of the bonding system
stems from the fact that not only does production methodology use ISO 9001 [3]
procedures for the testing of raw materials and product manufacture but also the final
product is both analysed and performance tested according to criteria devised during the
CPD programme. That the testing programme is relevant in relation to the original R&D
design of the product can be seen from the following example. The number of molecules
of bonding agent used in a test is very large. For example using a bonding polymer
oligomer with a MW of 50,000 and a test sample of 1 g, some 2.4 x 1018 molecules will
be tested. For a MW of 50,000 and solids content of say 20% and using 6.023 x 1023 as
the Avogadro number then 6.023 x 1023 x 0.2/50000 = 2.4 x 1018.
The FMEA concept was developed in the mid 1960s in the aerospace industry. It was
then taken up by sectors of the North American automotive industry and soon
85
afterwards became a standard procedure used for automobile component design. FMEA
asks: 1) What might go wrong, 2) What effect would this have, 3) What might cause it
to go wrong. The FMEA process is quantified by ascribing on a scale of 1 10 each of
the following. The likelihood of a failure occurring, the severity of the consequences of
failure, the likelihood of detection. A Risk Priority Number (RPN) is then obtained
from the product of these, i.e., multiplying the Occurrence by the Severity by the
Detection. Thus the RPN value which equals O x S x D can have a minimum value of
1 and a maximum value of 1000.
Although FMEA is an engineering concept and as such does not directly relate to the
methodology of single phase systems that are tested, nevertheless calculations can be made
to illustrate the type of RPN values that would be achieved if FMEA was used. FMEA in
the true engineering sense would only apply if products were not tested, but it was only
predicted that they would bond because of design and manufacturing procedures. An
example of an FMEA calculation on bonding agent production is:
Occurrence of failure: Because of product design and the ISO 9001 manufacturing
procedures this is seen as being remote hence a rating of 1.
Severity of failure: If the product did not perform as designed then the failure could cause
serious injury or death, i.e., catastrophic failure, hence a rating of 10.
Detection of failure: Because of the physical properties of a liquid coupled with product
testing of a large number of molecular components the probability of a defect reaching the
customer is remote, hence a rating of 1.
RPN: Thus the RPN is 1 x 10 x 1 = 10.
3.1.7 The Environment and Solvent Use
Solvents such as trichloroethane that historically were used for degreasing and to a
lesser extent as solvents for bonding agents were banned for being ozone depleting
chemicals (ODC). They are known to destroy ozone in the stratosphere where ozone
functions as a UV absorber protecting the earth from harmful radiation. Organic
solvents on the other hand as volatile organic compounds (VOC) act as photochemical
oxidants creating ozone in the lower atmosphere (troposphere). Here ozone is
considered harmful to both flora and fauna and is also implicated in the formation
of acid rain. The Montreal Protocol imposed restrictions on the use of substances
that deplete the ozone layer and ODCs have been largely phased out. On VOCs
however, the United Nations Economic Commission for Europe set targets for reducing
emissions in Europe by approximately 30% by 1999 compared to a 1988 base line.
86
The EC response to this was to issue EC Directive 84/360 [4] on air pollution from
industrial plant and this was implemented in the UK as the Environmental Protection
Act 1990, Part I [5] and TA Luft in Germany [6]. In the UK a series of Process Guidance
Notes were published by the Government for regional government (Local Authorities)
to assist in the implementation of this law. The time frame for compliance of the
Environmental Protection Act 1990, Part I as outlined in PG 6/32(97) [7] require that
fugitive organic solvent emissions from existing processes should be reduced by 25%
by 1 June 1998 and 50% by 1 April 1999, based on the annual organic solvent use
detailed in the application for authorisation. The requirements of this clause should
not apply where solvent emissions are less than 5% of total solvent use. These limits
apply to companies using over 5 tonnes per year of solvents.
3.1.8 Methods of Reduction in Solvent Emissions
In order to achieve the objective set down in Section 7(2)(a) of the Environmental
Protection Act 1990, Local Authorities are obliged to ensure that, in carrying on a
prescribed process, the Best Available Technology Not Entailing Excessive Cost
(BATNEEC) [8] will be used:
i) for preventing the release of substances and where it is not practicable, reducing the
release of such substances to a minimum and rendering harmless any substances
which are so released.
ii) for rendering harmless any other substances which might cause harm if released
into any environmental medium.
Thus solvents have to be reduced in line with targets, eliminated, recovered or

incinerated. In order to assist customers for whom solvent recovery or combustion is
not economically viable, Henkel decided to support the new EEC VOC Directives
using a philosophy similar to the BATNEEC philosophy stipulated by the UK
Department of the Environment and other national requirements, by developing
waterborne products to eliminate solvent emissions.
3.2 Substrates and their Preparation
The foundation of a good bond is a clean and stable substrate. The preparation of a
surface for bonding depends on the nature of the material which forms the substrate.
Substrates can be divided into the following categories: metals and polymeric. Polymeric
substrates can be further subdivided into organic and inorganic.
87
3.2.1 Mechanical Treatment of Metals
Solvent degreasing
The traditional method for the mechanical preparation of metals used a sequence of
degreasing, grit blasting and degreasing. The blasting removes friable surface oxide, which
if not removed would fracture and flake off when the bonded component was stressed in
use. The second degrease removes any dust that is on the gritted components, and also
removes oil that may have been present in the airline if the grit was air driven. The solvent
that was used historically was trichloroethane but concerns over ozone depletion have led
to its replacement with trichloroethylene. New degreasing equipment minimises the
emissions of solvents and so of VOCs. The pH of the solvent should be monitored and
adjusted to prevent the build up of acidic residues. Particular caution should be taken if
metallic dust being removed includes metals such as aluminium (it should also be noted
that aluminium containers should not be used for bonding agents containing chlorinated
solvents as the aluminium will react with the chlorinated solvents), zinc or cadmium that
could react with acidic solvents, forming Friedel-Crafts catalysts. Although Friedel-Crafts
(named after Charles Friedel 1832-1899 and James Craft 1839-1917) catalysts are usually
associated with acylation of aromatics, the same group of compounds seem to act as catalytic
degradants of halo compounds and polymers such as PVC.
Aqueous degreasing
Aqueous degreasing is a highly effective method of surface preparation prior to grit blasting. In
experiments Henkel has shown that organic residues from aqueous degreasing can be lower
than by solvent degreasing. To compare the cleaning effect of vapour degreasing and alkaline
cleaning methods the remaining organic carbon on the cleaned metal surface was determined.
On the surface of vapour phase degreased metals 12 14 mg/m2 of organic carbon was
detected, while on the alkaline cleaned metal surface 6 8 mg/m2 of organic carbon
was detected.
For water-based cleaning three types of systems are known:
Acid phosphate systems pH 3.5 5.5

Neutral systems pH 7.5 8.0
Alkaline systems pH 8.0 13.0
The acid phosphate systems will be considered in Section 3.2.5 on the chemical conversion
of surfaces.
88
Neutral systems
These are mainly liquid products containing surfactants and corrosion inhibitors, with an
apparent advantage that parts treated with such combinations do not need rinsing
afterwards. A thin protective film of oil or organic media is sometimes present on the metal
surface after machining to protect metal parts post manufacture. This temporary oil
protection coating of metals has to be removed before bonding. It is also important to
ensure that the protective oil is actually removed in the single stage degreasing process.
Neutral cleaning products do not require rinsing afterwards but the protective film of
corrosion inhibitor and residual surfactant remains on the metal surface. Although this
would be removed during blasting, the grit would be contaminated with these products
and after a while the surfactants will be applied onto the clean oxide free metal surface. If
the surfactant is not heat stable enough against high temperatures it will decompose and
the residues can cause corrosion under the bond during vulcanisation. Superficially the
single stage process seems attractive but for the reasons outlined it is not recommended.
Alkaline cleaning
This cleaning method is commonly used in metal industries. The process consists of cleaning
parts in a mixture of surfactant, sodium or potassium hydroxide, and combinations with
sodium carbonate, sodium silicate, borates and in special cases sodium gluconate.
Components may be treated by dipping or spraying methods. There are four main variables
in this type of process (see Figure 3.2), and these are:
Chemicals (concentration),
Temperature,
Time,
Mechanical action.
These variables are interrelated and if one variable is changed then others must be
altered to compensate. For example if a lower temperature is used then the time must
be extended, or it must be compensated for by increased mechanical action from
ultrasonic treatment to achieve the same time cycle. The greatest efficiency is obtained
by immersion, but spray systems give more mechanical action and the cleaning cycle
can be reduced. As oil and grease are emulsified by the surfactant, after a time the risk
of re-contamination of the parts being cleaned is very high, particularly if a dipping
method is used. For this reason it is recommended that a two-stage alkaline cleaning is
used. With this cleaning method a certain amount of electrolytes remain on the metal
surface and a final rinsing in a three-step cascade-shower is advisable. Difficulties with
89
Figure 3.2 Variables in the cleaning process
alkaline cleaning may occur with small oily parts that stick together, where the cleaning
solution cannot reach the whole surface. Other problems may arise when components
have small holes, flanges or notches, where cleaning solutions either cannot enter or
remain after the process. Nevertheless alkaline cleaning is an effective alternative to
vapour degreasing, and particularly the spray system which is already used in the field
of rubber-to-metal bonding production.
3.2.2 The Abrasion Process
Chilled iron grit is recommended for mild steel. Chilled iron grit should not be used
on stainless or non-ferrous metals, where particles can become embedded in the
substrate, forming galvanic cells that can cause underbond corrosion. In these cases
the blast media should be alumina or a non-metallic grit. Metal shots such as steel
shot should not be used. They are soft (malleable) and spread on the surface, giving
the impression of producing a clean surface, but in reality forming a layer of metal
on the substrate surface, that will peel off when the bond is stressed, giving bond
failure. Also steel shots impact the surface, creating craters like a lunar landscape.
This action tends to leave the oxide layer intact. Schematic diagrams of this are
shown in Figures 3.3 and 3.4. Electron micrographs have shown how steel shot
produces impacted craters, whereas chilled iron grit and aluminium oxide produces
a mechanically torn surface. Both aluminium oxide and chilled iron grit tear into the
surface producing a cleaned substrate.
90
Figure 3.3 Diagram showing soft (malleable) grit covering oxide layer
Figure 3.4 Diagram showing fracture of steel coated layer
Research into types of abrasives suitable for bonding was carried out because of field failure of
some bonded components. Grit recommendations based on research are given in Table 3.2.
Particular care should be taken to avoid grits that apparently clean the surface but whose
inherent deficiencies are masked to some degree by the ability of the primer to bond residual
particles to the surface. Because there is no guarantee that all of the oxide has been removed
by such grits there can be no guarantee of the reliability of such parts in service. The use of
such grits that plate or incompletely clean the surface of the substrate are not recommended
in FMEA terms. The use of such would increase the occurrence of higher R values in the
RPN system.
Cleaning by conditioning
Conditioning is a third way to clean metal surfaces. This involves leaving heavy metal castings
in the open air for some weeks to rust. Heavy metal castings frequently retain surface mill
scale from the casting process. The rusting of the castings enables oxidation to occur back to
the metal below mill scale and oil or cutting fluids on the surface. Parts are then grit blasted.
91
Table 3.2 Grit recommendations for achieving specific hardnesses

Grit HV HB HRc Recommended
Hard chilled iron grit 650 750 555 600 57 61.8 Yes
Tempered iron grit 455 475 430 447 44.5 46.8 No
Steel shot 470 530 442 493 46.4 50.3 No
Wire drawn steel shot Hardness not listed in literature No
Alumina Mohr Scale 9 Yes
Grades chilled iron
700-1000 60-80
available
HV Vickers hardness; HB Brinell hardness; HRc Rockwell hardness
3.2.3 Levels of metal cleanliness
It is very common to prepare a surface of a large component to Swedish Standard [9, 10,
11]. The original Swedish Standard is now incorporated into many national and
international specifications. Surfaces are defined as A-D according to the amount of
rust. An A surface has no rust or only slight rust whereas a D surface is heavily rusted
and shows pitting (craters or holes).
The degree of blasting is classed from Sa 1 to Sa 3 and this is shown together with
recommendations in Table 3.3.
Table 3.3
Sa 1 Sa 2 Sa 21/2
Sa 3
Surface (light (thorough (very thorough
(clean to metal)
blast) blast) blast)
A (no rust or slight rust) Yes Yes
B (some rust) No No Yes Yes
C (heavy rust but no
No No Yes Yes
pitting)
D (considerable pitting) No No No Yes
92
In general it is better to blast to Sa 21/2 or Sa 3 for surfaces used for bonding. Sometimes
a surface is stained with scale but is free from rust. It may be possible to grit to Sa 2 on
A and B surfaces but it is preferable to blast to Sa 21/2.
3.2.4 Time Window
The rate of re-oxidation of mechanically treated metals depends on the metal, the presence
of oxygen and the level of humidity. Guidelines for common metal substrates under
ambient conditions without dehumidification in a northern European climate are:
2 h for mild steel but

30 minutes for stainless steel, aluminium, brass, bronze and zinc
and only 2 minutes (approximately) for magnesium
It is very important that the primer is applied within the time window for the metal.
Solvent-borne coatings should be applied above the dew point. The start of the time
window starts at the end of the gritting and not at the end of the degreasing cycle. This
is shown in Figure 3.5. Other aspects referred to in the flow diagram will be dealt with in
subsequent sections.
Henkel Time Sequence for Bonding Agent Application
Temperature Apply Apply

Dilute with
Bonding condition the S tir the Pri mer Top Coat
correct
Agent bonding p roduct Dry Dry
Prep diluent
agent
Time
Window
Metal
Prep Degrease Gritblast Degrease
Hand-
ling
Do not handle Do not handle Do not handle

Wear Gloves Wear Gloves Wear Gloves
Direction of time
Legend
Criti cal time path
Time window
Figure 3.5 Time sequence for bonding agent applications
93
3.2.5 Chemical Preparation of Surfaces
It is possible to clean and phosphate in a single operation. This process of acid phosphate
cleaning combines the degreasing with a transformation of the metal surface by removal
of oxide and the phosphating of the metal. The process can be used for metals such as
steel, aluminium and zinc. This process produces an excellent surface for the adhesion
of lacquers but it is not suitable for rubber-to-metal bonding. Tests have shown that
the corrosion resistance of the components are not satisfactory.
Excellent bonding can be achieved with zinc phosphate and mixed metal phosphates
but the particle size and quantity of phosphate applied are very important. There are
two main physical forms of phosphate that are used in commerce. One is an amorphous
structure applied at a level typically below 4 g/m2 and the other an acicular (needle
shaped) structure typically applied at a level of 15 g/m2. The acicular form is used as
an absorbent substrate for coatings and oils used to enhance the phosphate layer as
protective coating. The acicular form is unsuitable for bonding as the crystal structure
can fracture under the bonding agent primer.
Phosphating should only be carried out on a flat surface, as a profiled surface, that has
been grit blasted for example, may not be able to accommodate even packing of
phosphate deposits and bare metal patches may be exposed [12].
The phosphating process usually involves cleaning of the metal, rinsing, surface
activation, and phosphate conversion producing an amorphous layer before a final
rinse and seal. This sequence is:
i) Alkaline degrease,
ii) Rinse,
iii) (Surface activation),
iv) Phosphate,
v) Rinse,
vi) Seal (Passivation),
vii) Rinse,
viii) Dry.
The surface activation step iii) is optional but is designed to produce a finer particle
structure. The sealing process (passivation) in step vi) historically used chromate but
environmental pressures have made this an optional step. Some alternative chemical
seals must be proved to be suitable for bonding. Sealing is done to improve the water
resistance of the layer.
94
The phosphate treatment must be carefully controlled to ensure the quality and
uniformity of the coating. The bonding primer must be applied within 24 hours of the
phosphating process.
For bonding, levels of application of zinc phosphate, should not exceed 4 4.5 g/m2 for
flat surfaces. Higher levels may lead to bond failure due to fracture of the phosphate
coating. If the phosphate layer on the metal component of the bonded part is to be
subjected to exceptional mechanical stresses, as in a stress relieving process shown in
Figure 3.6, then the level of zinc phosphate should be within the range of 1.3 1.9 g/m2
to avoid fracture of the phosphate layer. In the 1960s levels of phosphate were
recommended at below 2 g/m2 for bonding. With improvements in technology this
increased to around 4 g/m3 for increased protection. However the higher levels proved
unsuitable for bush bonding and below 2 g is recommended for this application.
Technological improvements could advance this figure.
With advancing technology higher levels of phosphate for greater protection of the metal
may in the future lead to modification of these recommendations.
Where high levels of phosphate are required for non-bonded areas as an anti-corrosion
layer the process is as follows:
i) Phosphate to a level technically suitable for the bonded component,
ii) Bond the component,
iii) Pickle to remove phosphate from non bonded areas,
Figure 3.6 Axial forces applied in stress relieving process
95
Figure 3.7 Diagram showing component with bonded layer and oil soaked crystalline
phosphate protective coating
iv) Re-phosphate to a level of 10 20 g/m2,
v) Oil dip or apply a protective surface finishing coating.
This is illustrated in Figure 3.7.
3.2.6 Future Developments

In recent years there has been much interest in coatings that can reduce the cost of the
final components, and also improve this performance in terms of environmental resistance.
Electrophoretic deposition of polymers on metal surfaces would be one example. Coatings
96
applied to substrates for bonding should not be thermoplastic and should provide an
even micron thickness. This technology is likely to be important in the future.
3.3 Bonding Agent Preparation
3.3.1 Solvent-borne Bonding Systems

Bonding agents can be clear solutions but they are frequently suspensions of solids in
polymeric solutions. In order to use the products full homogenisation is required.
Where solvent-borne products are exposed to lower temperatures the viscosity

characteristics of primer and top coats tend to differ (see Figure 3.8). The temperature
viscosity/graphs in Figure 3.8 show the importance of temperature conditioning during
the cold weather to retain the same solids content for a given spray viscosity. It is
important not to dilute top coats to a particular viscosity if the bonding agent is at a
low temperature. Always bring the bonding agent up to room temperature before
diluting. The best method is to always add an exact amount of diluent to an exact
amount of bonding agent.
Figure 3.8 Variation of viscosity with temperature
97
3.4 Bonding Agent Application and Use
3.4.1 Application Methods

Bonding agents may be applied in a number of ways. To make an effective bond an even
coat of the bonding system is required of the correct thickness. The method of application
is not important provided that an even coat of correct thickness is applied. Methods of
application are:
Brush,
Dip,
Electrostatic,
Flowcoat,
Reverse roller coat,
Roller,
Sponge,
Spray.
Typically 7 m of primer and 10 m of top coat are required for bonding. The thickness
depends on the profile of the surface. Smoother surfaces require less bonding agent and
heavily profiled surfaces require more bonding agent to ensure that the peaks are covered.
In a two-coat process it is important that the primer coat dries before the topcoat is
applied to prevent mixing and loss of the individual properties of each coat. For most
applications electrostatic spraying may not be suitable as not all components have a
suitable electrostatic profile for even coating. However where it is possible to use
electrostatic spraying it is very effective in reducing overspray.
3.4.2 Waterborne Bonding Systems

Storage temperatures of 5 30 C are recommended. Freezing and also long exposure to
direct sunlight must be avoided. The material should be temperature conditioned to 25
30 C prior to use. As with solvent-borne products sedimented solids should be brought
into suspension by careful agitation for at least 30 minutes before use. When stirring avoid
vortex formation that will suck in air and cause foaming. For the same reason waterborne
products should only be stirred and never shaken, as this will produce a stable foam.
Impeller stirrers with blades 20 30 cm long can be used at up to 60 rpm. Shear discs 8 cm
in diameter can be used at speeds up to 700 1000 rpm. After the solids are brought into
suspension the products should be continually stirred at a moderate speed. Dried bonding
agent on the walls of containers will not re-dissolve and loose particles could block spray
equipment. In-line 500 m filters are recommended to prevent this.
98
3.4.3 Bonding Agent Thickness

As some surfaces to be coated may give an uneven coating thickness, care should be
taken not to exceed maximum coating thickness values (see Table 3.4). The correct
coating thickness should be selected, because layers of less than 10 m may cause
bond failure, and too thick a layer may cause mould fouling or film delamination
and cracking during the filling of the mould. However prebake resistance of bonding
agent is extended with thicker layers. Tests should be carried out to verify suggested
values in each case, as the bondability of compounds will vary according to
formulation.
Table 3.4 Bonding agent coating thickness

Chemosil Vulcanisation Vulcanising Prebake Recommended thickness of
(Henkel) method temperature resistance the dried film
Minimum 5 m
Primer
Recommended 8 10 m
211 or
Stress corrosion resistance
X2138
10 15 m
130 180 C Recommended 10 15 m
222 or
C, T, I Optimum up Normal In some circumstances up
220
to 170 C to 30 m
Greater than
XV5524 Optimum Chemosil 222 Recommended 10 20 m
C, T, I
XV4250 130 180 C and less than up to 30 m possible
Chemosil 411
130 200 C Minimum 10 m
Very good up
411 C, T, I 180 C Recommended 15 20 m
to 180 C
preferred up to 30 m possible
Minimum 10 m
Recommended 15 20 m
231G C, T, I 130 180 C Normal
Apply two coats if
necessary
X6070 C, T, I 130 170 C Normal Recommended 15 20 m
Less than
X6025 C 90 170 C Recommended 15 20 m
Chemosil 222
C = Compression moulding I = Injection moulding T = Transfer moulding
99
3.5 Post Vulcanisation Bonding
Cured rubbers may be bonded to metals or to cured or uncured dissimilar rubbers with
the aid of Chemosil bonding agents. Bonding takes place using heat and pressure, and
bond line temperatures in excess of 100 C are usually required.
3.5.1 Post Vulcanisation Bonding Applications
Post vulcanisation (PV) bonding gives enhanced opportunities in the design of bonded
components, and examples of bonded components by this method include the following:
Automotive concentric suspension bushes, where the rubber is bonded to the inner
metal tube by conventional in-mould bonding, then bonded to the outer tube by a PV
bonding technique,
Automotive engine mounts, where vulcanised rubber is PV bonded between metal

plates,
Bridge bearing pads, where vulcanised rubber blocks are assembled in a sandwich
construction between a series of metal pieces and then the PV bonding technique is
applied.
3.5.2 Choice of Bonding Agent for Post Vulcanisation Bonding
Chemosil products suitable for use as PV bonding agents are Chemosils X6025, X6070
and 411. The choice of bonding agent is dependent on the rubber type, the nature of the
substrate bonding surface, the bonding temperature and the bonding pressure applied.
Chemosil PV bonding agents will bond the following rubber/substrate combinations:
Rubber range - vulcanised butyl rubber, CP, EPDM, CSM, NR, NBR and SBR rubbers.
Substrate range - using Chemosil 211 primer, the PV bonding agents will bond ferrous
and non-ferrous metals and plastics. They can be used as one-coat systems to bond
vulcanised rubbers to themselves or to other vulcanised rubbers.
Chemosil X6025 Recommended for situations using low bonding temperatures (down
to 100 C) and low bonding pressures.
Chemosil X6070 used with Chemosil 211 for bonding to metal substrates. Bonding
temperatures above 130 C are recommended.
100
Chemosil 411 Bond cure temperatures above 120 C are recommended.
To bond to metal Chemosil 211 is recommended as a metal primer and compression of

5 to 10% during the curing cycle is recommended.
Certain waterborne systems are available which are capable of PV bonding.
3.5.3 Rubber Substrate Preparation for PV Bonding

Vulcanised rubber surfaces must be thoroughly cleaned and degreased prior to Chemosil
application. A light abrasion using a wire brush should be followed by degreasing to give
a good bonding surface. PV bonding of non-polar rubbers such as butyl, EPDM, NR and
SBR may be improved if the surfaces are chlorinated or subjected to acid cyclisation treatment
to activate the bonding surface. Chemlok 7701 primer will improve bond performance if
applied to the cured polymer surface immediately before bonding agent application.
3.5.4 Metal Substrate Preparation
All oil, grease and other soluble contamination should be removed by solvent degreasing
or alkaline cleaning. Rust, scale and other non-soluble contaminants should be removed
by mechanical or chemical methods. Grit blasting is the most commonly used mechanical
method, but wheel abrasion, grinding, wire brushing, emery cloth or steel wool can be
used. Chemosil 211 primer should be applied as soon as possible after the surface
preparation to reduce the risk of contamination or oxidation of the substrate.
3.5.5 Methods of Application
Chemosil 211, X6025, X6070 and 411 contain dispersed solids, consequently they must
be thoroughly stirred before and at frequent intervals during use. The most consistent
bonding performance is obtained when Chemosil is applied to both bonding surfaces.
Therefore when bonding to a metal substrate, apply Chemosil 211 primer, allow to dry
and apply recommended Chemosil covercoat to both the primed metal and the vulcanised
rubber bonding surface.
Film thickness
A dry Chemosil covercoat film thickness of between 15 30 m is recommended. A
Chemosil 211 primer dry film thickness of between 5 10 m is recommended.
101
Drying
At ambient temperatures allow at least 60 minutes drying time between coating and
bonding. At elevated temperatures up to 90 C drying time can be considerably reduced.
High air flow will give the most efficient drying conditions.
Assembly of coated components

Once the Chemosil coated components have been dried they can be assembled and PV
bonded. Care should be taken to avoid damaging or contaminating the Chemosil coating.
Clean cotton gloves should be worn when handling coated parts.
The assembly of concentric bush components which involve an interference fit between
the inner rubber core and the inner and outer metal cylinders, can be lubricated by the
application of a small amount of a rubber process oil. This will reduce the risk of damaging
the Chemosil film during component assembly. Process oils such as Circolight Oil (Sun
Oil Company) or Petrofina 2059 (Petrofina UK Ltd.) are suitable.
Components such as engine mounts and bearing pads, must be clamped or otherwise
compressed during bonding. A compression ratio of 5 to 10% based on the initial
dimensions of the rubber component will give optimum bond performance. Compression
must be maintained throughout the PV bonding cure cycle and until the bonded component
assembly has cooled to below 50 C, see Table 3.5.
PV bonding cure cycle

The component assembly should be heated to give a bond-line temperature of between
100 C and 160 C for 15 to 60 minutes. Individual cure cycles are determined by the
component size and the method of heating. Experimentation is often required to identify
the most effective bonding conditions.
Handling bonded components

Cool down period: it is very important to allow the PV bonded components to cool
down under compression to obtain optimum bond performance. Once the component
has cooled to below 50 C then the compression can be relieved.
Post bond treatments: treatments such as machining, painting, anodisation or

electroplating should not affect bond performance.
102
Table 3.5 Effect of cure cycle/temperature on PV bond performance

Effect of compression on PV bonded performance
Compression Bond Strength
% N
0 800
2 2100
4 3000
6 3200
8 3300
10 3300
Notes:
1. Test method: ASTM D429-02C [13]
2. Bonding agent: Chemosil 211 primer/X6025 covercoat
3. Substrate: grit blasted mild steel
4. Rubber: vulcanised NR, vapour degreased
5. PV bonding cycle: 45 minutes at 150 C, air circulating oven
3.6 Waterborne Bonding Systems
3.6.1 History
Work on waterborne bonding systems was first begun in the early 1970s and during this
time the main requirement was in-can stability. By the 1980s stable products were made
that could be used on phosphated surfaces only. By the early 1990s bonding agents for
grit blasted surfaces were produced and by the late 1990s products that were superior in
some instances to solvent-based products were being made.
3.6.2 Differences Between Solvent and Waterborne Bonding Agents

Bonding agents, both solvent and waterborne, are based on especially designed crosslinkable
polymers that will bond to both rubbers and substrates. In solvent-borne bonding agents
molecules are entangled and give a continuous elastic layer that has good mechanical strength
in the uncured state. This is shown schematically in Figure 3.9.
103
Figure 3.9 Schematic diagram of polymer entanglement in solvent
When products using a solvent vehicle are deposited on a surface they form a continuous
elastic layer that has good mechanical strength and film properties in the uncured
state. Waterborne bonding agents are dispersed in water as micelles (small particles).
Uncured the micelles are separate and discrete having only surface cohesion between
particles. When dried they coalesce and form a continuum in the bonding layer. This is
shown schematically in Figures 3.10 and 3.11.
When applied in conventional ways to cold surfaces they remain as discrete particles
which although individually elastic do not form such a dense and continuous elastic
film as do solvent-borne products. However spraying on to pre-warmed components
causes the micelles to start to coalesce and good film properties can be achieved.
Figure 3.10 A schematic diagram of polymer micelles in aqueous suspension
104
Figure 3.11 A schematic diagram of polymer micelles starting to coalesce
Although waterborne bonding agents can be air dried and successfully bonded the
mechanical properties of film is greatly enhanced by heat application which causes the
micelles to coalesce.
3.6.3 Suggested Spraying Equipment and Conditions

High velocity, low pressure (HVLP) equipment is recommended. Spray guns can be
obtained from Walther, Binks, De Vilbiss, Graco or Sprimag are suggested.
Line pumping pressure 0.05 0.08 MPa [0.5 0.8 bar]

Nozzle 0.8 mm is preferred
Gun inlet pressure (HVLP) 0.3 0.4 MPa [3 4 bar]
Nominal atomising pressures 0.05 0.08 MPa (with fan open) [0.5 0.8 bar]
Dilution Typically undiluted or diluted with up to 10% of
de-ionised water
3.6.4 Application and Substrate Temperatures
Spraying pre-warmed surfaces enables excellent bonding films to be produced. Spraying

at high pressures should be avoided, as this will cause powdering of the bonding film.
105
Metal parts can be pre-heated to 40 70 C depending on the heat sink characteristics

of the component. Several light passes with a spray gun produce a better film than one
heavy application. If higher temperatures are used it is of the utmost importance that
the component surface is wetted and not dry sprayed. The surface should remain wet
for at least 5 seconds to allow complete wetting of the substrate. The primer will be
dry after 30 45 seconds when the top coat can be applied. The topcoat may be
applied to surfaces preheated to 40 60 C. Air temperatures in a drying tunnel up to
120 C may be used provided the component temperature does not exceed 80 C. The
top coat should dry within a minute.
3.6.5 Film Thickness
Primer should be applied at a thickness of 10 3 m and the top coat should be applied
at a thickness of 12 5 m. Coating thicknesses should not exceed 15 m for primer,
20 m for top coat.
3.6.6 Layover
Coated parts may be stored for up to four weeks prior to bonding provided the components
are kept clean and dry.
3.6.7 Progress in Performance
Over the years there have been significant advances in the performance of waterborne
products. These include not only in-can stability and assured performance but also meeting
the needs of more advanced specifications for heat and environmental resistance. One of
the deficiencies of waterborne products was prebake resistance, and improvements in
technology here have lead to the production of waterborne products that are superior to
the best of solvent-based products. In these charts the waterborne primer numbers increase
chronologically in the development sequence XW1160/1180/1190 and the top coats
XW7480/7484/7500 over an approximately five year period. The reference products are
the solvent-based primer Chemosil 211 and top coated with solvent-based Chemosil
411. Figure 3.12 shows adhesion values and Figure 3.13 shows rubber retention using
ASTM D429-02 [2]. For further details on rubber bond mechanisms see Section 3.10.
The bondability table (Figure 3.14) shows a bonding agent and rubber matrix. The
Supercovers such as Chemosil 411 will bond difficult rubbers such as EPDM. Waterborne
products such as Chemosil XW7484 or XW7500 have Supercover capability.
106
Figure 3.12 Adhesion at a prebake resistance of semi-EV NR at 175 C
100
Rubber Retention (%R)
90
80
70
60
50
40 XW7480/XW1160
30 XW7484/XW1180
20 XW7500/XW1190
10
411/211
0
4 min 6 min 8 min
Prebak e Tim e
Figure 3.13 Rubber retention at a prebake resistance of semi-EV NR at 175 C
Figures 3.15, 3.16 and 3.17 show two NR compounds, an SBR and an NBR bonded
with solvent-borne Chemosils 211/220, a hybrid solvent-borne primer Chemosil 211
with waterborne top coat Chemosil XW7484 and a waterborne system of Chemosil
XW1180 primer and XW7484 top coat. Boiling water tests (95 98 C for 2 hours)
show 100% rubber retention in all cases (see Figure 3.19).
107
Chemosil Elastomer Bondability

220 411 7484
NR
IR
BR
SBR
NBR
CR
IIR
BIIR
CIIR
CSM
ECO
ACM
HNBR
EPDM
Figure 3.14 Chemosil rubber bondability
kN 7
6
5
4 1180/7484
3 211/7484
211/222
2
1
0
NR1 NR2 SBR NBR
Figure 3.15 Tensile strengths using ASTM D429-02A, Method F

(P25 buffer test)
108
%RF
100
90
80
70
60 1180/7484
50 211/7484
40 211/222
30
20
10
0
NR1 NR2 SBR NBR
Figure 3.16 Rubber retention after hot water test
kN 3.5
3
2.5
2 1180/7484
211/7484
1.5
211/222
1
0.5
0
NR1 NR2 SBR NBR
Figure 3.17 Tensile strengths using ASTM D429-02, Test C [13]
3.7 Health and Safety in the Workplace
3.7.1 The Safety Data Sheet
The function of a Health and Safety Data Sheet (SDS) [14] is to advise, protect and
provide guidelines on the use of a product. The degree of risks and handling procedures
in Europe are codified by using a standard list of R risk phrases and S safety phrases in
a safety data sheet. However information in Section 2 Composition/Information on
109
Ingredients and Section 3 Hazards Identification in a SDS is commonly confused with

Section 15 Regulatory Information. Sections 2 and 3 describe listable constituents that
are part of the manufacture of a product and the hazards associated with them, but these
products may or may not be present as such in the final product. Section 15 is concerned
with the final product. Technologists and works engineers should be aware of this, as
operatives using SDSs frequently misread them on this account.
3.7.2 Perspective
The philosophy of science and technology is to obtain utility by harnessing the forces of
nature and its elements. In the chemical industry useful products are made from reactive and
sometimes dangerous substances. Bonding agents along with rubber chemicals are by their
very nature reactive products, and could not be used to make the end product if they were
not reactive. The duty of the chemical engineer is to provide a safe working environment for
the manufacture and use of reactive and possibly hazardous intermediates. It is the duty of
those who use and handle such products to do so with care and to follow safety guidelines
and procedures. It is also the duty of the industrial toxicologist on the one hand to look for
unforeseen hazards, while on the other it is that of the industrial chemist to produce less
dangerous products wherever possible. As part of the Henkel Responsible Care Programme
products were developed to be lead free, and solvent free. Chemosil bonding agents are
composed of high molecular weight heat reactive polymers in a liquid carrier. This approach
enables minimum hazards at the point of use. Typically the main hazards are solvents but
some grades contain inorganic lead salts. In all instances lead free versions are available and
waterborne products were designed to be free of heavy metals such as lead. Nevertheless
there should always be positive ventilation in manual spray operation areas to carry fume
particles away from operatives, and to ensure that solvent concentrations do not exceed the
threshold limit values (TLV) for solvents which are stated in the Exposure Controls/Personal
Protection section of the SDS. Face masks should always be worn to ensure that spray
particulates are not inhaled, and polychloroprene or NBR gloves should be worn so that
solvents are not absorbed through the skin. As ignition of solvent is the main immediate risk,
care should always be taken to ensure that equipment is earthed so that fire is not caused by
static. Also if a site does not have a policy requiring safety shoes with non-spark soles for all
employees, then areas in which solvents are should be restricted zones to those wearing non-
spark safety shoes. Safety Officers should carry out regular audits, and new employees always
given training in safety and personal protection procedures.
3.8 Bonding Agent Testing
Bonding agents after manufacture are screened with a series of tests involving peel tests
and exposure to hot water. These involve the use of the ASTM D429-99B Peel (modified
110
at 45 degrees). The moulding is typically compression moulding but it could also be

transfer or injection. This bond peel test has the virtue of being simple and the same
component design can also be used for sweep tests if injection or transfer is used.
The bond peel test is shown in Figure 3.18. A metal coupon 60 x 25 x 1.5 mm is masked
and has bonding agent coated in the middle 25 mm. The coupon after moulding is
inserted in a tensile machine. The mode of bond failure should be noted. This should be
recorded as % of each type of failure. RF denotes rubber failure, CM denotes failure
between the primer and the metal, RC denotes failure between the rubber and the bonding
agent. Supercover bonding agents create a highly crosslinked layer of rubber in contact
with the bonding agent. This layer is usually harder than the bulk of the rubber and the
tear may be along this line of harder rubber. This is referred to as TR which denotes thin
rubber. This should not be confused with RC failure which is most commonly due to
inadequate mixing of the top coat. CP would denote failure between primer and covercoat.
As part of the QC testing bonding agents are also subjected to a boiling water test. The
boiling water test is an accelerated test that will determine inadequate substrate
preparation, unsuitable bonding agent or an inadequate bond. This can be done by tying
back the rubber so that the bond line is stressed but a more scientific method is to use the
Henkel test as shown in Figure 3.19.
Other ASTM test methods are outlined in Appendix 3.1.
Figure 3.18 ASTM D429-02, Method B, peel (modified at 45 degrees) [2]
111
Figure 3.19 Schematic diagram for hot water test
3.9 Shelf Life Considerations
All reactive products will chemically combine in the fullness of time. An aspect which is
important is the rate of reaction. For example reactive rubber solutions mixed with
isocyanates will have a pot life of only a few hours. Rubber bonding agents however
have long shelf lives of many years in some instances but nevertheless it is important to
qualify that by defining a temperature. Storage at ambient north European temperatures
much below 20 C is very different from hot climates where temperatures are constantly
greater than 30 C. Also storage in temperate climates in stores that are heated can be as
demanding as a hot climate.
Chemosil bonding agents are heat activated products that, when stored at ambient
temperatures, give for the most part, very long shelf lives of many years. A period of
12 months has traditionally been used, in most instances, as a nominal period of shelf
life. This not only served as convenient means of identification for stock rotation but
also gives customers a frame work of guarantee for the products that they are purchasing.
With the advent of quality systems and the need for more precise documentation, defined
details of shelf life are required particularly where there may be only occasional use of a
particular grade. For this reason it is useful to consider categories of shelf life and re-
certification procedures.
112
3.9.1 Shelf Life Categories
SL0 Chemical substances stored in suitable containers that remain unchanged

indefinitely for example, solvents and water.
SL1 Products that have a very long chemical shelf life of many years. Some increase in
viscosity with age may be exhibited but this does not necessarily affect the bonding
capability of the product.
SL2 Products that have a very long shelf life as in SL1 category but are to some degree
thixotropic in nature. The thixotropy should not be confused with an SL1 product
that has self reacted.
SL3 Products that are new and have been ascribed a tentative shelf life because time
data on the true shelf life is not yet possible.
SL4 Products that have a genuine shelf life that is limited, which require very close
monitoring and stock control.
SL5 Products whose ultimate shelf life is affected when containers are opened and
require particular handling to achieve the same shelf life as in unopened containers.
It is quite possible to subdivide these categories further if required. For example SL3
might be combined with SL5.
3.9.2 Procedures for Re-certification of Bonding Agents
It is prudent to have bonding agent test procedures so that products are not needlessly
discarded and also that bonds are not made with products that are below an accepted
level or standard.
3.9.2.1 Procedures for Re-certification of Bonding Agents in Classes SL1 and SL2
Test interval
The bonding agents should be examined at six monthly intervals or other intervals as
defined by a customer to suit its requirements, to determine that the products are in a
liquid state and have not chemically reacted and solidified.
Record
A record should be kept of the finding.
113
Viscometry
Where viscometers are available the viscosity should be recorded. Viscometers such as
the Brookfield LVT are recommended. Flow cups may also be used although they are
difficult to calibrate. Bubble tubes such as Gardiner Tubes can be used for clear products.
Viscosity sensitivity
If a process is viscosity sensitive this should be noted and a standard drawn up so products
are always used within the prescribed limits.
Re-certification period
Products that have not gelled or solidified and are covered by points test interval, record,
viscosity and viscosity sensitivity may be used by a customer for a further period of
6 months. Other pre-defined periods may be used for test intervals.
3.9.2.2 Procedures for Re-certification of Bonding Agents in Class SL3

Bonding agents of class SL3 are by definition new products that require monitoring
beyond the initial shelf life indication. It is suggested that products in this category are
carefully monitored using procedures as for products of categories SL1 and SL2. If there
is any doubt about the suitability of a product within this category technical service
assistance should be sought.
3.9.2.3 Procedures for Monitoring of Bonding Agents in Class SL4

Bonding agents in this category have a restricted shelf life and should be monitored as
outlined for bonding agents of categories SL1 and SL2 but at weekly or monthly intervals.
3.9.2.4 Procedures for Re-certification of Bonding Agents in Class SL5
Moisture-sensitive bonding agents

When a product is used on an intermittent basis and is likely to be affected by exposure
to atmospheric moisture it is recommended that the product should be packed off into
smaller containers to maximise its utilisation. The following information includes general
advice on handling products of this category as well as testing procedures.
114
Viscosity
Large drums should be fitted with desiccant traps to prevent moisture ingress to part
used drums. Smaller sized containers should have lids replaced immediately if not being
completely used. Viscosity tests and procedures should be in accordance with testing
for SL1 and SL2 category products.
Clarity
Cloudiness of clear products is not necessarily a sign that the products are unsuitable. A
slight haze does not affect the product unless otherwise advised. A haze standard should
be drawn up for products that are likely to be used on an intermittent basis.
Photosensitive sensitive bonding agents
Products that are light-sensitive are supplied in opaque containers. Re-packing of

such products to prevent repeated exposure to light should be into suitable opaque
or dark brown glass containers. Used material should not be put back into the bulk
container.
Any photochemical reaction will exhibit itself by an increase in viscosity or reduced

clarity. Tests should be carried out as indicated above in the appropriate sections.
3.10 Troubleshooting
In the event of bond failure it is important to determine the location of the failure. This
can be between the bonding agent primer and the metal or between the rubber and the
bonding agent. For historical reasons (this dates back to rubber tie layers before modern
bonding agents) the failure between the primer and the substrate was known as CM
failure (Cement/Metal) and the failure between the rubber and the bonding agent is
known as RC failure (Rubber/Cement).
There is also the theoretical possibility of failure between the primer and the top coat
which could arise through contamination, or other reasons such as using a primer and
top coat that were not designed for each other. A schematic diagram illustrating CM
and RC failure is shown in Figure 3.20.
115
Figure 3.20 A schematic diagram showing CM and RC failure
CM failure may be due to:
Poor primer preparation

Inadequate stirring,
Incorrect dilution,
Out of shelf life of product.
Inadequate stirring can cause bond failure where a non homogenous mixture is applied.
Use of incorrect diluent, such as xylene in a ketone based primer, can cause instability in
the bonding agent primer, resulting in selective precipitation or disruption of the surface
morphology. Most Chemosil primers have long shelf lives and this is not usually regarded
as a problem.
Poor primer application
Dry spraying,
Inadequate drying,
No primer or incorrect product.
116
In automated systems it is important to ensure that primer is actually applied. One solution
to the problem is to use a product such as Chemosil 211Y primer which is designed to be
used in processes with optical sensometery to differentiate the primer from grey phosphate
surfaces. Dry spraying occurs where the solvent has evaporated before the bonding agent has
wetted out the metal component. The answer is to use a slower diluent, for example MIBK in
place of MEK, or to alter the spray gun conditions. No primer at all can arise if a line is
stopped on an automated line. Inadequate drying will occur if the top coat is applied to a wet
primer surface, so that the layers were diffused, giving reduced properties of both layers.
Incorrect metal preparation
Contaminated blast media,

Worn blast media,
Contaminated degreaser,
Inadequate conversion coating (A coating produced by chemical or electrochemical
treatment of a metallic surface that gives a superficial layer containing a compound
of the metal),
Outside of the time window.
Worn blast media is the most likely cause of insufficient metal preparation. Time windows
will be reduced in humid climates.
RC failure may be due to:
Poor top coat preparation

Inadequate stirring,
Incorrect dilution,
Out of shelf life of product.
Inadequate stirring is probably the greatest single cause of bond failure.
Poor application
Dry spraying,
Substrate too hot,
117
Inadequate film thickness,

Inadequate drying,
Incorrect bonding agent,
Contaminated spray air lines.
This is an important section. Dry spraying has already been dealt with under CM
failure but a too hot substrate also causes bond failure due to failure to wet out. Linked
to this is production line stoppage where parts either in a drying oven after primer
application or after the final coat of bonding agent is applied may be overcooked and
so produce visually perfect parts that in reality are parts that will fail in service. Where
a production spray line stops, parts that were in the heating tunnel should be removed
for recycling. Adequate film thickness is more important where EV and SEV systems
are being used. Frequently Supercovers are used to minimise this possibility of failure
because they are more reactive at lower micron thicknesses. Spotty spraying is usually
associated with water in a spray line. This tends to show up more with top coats
because ketones in the primers have some capacity to absorb water. The solution is to
empty or even fit traps to the air line.
Moulding operation problems
Deflashing
Cryogenic deflashing should be controlled so that only the flash is embrittled. If the
polymer in the component becomes brittle the bond could fracture.
Contamination
Contamination with mould release agents or substances that will prevent bonding must
be avoided.
Leaking moulds
To achieve a bond the rubber must be stationary in the mould. Leaking moulds keep the
rubber moving and lead to bond failure.
Prebake of bonding agent
Bonding agents react with the rubber at moulding temperatures. Excessive time in hot
moulds before moulding can lead to pre-cure of the bonding agent, thus giving rise to
bond failure.
118
Platen temperatures
Uneven temperatures will cause uneven bonding.
Layover of coated parts
Long layovers can lead to contamination unless in a sealed container.
Demoulding
Hot tear strengths of bonds immediately after moulding may be less than the final bond
strengths achieved by a post cure.
Rubber
Ensure specified rubber was used and within shelf life.
A troubleshooting flow chart may be used to aid in diagnosis of bond failure, see
Figure 3.21.
Figure 3.21 Troubleshooting flow chart to determine type of bond failure
119
3.11 Summary
In conclusion it may be said that it is possible today, almost a century and a half after the
first rubber to metal bond was created, to bond virtually any rubber to any substrate.
This is a testament to the creativity of chemists and the energy and enterprise of those in
the rubber bonding industry.
The real message however to each generation of technologists is not only to rise to the
challenge of achieving ever improved quality by careful control of variables, or producing
products to meet more demanding specifications, but also a personal one of quo vadis.
In a world where plate tectonics will never be a thing of the past, the need to guarantee
a universal freedom from fear of the natural world in homes, as well as in the
transportation infrastructure of roads and bridges, which can be subjected to the forces
of nature is a challenge that technologists and design engineers must meet. However, by
building on the experience of the past the future can be viewed with confidence.
Acknowledgements
The authors wish to thank Henkel KGaA for permission to publish this information and
are particularly indebted to Dr Klaus Marten of Henkel AIA for encouraging the milieu
of excellence.
Information supplied by Henkel AIA-SR Team (Europe)
Heinz Alberts, Dieter Beiersdorf, Tom Carey, Richard Prince, Klaus Schrmann,
Rainer Wefringhaus.
References
1. C. Sanderson, inventor; no assignee; UK Patent 3288, 1862.

2. ASTM D429-02 A
Standard Test Methods for Rubber Property - Adhesion to Rigid Substrates.
Method B - 90 Stripping Test - Rubber Part Assembled to One Metal Plate, 2002.
3. ISO 9001
Quality Management Systems - Requirements, 2000.
4. EC Directive 84/360.
5. Environmental Protection Act, 1990.
120
6. T. A. Luft.
7. PG6/32, 1997.
8. Introduction to Part 1 of the Act. Guidance Note 4 (GC4) - Secretary of States

Guidance on the Interpretation of Terms Used in the Process. Guidance Notes,
HMSO.
9. SIS 05 59 00
Preparation of Steel Substrates Before Application of Paints and Related
Products - Visual Assessment of Surface Cleanliness, 1989.
10. BS 7079
Preparation of Steel Substrates Before Application of Paints and Related
Products, 1990.
11. ASTM D2200-95 (2001)el

Standard Pictoral Surface Preparation Standards for Painting Steel Surfaces, 2001.
12. K. Schrmann, Study of Phosphate Surfaces, unpublished work by Henkel KGaA.
13. ASTM D429-02A

Standard Test Methods for Rubber Property - Adhesion to Rigid Substrates Method
C - Measuring Adhesion of Rubber to Metal with a Conical Specimen, 2002.
14. Safety Data Sheets for Substances and Preparations Dangerous for Supply
Approved Code of Practice. HMSO ISBN 071760859X.
15. ASTM D429-02A

Standard Test Methods for Rubber Property - Adhesion to Rigid Substrates,
Method A - Rubber Part Assembled Between Two Parallel Metal Plates, 2002.
16. ASTM D429-02A

Method D - Adhesion Test - Post Vulcanisation (PV) Bonding of Rubber to
Metal, 2002.
17. ASTM D429-99E

Method E - 90 Stripping Test - Rubber Tank Lining - Assembled to One Metal
Plate, 2002.
121
Appendix 3.1
ASTM Test Methods
ASTM D429-02, Method A [15]

Butt, tensile test using compression moulding (see Figure 3.22). This is not widely used
in rubber to metal bonding.
ASTM D429-02, Method B, Peel (Modified at 45deg) [2] is described in Section 3.8.
ASTM D429-02, Method C, Conical peel test [13] This has the objective of evaluating
bonding agents at a high stress point at the tip of the insert. Moulding is typically transfer.
The disadvantages of the test are the expense of the inserts, and ensuring that the points
are equivalent in all specimens as this affects results (see Figure 3.23).
ASTM D429-02, Method D, Post Bond Vulcanisation butt test [16]. Parts are clamped
in a jig and put into an autoclave or oven.
ASTM D429-02, Method F. This test was originally devised by Henkel (and is known in
Europe as P25 Buffer test) because of the cost of inserts in ASTM D429-99C. This
subsequently became ASTM D429-02, Method F. This has proved extremely valuable
and reproducible and also has the advantage of using low cost inserts (see Figure 3.24).
Figure 3.22
122
Figure 3.23
Figure 3.24
123
124
4
Bonding Rubber to Metals with Waterborne
Adhesive Systems
B. Crowther (Sections 4.1 and 4.2) and
R. Woodcock (Section 4.3)
4.1 Introduction
Traditionally, since their development in the 1940s, bonding agent systems for bonding
rubbers to metals have used organic solvents as the dispersing and carrying medium for
the system of polymers, resins, curatives and fillers in their makeup. The solvents may be
single systems or mixtures, aliphatic or aromatic in nature. Dilution of the bonding
agent systems on the factory site has also necessitated the use of organic solvents. Organic
solvents have the ability to easily wet out most surfaces to which bonding agents are
commonly applied. They also lift any small residual contamination spots left after
degreasing, by solubilisation, thus avoiding any likely service problem resulting from
such minor contamination.
Long term experience of the use of organic solvent-based bonding systems by both rubber
bonded product manufacturers and their customers, with the accumulated knowledge of
the performance of their products in adverse conditions, is a further factor mitigating
against swift acceptance of bonding systems using other than organic carriers.
Environmentally the use of the organic solvent systems is not acceptable. There are various
reasons for this resistance to the continued use of organic solvents:
they create a health hazard in the factory atmosphere,
organic solvents are generally inflammable and present an explosion hazard,
organic solvents are expensive,
there are disposal problems associated with solvents,
operatives require protection from fumes and addictions,
organic solvents in the presence of direct sunlight can form low-atmosphere ozone,
which can be extremely detrimental to human health.
Costs to industry in controlling the use of solvents in industrial and urban environments,
current environmental legislation, coupled with high insurance costs for factories using
125
Commercial rubbers
solvent systems, all add to the forces pressurising suppliers for changes to non organic
solvent-based bonding systems.
4.1.1 Solvent Elimination by the Rubber Industry

The use of waterborne bonding systems has been driven forward by the worldwide
concern about environmental pollution emanating from the use of solvents by industry
in general.
A number of rubber manufacturing processes involve the use of solvents, which in the
past were often vented to atmospheres after fulfilling their purpose in the manufacturing
process. Processes involving solvents include:
Manufacture of adhesives,
Rubber doughs and solutions for spreading to substrates,
Degreasing of metallic and plastic substrates for rubber bonding,
Bonding adhesive solutions.
The latter two processes are of immediate concern to the reader in the context of this book.
Worldwide limits for solvents in the atmosphere were discussed and set (and subsequently
updated) at a conference in Montreal in 1988. The protocol issued after the conference,
the Montreal Protocol, laid down a timetable for solvent use reduction for
chlorofluorocarbon solvents and specifically for carbon tetrachloride and methyl
chloroform. The use of the former to be eliminated by 1997, and the latter to be reduced
by 70% by the year 2000, and then to be totally banned by 2005.
As expected, these limits have not been met in the UK. The pertinent act for the UK is the
Environmental Protection Act 2990 Pt 1, with specific guidance notes for the Rubber
Industry, Process Guidance Notes 6/28 (92) which applies to companies using over
5 tonnes of solvent per year. All participants at the Montreal Conference drew up their
own legislation, which can be determined by the reader from their own countrys
controlling bodies for environmental control.
The modifications found necessary for UK compliance were incorporated into the Act in
1997, with a 50% reduction to be achieved by 1999 and a 67% reduction by the year
2007. Beyond 2007, new legislation will inevitably be introduced.
Participating countries in the Montreal Protocol have their own reduction targets and no
doubt are amending their legislation in a similar manner to the UK (see also Section 3.1.7).
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Bonding Rubber to Metals with Waterborne Adhesive Systems
4.1.2 Techniques Necessary in Bonding of Rubber to Meet Local

Environmental Pollution Limits
By changing from solvent degreasing to aqueous degreasing systems a 25% reduction in

pollution can be achieved. To meet the next target reduction of 67% solvent emission it
will be necessary to use only waterborne bonding systems for rubber to substrate bonding.
Readers must make themselves aware of their own countrys legislation and solvent limits,
and ensure that the manufacturing processes comply with the current requirements.
4.2 Waterborne Bonding Systems (see also Sections 3.4.2 and 3.6)
Use of water as the carrier for bonding systems seems to be the obvious answer to most
of the problems encountered with solvent-based adhesives. However, use of water for
the application of bonding systems has a number of shortcomings, which have made the
development of the new systems difficult and slow to be presented to and accepted by,
the marketplace.
Waterborne bonding systems do not have the same ability as organic solvents to wet
out the metal surface or solubilise any greasy contamination during bonding agent
application to the metal surface. Another factor is quick evaporation of the alternative
carrier from the applied adhesive film. Use of water requires higher temperatures for its
removal from a deposited film of adhesive. Incomplete removal will result in porous
adhesive layers, or even in underbond corrosion at the metal surface.
4.2.1 Structure of Organic Solvent-based Bonding Systems
The conventional bonding systems used for many years by the bonding industry are two
phase systems. The resin and polymer phase is a solution, whilst the second phase,
comprising the accelerators and other additives of organic or inorganic origin, is in the
form of finely divided suspensions within the first phase.
4.2.2 Structure of Waterborne Bonding Systems
Bonding agents with water as the carrier are multiphase systems. The polymer phase
consists of an emulsion (or latex) within a continuous phase of water and the second
phase of organic and inorganic materials is dispersed within the liquid phase. The fact
that the polymer system is based upon latex technology reflects upon the stability of the
latices being used and their protective stabilisation against flocculation. Obviously bonding
agent suppliers will compound their systems to achieve maximum stability, but outside
127
forces, such as water evaporation, vigorous agitation, low or too high temperatures,
addition of solvents or diluent water containing salts of polyvalent heavy metals, may
well result in irreversible flocculation.
4.2.3 Fundamentals of Waterborne Bonding Agent Application

Moore [1] discusses the surface energy requirements of the application of bonding agent
to metal surfaces and reviews the thermodynamics of wetting. Critical aspects of the
process of application are concerned with the initial scrupulous cleaning of the metal
and its surface topography, to ensure that no traces of oil are trapped after grit blasting.
Cleaning with chlorinated solvents generally eliminates any problem in this area, but as
legislation prohibits their use and resort has to be made to other cleaning methods, then
problems are envisaged. Moore concludes that adhesive wetting is ultimately a function
of the surface tension of the adhesive and the level of oily residue on the metal surface. A
method of determining surface tension, which has been derived from a technique used
by the printing industry [2] for determining the wettability of corona treated polyethylene
or polypropylene using surface tension pens, has been adapted by Morton International,
to determine the effectiveness of metal cleaning methods.
4.2.4 Waterborne Bonding Systems in Factory Usage

In use, care must be taken to ensure that the possibility of drying out of the bonding
system at the edges of dip tanks, paint pots and on and in spray-guns, is not allowed to
occur, for contrary to the experience of such deposits with solvent-based systems, water
will not dissolve them back into the system. Attempts to reincorporate hardened bonding
agent, in the hope that it will redissolve, will result in the bonding agent in use being
contaminated with hard bits. Evaporation of water from the bonding agent during use
will also result in flocculation if the water loss is too great. Forces come into effect due to
the closer proximity of the latex particles to each other as evaporation proceeds. Collision
between particles results in flocculation. Similar effects occur as the result of extreme
temperatures. Too low a temperature allows the formation of ice crystals, which results
in a lowering of the volume of the water phase and thus a closer proximity of the latex
particles and hence more likelihood of collision and flocculation. Conversely, at high
temperatures the influence of the temperature is to considerably speed up the movement
of the particles, and thus the opportunity for collision and flocculation rises rapidly.
Dilution of the relatively high solids material can be carried out using deionised or distilled
water, definitely not tap water.
The agitation normally required to prepare bonding agents for factory use after transport or
storage, to lift any dispersed ingredients into complete suspension, must be carried out carefully
128
with waterborne systems. Too violent an agitation by high-speed or planetary type mixers
must be avoided. Drawing in of air by this type of mixer will cause frothing, due to the
surfactants necessary to stabilise the latex system. Stirring at less than 60 rpm is recommended.
The stirring should be carried out for a minimum of 8 hours after long storage, or for 2 3
hours if the bonding agents have been allowed to settle for a couple of days.
4.2.5 Metal Preparation - For Waterborne Bonding Systems

The cleaning of metals for the application of waterborne bonding systems is much more
critical than for solvent-based systems. Scrupulously clean metals are vital, to ensure
maximum wettability of the bonding surface. Bond [3] suggests that calcium modified
phosphating of metals is preferable to conventional grit blasting with its potential for
re-infecting the metal surface after degreasing by using contaminated grit. Proper
housekeeping should eliminate such problems.
With the advantages and disadvantages of these systems it is still going to be difficult to
convince customers that the reliability of the bonded products using waterborne adhesives
will be as good as for products produced with solvent-based systems.
4.2.6 Waterborne Bonding Agent Application

Application of the waterborne systems is similar to solvent-based system with some
fundamental differences. The drying time necessary for the applied coat of bonding agent
is longer, but can be speeded up to some extent by applying the waterborne adhesive to
metals which have been preheated to 60 C. Drying oven temperatures should be increased
to 104 C and air speed increased in drying tunnels to encourage evaporation. Coated
metals can be baked at up to 170 C for 5 minutes to prevent compound flow distortion
or removal, without problems.
Applied film thickness is critical for use of these systems. If the film is too thin, then
spotty bonding will result. Too much bonding agent applied will result in delamination
and will cause flaking. Best film thicknesses have been determined by Bond [4] to be:
primer 5.0 10.2 m

topcoat 12.7 15.4 m
giving a total film thickness of 17.7 25.6 m
These levels of primer and adhesive cover were found to be resistant to salt cabinet
attack after 72 hours, even if metals had only previously been grit blasted, without any
chemical treatment of the metal surfaces.
129
Correct viscosity of the applied bonding agent must be controlled by methods other than
those used with solvent-based systems. Cup or rotary viscosity testers are not reliable
methods of determining viscosity of emulsions. Hydrometer testing of specific gravity is
a more reliable way of measuring viscosity and hence controlling deposited film thickness.
4.2.7 Waterborne Bonding Agent Storage Stability
In general, the storage stability of waterborne systems is good. However, the viscosity of
one grade of Chemlok 855 is known to increase after storage periods in temperatures of
approximately 40 C, until it appears to be gelled. With high shear stirring, this gel
quickly breaks down to its working viscosity, without any impairment of performance.
Room temperature storage of this grade is 3 months, with little viscosity change.
4.2.8 Non Bond Advantages of Waterborne Bonding Systems
There are some advantages from using waterborne bonding agents:
The removal of atmospheric pollution from solvents.
Elimination of fire hazards and thus decreased insurance premiums.
Ease of spillage removal - simply wipe up using warm water containing detergent.
Disadvantages include the problems of careful handling to prevent flocculation, and the
higher heating costs from metal warm-up prior to and after bonding agent application.
4.2.9 General Comments - Waterborne Bonding Agents
In general terms the primer coats developed by the various manufacturers have a greater
affinity for the metal surface, being designed to fully wet out the metal surface. They also
tend to be somewhat rigid in nature, having a high crosslink density. The rigidity of the
primer coat acts as a mechanical, as well as a chemical, key to the metal surface. The
bonding agent with the higher affinity for the rubber is much more flexible in nature,
thus acting as a stress distributor between the layers of materials. Different rubbers require
different mechanisms to achieve crosslinks between the system of the bonding agent and
the bulk rubber. With the large variety of rubbers available, of both thermosetting and
thermoplastic types and a wide variety of substrates to which they have to be bonded, it
is very evident that the dream of a single universal bonding system for all rubbers and
metals, is likely to remain just that - a dream.
130
4.3 Waterborne Bonding Agents - A Factory Experience
The initial objective has been the replacement of the solvent-based top coat. This
has been highly successful being less prone to mould fouling or lamination within
the rubber matrix than the Chemosil 411/Thixon 530 type solvent systems, due
to the fact that the waterborne top coat (Chemosil XW 7484 now Chemosil 7500)
is intermediate in its reactivity between Chemosil 220 and Chemosil 411 solvent-
based materials.
The main problem with waterborne materials is that they need to be applied to warm
metals which helps to break down the micelle structure in the system and so produce
a continuous film, otherwise the material will flake off.
By using thinner films the waterborne material competes in economic terms with the
solvent-based Thixon 530/Chemosil 411 type, bearing in mind the advantage of higher
solids content in the waterborne material, thus concentrating the active ingredients in
any given volume of dried adhesive film.
Because of the need for preheated metals it is necessary to modify some equipment,
but this should not be a major financial factor. There will however be some increase
in energy consumption but this will be less than the costs involved for solvent
entrapment. Because of the need to preheat metals, especially for primer application,
it has been simpler, initially, to introduce waterborne top coats on solvent-based primer.
Waterborne bonding agents can also replace the Chemosil 220/Chemosil 520 solvent-
based types due to the reduced level of fouling, and this replacement has already
commenced even though the economics dictate that this is marginally more expensive.
If only waterborne systems are being used in spray machines then less downtime is
necessary to clean out the spray system between adhesive types. With mixed systems
rigorous cleaning is necessary to prevent solvent/waterborne systems contaminating
each other.
4.3.1 Thickness Effects

The application of thin films assists rapid drying and prevents crazing or flaking of the
dry film.
Table 4.1 shows that surprisingly thin coats produce an effective bond. However in practice
it would not be advisable to aim below 5 m on any metals other than flat plates. Any flow
of bonding agent when applied to a shaped metal could result in excessively thin spots.
131
Table 4.1 Effect of changing the ratio of Chemosil XW7484 (now XW7500)
applied to a 9 m coat of Chemosil 211 primer
Ratio of Chemosil Average peel bond strength N/mm
Chemosil % Solids XW7500
XW7500:water thickness, m 40 IRHD NR 55 IRHD NR
100:0 30.6 21.1 8.5 20.3
75:25 23.0 12.7 8.5 19.3
67:33 20.4 9.6 8.8 16.5
60:40 18.0 8.8 8.5 18.1
50:50 14.7 5.5 8.2 16.5
40:60 12.1 3.6 8.5 15.8
In all cases the rupture was rubber/rubber
IRHD: International Rubber Hardness Degree
Also other factors play an important role regarding thickness:
As a general rule the top coat should be twice the thickness of the primer. Otherwise
the primer may consume too high a proportion of the crosslinking agent from the top
coat, leaving insufficient agent for the satisfactory reaction between top coat and
rubber curing system. This applies to solvent and waterborne materials.
Thicker top coats entrap the crosslinking agent resulting in improved pre-bake
resistance (see below) with a thicker coat.
Thicker coats are required for soft compounds (below 45 IRHD).
The work to date, therefore does indicate good tolerance to thickness variation but when
all factors are considered the preferred thickness should be a primer coat of 5 7 m and
a top coat of 10 14 m. Limits determined on a factory basis differ from those found
under laboratory testing (see Section 4.2.6).
It is not advisable to change the spraying technique to achieve the required coating
thickness but rather to modify the level of dilution. There is no significant effect on
drying time on warm metals when these materials are diluted. Dilution levels above 15%
are not recommended.
132
4.3.2 Pre-bake Resistance

When bonding agent treated metals are introduced to a mould cavity they must be capable of
withstanding the mould temperature for sufficient time to allow compound to enter the mould
to form the product, before the adhesive has lost its ability to effect a bond to the rubber.
Pre-bake resistance is an important aspect. This is especially so with interleaf bushes

which have three relatively thin metals per bush, moulded in a 28 cavity mould. The
loading time for 84 metals for such a mould charge is quite long and experience to date
has shown that a minimum of 7 minutes pre-bake resistance at 170 C is preferable.
There is also a thickness effect on pre-bake resistance. In the above evaluation the thin
coats had 4 m primer and 7 14 m top coat, whilst thick coats were 8 14 m primer
and 10 18 m top coat (see Figure 4.1).
Figure 4.1 Effect of application thickness of bonding agent Chemosil 211

Chemosil 211 (primer: solvent-based); 411: Chemosil 411 (topcoat: solvent-based);
XW7500: Chemosil XW7500 (topcoat: waterborne); AP10: Thixon AP10 (primer:
waterborne); 5005: Thixon 5005 (topcoat: waterborne); XW1190: Chemosil XW1190
(primer: waterborne)
133
With some waterborne bonding agents, pre-bake resistance was reduced with thinner
films of some adhesive products but not with other types.
Whilst the Chemosil XW7484 (now Chemosil XW7500) gave the best results with solvent-
based primer, the pre-bake resistance was reduced when used with a waterborne primer.
Similarly the Thixon 5005 was marginally better with solvent-based than with
waterborne primer.
4.3.3 Primers
Application of primers to warm metals is not a problem with most operating systems.
The limiting factor with all waterborne systems is the retention of sufficient heat in the
metal to be able to spray both primer and top coat without reheating the metal after
primer application.
4.3.4 Polymer Range

To date Chemosil XW7484 has been evaluated against a range of polymers and bonding
has been successful with NR, IIR, NBR and peroxide vulcanised EPDM and unsuccessful
with CR and Vamac. Chemosil XW7484 has now been replaced by Chemosil XW7500
which will also bond CR components. Several other materials on the market such as
Thixon 5005 are also claimed to be satisfactory with CR.
The results are interesting in that in all cases there is a 7.5 9.0% reduction in bond
strength with a waterborne top coat, but the rupture still occurs in the rubber matrix
(see Table 4.2).
4.3.5 Product Range

The range of waterborne materials available has proliferated recently and some of the
current materials are listed in Table 4.3. The list includes the Chemlok (USA) range
which were reported in Rubber Technology International [6]. However these materials
are not manufactured by Henkel who appear to have their own XW range of materials
(see Section 3.6).
4.3.6 Current Disadvantages of Waterborne Bonding Agents

Aqueous bonding agents contain polymer and resin emulsions and pigment dispersions,
both stabilised with surfactants. The inherent polarity of water makes it much more
134
Table 4.2 Polymer type (bond strength in MPa)

Bonding system NR NR NR NR
Solvent-based 10.8 7.25 6.05 6.55
Waterborne 9.9 5.7 5.5 6.05
% Reduction in
8.3 7.6 9.0 7.6
bond strength
Table 4.3 Current waterborne bonding agents

Company product name Designation Application
Thixon AP10 Primer
5005 General purpose coat
5100 Improved environmental resistance
2500 One coat system
Megum 23501 Primer
Chemosil XW 1190 Primer
XW 17864 Increased flexibility primer
XW 7500 General purpose coat
Chemlok (USA) 805 Primer
8003 Primer
8006 Primer
8007 Primer
Cilbond 60W Primer
R-6100 General purpose coat
R-6100 General purpose coat
R-6180 PU bonding
135
difficult to keep aqueous adhesives stable, and destabilisation can occur with changes
in pH and temperature extremes. The material must be kept frost free.
It is always necessary to preheat the metals.
They are more sensitive to pressure loss resulting in edge defects with old leaky moulds.
The action in this case is to refurbish the mould and not seek an alternative bonding
agent.
Surfactants tend to foam with high speed mixing. When hand painting only brush in
one direction.
To date many waterborne bonding agents have proved unsuitable for high bulk metals,
such as metal castings, unless a level of preheating is given to the prepared metals
prior to loading in the mould. Thixon 5100, however, is suitable for this application
being more reactive. It also has a shorter pre-bake time which does not present a
problem with thick metals that are slower in achieving activation temperatures.
References
1. M. J. Moore, Presented at the 145th ACS Rubber Division Meeting, Chicago, IL,
USA, Spring 1994, Paper No.50.
2. Tappi Method T 698 cm-91, Determination of Wetting Tension of Polyethylene

and Polypropylene Films and Coatings (Modified Visking Analytical Technique),
The Pulp and Paper Institute Atlanta, Georgia, 1983.
3. K. Bond, Adhesives Age, 1990, 33, 2, 22.
4. T. Plasczynski and K. M. Bond, Presented at the 146th ACS Rubber Division

Meeting, Pittsburgh, PA, USA, Fall 1994, Paper No.92.
5. M. J. Moore, Presented at the 145th ACS Rubber Division Meeting, Chicago, IL,
USA, Spring 1994, Paper No.43.
6 T. Plasczynski and D. Mowrey, Rubber Technology International, 1996, 128.
136
5
Rubber to Rubber Bonding
R. Joseph
Rubber to rubber bonding is unique in that both the substrates are flexible and of
comparatively low strength. Bonding of raw rubbers/rubber compounds and their
covulcanisation is important in industrial operations such as tyre building, while bonding
of vulcanised rubbers is important in operations such as precured (cold) retreading.
Bonding of vulcanised rubbers to unvulcanised rubbers is also important in conventional
(hot) retreading processes. There are a wide variety of variables affecting rubber to rubber
bonding, such as the chemical composition of the rubbers, their compatibility/
incompatibility, their molecular weights and their distributions, additives, crystalline
and amorphous contents, surface nature and chemistry, crosslink densities, etc.
5.1 Bonding of Unvulcanised Rubbers
5.1.1 Tack/Autohesion
Uncured rubbers at a temperature above their Tg can easily flow into intimate contact
resulting in firm adhesion because of their molecular mobility. The ability of two uncured
rubber surfaces to adhere together upon contact after the application of moderate pressure
for a relatively short time is known as absolute tack (tack) [1]. Interdiffusion of chain
segments across the interface is considered to be a major factor for developing tack.
Tackiness between surfaces of the same rubber or rubber compounds having the same
composition is referred to as autohesion or autohesive tack. An optimum tack is necessary
for operations such as tyre building where the various parts, the impermeable lining, the
reinforced carcass and the tread, are all usually made from different rubbers and have to
hold together until the tyre is vulcanised in the press. Removal or repositioning during
the building process becomes difficult with very tacky compounds in addition to promoting
air entrapment. Further, uniform distribution of accelerators and sulphur in very tacky
compounds at the final stage of mixing is also difficult. On the other hand, less tacky
components may tend to fall apart before curing.
The green strength (strength of an unvulcanised rubber compound) of an rubber is the

upper limit of the tack [2]. The ratio of the absolute tack divided by the green strength is
sometimes referred to as relative tack. When the relative tack is close to one it may be
137
Commercial rubbers
assumed that almost complete contact and interdiffusion has taken place between the
two surfaces and that the tack is green strength limited. But, a low value of relative tack
shows that very little contact and interdiffusion has taken place and that the tack is
interdiffusion limited. Amorphous polymers which do not crystallise under strain rely
completely on chain entanglements to provide green strength and hence significant chain
interdiffusion is required in order to develop high tack. Polymeric molecules from the
two contacting surfaces must diffuse a sufficient distance across the interface to become
entangled so as to develop a strong tack, which can resist stress. After sufficient
interdiffusion, if the rubber is capable of strain crystallisation (the tendency of structurally
regular rubbers to crystallise upon deformation) it can boost the tack to much higher
levels. Hence, a strain crystallising rubber like natural rubber (NR) can develop very
high tack. The advantage in this case stems from the fact that strain crystallisation does
not occur during the interdiffusion or bond forming step and hence it does not interfere
with this step. Further, in the case of strain crystallising rubbers less interdiffusion may
be sufficient to develop good tack.
Polybutadiene rubber (BR) can be modified by reaction with isopropyl azodicarboxylate

(IAD) to improve its bonding. The Tg of the modified polymer increases with its IAD
content. Eventually at high levels of modification two Tgs are observed indicating the
presence of two phases. The tack and the green strength of BR are found to increase with
IAD content. However tack reaches a maximum at 28% IAD content and decreases
thereafter while the green strength continues to rise [3]. This is because at low levels of
IAD, the green strength is enhanced without much loss in molecular mobility. But at high
IAD levels the tack decreases due to a severe reduction in chain mobility, thereby
prohibiting the formation of an extensive tack bond. Although crystallinity may improve
green strength, it severely limits the chain mobility required for bond formation. Hence
partially crystalline ethylene propylene rubbers (EPR) or ethylene propylene diene rubbers
(EPDM) have very poor tack [4].
The tack or autohesion of raw rubber/rubber compounds depends on a number of factors,

such as polymer characteristics like structure and molecular weight, type and amount of
compounding ingredients like fillers and plasticisers, rate of crosslinking, presence of
tackifying resins and surface conditions such as oxidation or bloom which may occur
during processing or storage.
In the case of NR, tack or autohesion passes through a broad maximum with increasing
molecular weight and thereafter decreases [5] (see Figure 5.1).
This broad maximum occurs due to a proper balance between contact diffusion and
green strength/intermolecular attraction at intermediate molecular weight. The diffusion
of the rubber molecules across the interface increases as the molecular weight decreases,
138
Figure 5.1 Effect of NR molecular weight on autohesion

(Reproduced with permission from C. K. Rhee and J. C. Andries, Rubber Chemistry and Technology,
1981, 54, 1, 101, Figure 8, p.111. 1981, Rubber Division, American Chemical Society Inc.)
but the green strength/intermolecular attraction per molecule decreases. Hence rubbers
in the liquid form having very low molecular weight cannot develop good tack due to
their poor cohesive strength even though they can easily diffuse across the interface. The
effect of contact time on autohesion is also shown in Figure 5.1. The autohesive bond is
found to get stronger as the contact time increases, probably due to higher interdiffusion.
Even though NR has superior tack compared to styrene butadiene rubber (SBR) the
influence of the molecular weight can detract from this advantage enjoyed by NR. Since
NR undergoes chain scission upon mastication, moderate amounts of mixing will improve
its tack as the molecular weight is reduced. However, upon prolonged mixing the tack of
NR can become quite low. SBR, on the other hand, is less sensitive to shear degradation
and hence its tack will be less altered by mastication. However, the broad maximum in
tack exhibited by NR is practically advantageous since it can accommodate considerable
variation in mixing history of NR-containing stock without much loss in the tack.
5.1.2 Influence of Vulcanisation System
The composition of the vulcanisation systems and the dynamics of vulcanisation can
affect the bond strength significantly [6]. The flow behaviour of the stocks is controlled
by the vulcanisation rate. During vulcanisation gradual transition from plastic flow
139
state to elastic state takes place. After vulcanisation the rubber loses its capacity for
cohesion. Thus the fusion of separate layers can only take place in the initial stage of
vulcanisation. In general, a system which vulcanises more slowly promotes favourable
conditions for autohesion.
In the bonding of different rubbery compounds the unvulcanised boundary layer does
not promote bond strength. The process of covulcanisation is possible if the two phases
vulcanise at an identical rate. Mechanical non-uniformity and sharp alteration in the
modulus and other properties lead to setting up of zones of over stressing and conditions
of deformation in the boundary layer, which may lead to intensive fatigue and destruction.
As the concentration of oxygen and oxygen compounds will be high in the boundary
layer, fatigue takes place more intensively in the surface layer than in the bulk of the
rubber. In the case of rubbers like SBR and polychloroprene (CR), the bond strength
depends upon the interface crosslinking as they differ in the cure rate as well as the
curing system. Even when two partially crosslinked sheets made from SBR and CR are
bonded together by further vulcanisation the bond strength is found to be highly dependent
upon the degree of interface crosslinking [7].
5.1.3 Influence of Filler Type
The level and type of filler is another significant factor, which controls the tack or
autohesion. In the case of reinforcing fillers the major parameters affecting the tack are
the extent of reinforcement of the rubbers by the filler and the extent of decrease in
surface mobility of rubber molecules due to the presence of the filler. It is interesting to
note how these two parameters affect the tack of rubbers like NR and SBR. NR which
has a higher chain mobility compared to SBR is more influenced by the reinforcement
effect while SBR by the chain mobility effect. In the case of NR, addition of high abrasion
furnace (HAF) black up to 40 phr substantially enhances the tack compared to the unfilled
compound, and this remains unchanged with contact pressure since the effect of
reinforcement predominates over the effect of decrease in mobility in this range. However,
addition of carbon black above 40 phr marginally reduces the tack since the effect of the
decreased chain mobility predominates over this level. When the rubber is mixed with
carbon black, bound rubber is formed on the surface of the filler. The amount of bound
rubber increases with increase in surface area and structure. Hence the tack is reduced
with decrease in the particle size or increase in the structure of carbon black.
In the case of SBR, which cannot easily achieve bond formation, when 40 phr of easy
processing channel (EPC) black is added the tack is reduced and then remains almost the
same during mastication. The filler in this case further restricts chain mobility, reducing
interfacial interactions and thus leading to lower tack. If an SBR can be synthesised with
140
a sufficiently low MW the relative tack can be made close to unity. However, in this case
tack would be low due to the poor cohesive strength, but addition of carbon black to
such a polymer would be expected to increase tack. Therefore it may be concluded that
the effect of carbon black addition on tack depends more on the rubbers ability to
achieve bond formation than its chemical nature. The bond strength between two different
rubbers like NR and BR is found to depend on the strength of the weaker substrate [8],
as the two rubbers have similar cure rate, and types of curing system. The reinforcement
of the weaker substrate, BR, by carbon black or silica improves NR/BR bonding.
5.1.4 Effects of Plasticisers/Process Oils
The autohesion of rubber compounds is found to marginally decrease with increasing

amounts of plasticiser/processing oils such as aromatic, naphthenic or paraffinic [5].
Since plasticiser/processing oil improves the chain mobility of the rubbers this behaviour
shows that interdiffusion alone cannot explain all the factors associated with tack or
autohesion. But if the modulus is maintained at a constant by the addition of carbon
black, oil essentially has no effect on adhesion [9].
5.1.5 Effects of Tackifiers
The bonding of rubbers can be improved by addition of different tackifying resins like
phenol-formaldehyde, coumarone-indene, wood rosin and maleated liquid BR. Tackifiers
generally have MW in the range 500 2,000 with broad MW distributions. The amount
of tackifying resins that are added to rubbers varies widely depending upon the end use.
When formulating a pressure sensitive adhesive, large amounts of tackifier, as high as
50 100 phr, can be added to an rubber of relatively high MW since the adhesive does
not need a very high cohesive strength. When preparing a tyre stock much lower amounts
of tackifier, in the 1 10 phr range can be tolerated. The resin concentration is always
found to be higher on the surface of the compound compared to the bulk due to the
solubility/insolubility of the resin in the rubber at mixing and ambient temperatures.
Hence the presence of the resin can assist tack formation even when its total concentration
is low. Tackifying resins such as maleated liquid BR have an edge over conventionally
used resins, as they can undergo vulcanisation under identical conditions and using the
same chemical curatives common to the rubber industry, and they are compatible with
most rubbers [10]. The tackifying resin can also prevent tack degradation during ageing.
The initial adhesion is not changed significantly by adding up to 5 phr phenolic resin.
However after ageing at 80% relative humidity, retention of tack was improved when
the tackifier had been added. The phenolic resin acts as an antioxidant to prevent surface
crosslinking, as oxidation of rubber compounds can lead either to crosslinking or chain
141
scission depending on the rubber type and compounding ingredients. The solubility of a
resin in rubber is also an important factor in deciding the properties of the resulting
compound. If the resin is insoluble it can act only as filler, and its effect on the compound
depends upon how finely it is dispersed.
5.1.6 Effects of Other Ingredients
The direct bonding between nitrile rubber (NBR) and fluorocarbon rubber (FKM) during
vulcanisation can be improved by addition of calcium hydroxide to the NBR compound,
increasing the dosage of vulcanisation accelerator (organic phosphonium salt) in the
FKM compound, and introducing a diethyl amino group as a functional group in NBR
[11]. This makes it possible to obtain a low cost fuel hose having a thin inner tube made
of FKM and an outer tube of conventional NBR. The inner tube made of FKM provides
excellent resistance to fuels like oxidised gasoline (sour gasoline) and to alcohol-containing
gasoline (gasohol).
5.1.7 Effects of Surface Modification
The adhesion of non-polar materials such as NR based thermoplastic rubbers (NRTPE)

and EPDM/PP (polypropylene) based thermoplastic rubbers (EPTPE) to polar substrates
is normally difficult and the strength of the resulting bond is rather weak unless a suitable
primer is used. The surface halogenation of NRTPEs such as NR/PP blends is found to
improve their ability to bond to acrylic and other substrates. Halogenation improves the
surface energy and surface roughness of the thermoplastic rubber which facilitates its
bonding to substrates such as acrylic without a primer [12]. Figure 5.2 shows the variation
in the surface roughness of an NRTPE with chlorination.
Indeed, all NRTPEs whose surfaces are either chlorinated or brominated have up to a
ten times increase in bond strength. In contrast, EPTPEs such as EPDM/PP blends show
no improvement in bond strength, since such materials do not have the necessary residual
unsaturation to permit chemical addition of chlorine or bromine. The bond strength of
EPTPEs can however be improved by gaseous fluorination of the surface.
Some efforts have also been made to improve the tack of synthetic rubbers by other surface
treatments such as ozone exposure [13] and irradiation of stocks containing photosensitisers
and phenolic resins [14]. If the surface treatment can result in the reduction in MW of the
surface molecules, it can contribute to the increased mobility of these molecules resulting
in improved tack. However, this layer should remain as a thin boundary layer, otherwise it
can result in reduced cohesive strength. Another way of improving the strength of tack
142
a) NRTPE untreated control
b) NRTPE after chlorination
Figures 5.2a and 5.2b Scanning electron micrographs of NRTPE surface at a

magnification of x 206
Reproduced with permission from M. D. Ellul and D. R. Hazelton, Rubber Chemistry
and Technology, 1994, 67, 4, 582, Figures 12a and 12c. 1994, Rubber Division,
American Chemical Society, Inc
143
bond by irradiation is by grafting phenolic resin onto the rubber chain, and subsequent
interaction of these polar moieties across the interface. Yet another method of improving
the tack is by applying a thin layer of a very tacky compound over the non-tacky compound.
5.1.8 Effects of Surface Roughness
Another important factor, which determines the bond strength, is the surface roughness
of the substrates. Even though surface roughness can increase the contact area, good
contact between the substrates can be attained only by squashing the surface asperities
(unevenness or protrusions). Elastic strain energy tends to force the rough surfaces apart,
but there can be an improvement in bonding due to the enhanced surface area. When an
uncrosslinked layer of SBR compound is crosslinked in contact with a fully crosslinked
SBR layer a higher bond strength is obtained when the fully crosslinked sheet has a
rough surface, thus creating an increased bonded area [15]. In this case since one of the
substrates is uncrosslinked it could easily flow into the surface pores. However when a
lightly crosslinked layer of SBR compound was cured in contact with a fully crosslinked
SBR sheet having a rough surface it spontaneously debonded, whereas that bonded to a
sheet having a smooth surface had appreciable autohesion.
5.1.9 Influence of Contact Time/Pressure/Temperature
Three variables not related to the rubbers or their additives that may affect tack/autohesion
are the conditions of bond formation, namely contact time, contact pressure and contact
temperature. Of these three variables, the first two, contact time and pressure, are
interdependent. On increasing the contact pressure or time, enlargement of the effective
contact surface occurs by the flow process and an increase in the adhesive strength results.
Effective contact area is considered to be the sum of the domains of the contacting surfaces
in which the adhesive force operates. Optimum contact is reached when the contact
pressure exceeds the saturation pressure of the particular system. Saturation pressure is
defined as the pressure above which, at constant time, no further increase in pressure
produces an increase in the adhesive force. If the surface roughness of the samples is
smoothed out by suitable preparation, the optimum contact on the corresponding pressure
can be reached in a very short time. After a certain contact time, the contact zone
disappears and a homogeneous system is obtained. The autohesive strength is then equal
to the green strength of the uncrosslinked rubber.
In general, tack increases and reaches a plateau after sufficient contact time or pressure.
When the plateau is reached, complete contact and interdiffusion have occurred, and
tack is identical to green strength. Even for very short contact times the tack of NR is
144
sufficiently high whereas SBR with a similar MW to the NR takes a much longer time to
attain good bonding. This shows that NR is able to make contact and/or interdiffuse
more rapidly than SBR.
For SBR, the strength of autohesion continues to increase even as the time of contact is
increased to as high as a thousand seconds, even though the increase in strength is more
rapid in the early stages [16]. Almost similar behaviour was observed in the case of BR,
EPR and epoxidised natural rubber (ENR). Interfacial failure occurred when ENR adhered
to itself at short contact times. But the peel energy was found to be directly proportional to
the duration of contact up to a contact time of about an hour when cohesive failure occurred.
In contrast a contact time of less than a minute was sufficient for two NR test pieces to fail
cohesively. When NR and ENR-50 (NR with 50% epoxidation) are bonded together the
upper limit of adhesion was found to be the strength of the weak adherend (NR) [17].
In the case of NR, when contacting was carried out at room temperature, with subsequent
bond strength measurement at another temperature, tack decreased with increase in test
temperature. This is probably due to the decrease in green strength at elevated
temperatures. However, when the samples are pressed together at elevated temperature
before testing the bond at room temperature, tack increased with increase in the bonding
temperature due to the improvement in bond formation probably resulting from the
increase in the rate of interdiffusion with increase in temperature.
The combined effect of increasing the contacting as well as testing temperature will be
the net effect of the increase in tack due to better bond formation and the decrease in
tack due to lower green strength. Since the relative tack of NR is close to one at room
temperature, use of an elevated contacting temperature may not improve the tack
significantly, and hence it is likely that tack will decrease at elevated temperature due to
a lower cohesive strength. The temperature dependence of the tack of SBR is quite different.
Since the extent of bond formation is quite poor in this case, having a low relative tack at
room temperature, the improvement in bond formation at an elevated temperature can
compensate for the corresponding loss of green strength, resulting in a tack which remains
more or less the same with increase in temperature. The strength of autohesion of SBR,
where both the contact and detachment were made at the same temperature, were almost
identical at 3 C and 25 C [16].
5.1.10 Effects of Blooming
In the bonding of unvulcanised rubbers blooming of ingredients such as sulphur and

antioxidants is a serious problem. It is found that some of the bloomed materials melt at
about 90 C while others remain as large flakes (see Figure 5.3) [18].
145
Figure 5.3 Surface bloom of sulphur cured natural rubber

(Reprinted from A. D. Roberts, Wear, 1997, 42, 119, Figure 7, with permission
from Elsevier Science)
While the former creates little problem during the bonding of unvulcanised pieces via
crosslinking, the latter leads to severe loss of bonding strength. Sulphur blooming may be
prevented by the use of insoluble sulphur, and controlling the mixing temperature as insoluble
sulphur gets converted to the soluble form at about 90 C. In conventional retreading
compounds, the amount of soluble sulphur used is below its solubility limit (the balance
being insoluble sulphur) to control the sulphur blooming during storage. Ingredients like
wax are usually not added to such compounds, to avoid their blooming, even though they
can give protection against ozone and UV degradation. In some applications such as tyre
building, a solvent wiping is given over the partially built assembly before fixing the next
component. A fast evaporating solvent like naphtha is commonly used for this purpose. The
solvent partially dissolves the substrates and plasticises the surfaces. This gives rise to
considerable increase in the free surface due to the change in the surface texture and the
mobility of the polymer chains in the interface in addition to removing any bloomed ingredient.
5.1.11 Effects of Ageing
Uncured rubber compounds, aged in the laboratory or external atmosphere, exposed to

ozone or UV radiation including sunlight, suffer a reduction in their subsequent cured
146
interfacial adhesion [19]. This reduction in bond strength is dependent upon the rubber
used. It has been shown that exposure of uncured rubber surfaces causes an appreciable
reduction in the subsequent vulcanised adhesion properties. In the case of UV irradiation,
compounds containing higher proportions of NR are the most susceptible to adhesion
failure. Compounds based on other rubbers such as BR, CR, NBR, synthetic polyisoprene,
hypalon, etc., also show poor resistance to UV radiation, judged from their respective
cured interfacial adhesion strengths. It appears that when the rubber compound is exposed
to ozone or sunlight/UV radiation, the reduction in tack is due to the formation of an
insoluble surface skin. The reduction in tack is found to be greater for rubbers having
higher unsaturation. The deteriorating effect is found to be increased for compounds
containing carbon black of higher particle size. A 5% HAF black dispersion in naphtha
applied at the interface promoted good bonding in an NR based compound exposed to
higher dosage of UV radiation or ozone due to improved resistance to these degradants.
Solvent scrubbing can restore the interfacial adhesion to some extent. The addition of fast
blooming waxes is also claimed to give some protection against UV radiation and ozone
exposure, by blooming to the surface and forming a protective layer over the surface.
The effect of ageing time and environment on the tack of rubber compounds is of great
practical importance. Tyre retreading compounds must maintain good tack several
days after being processed. Reduction in tack was found to be less for butyl rubber
compounds than SBR or NBR. A rubber with a higher degree of unsaturation undergoes
more surface crosslinking and this prevents the good contact and interdiffusion required
to maintain tack.
The effect of humidity on tack depends upon the hygroscopic nature of the rubber, and
the compounding ingredients used in a specific stock. Unlike oxygen that reacts chemically
with rubber, moisture is physically adsorbed on the surface. The autohesion of SBR
compounds decreases more rapidly on high humidity ageing compared to that of NR,
due to the more hygroscopic nature of the former. When the amount of water absorbed
is high it will form a barrier to bond formation, even though minor amounts of water
absorbed on the surface will have practically no effect on bond formation.
5.1.12 Testing of Tack/Autohesion Levels
Two types of test geometry have been commonly used for testing tack/autohesion [20]:
1) a butt joint in which the test surfaces are contacted and then pulled apart in tension,
2) a peeling joint in which joined samples are stripped apart by peeling, usually at an
angle of 90 or 180.
147
The 180 peel test at a constant strain rate is the most commonly used test method for
determining the bond strength, since it gives a direct measure of the energy per unit area
required to separate the surfaces. Further, whereas the tensile test gives only a single estimate
of the bond strength, peel test yields a trace, which shows how the force varies along the
whole distance peeled. In either case, before testing, two test specimens are brought together
under a light pressure (few kPa) for a short time (usually a few seconds or minutes).
It is well known that the green (cohesive) strength of an rubber increases with testing
rate. Even though little data is available on the effect of testing rate on tack/autohesion,
tack is found to increase with test rate, as expected due to the close relationship between
tack and green strength. However, this statement should be very cautiously applied,
because for many rubbers there is a certain rate of testing above which tack decreases
very sharply. This sudden drop in tack as test rate is increased is much larger for NR
than many other rubbers. It is interesting to compare the tack of NR and that of SBR as
a function of test rates. At low peel rates, NR has substantially higher tack than SBR.
However, as the rate is increased the difference narrows and at still higher test speed,
tack of NR declines abruptly and hence the tack of SBR exceeds that of NR [21]. This
shows that the conditions of bond separation can markedly alter the comparison between
the tack of different rubbers. The abrupt decrease in tack at high peel rates is attributed
to a change in the viscoelastic response of the rubbers from viscous flow to more elastic
behaviour. The effect of variation of peel rate and test temperature on the peel fracture
energy of plasticised poly(vinyl chloride) (PVC) which is rubbery in nature and
hydrogenated NBR has been reported [22]. As the peel rate is reduced from 50 to 0.5 mm/
min, there is a substantial decrease in peel fracture energy. A similar decrease is also
reported when the test temperature is increased from 25 C to 100 C.
5.1.13 Adhesion Theories
The most widely used and successful theory which explains tack or autohesion is the
diffusion theory of adhesion of Voyutskii [23]. He suggested that if two rubber surfaces
were in sufficiently close contact, part of the long chain molecules on the surface would
diffuse across the interface. The surface molecules will interpenetrate and eventually the
interface will disappear and the two parts will have become one. For such an interdiffusion
to take place, the molecules must be relatively mobile, which further requires that the
rubbers must be above their glass transition temperature and that there should not be
any appreciable degree of crosslinking in either of them. There is some experimental
evidence that such diffusion takes place across the interface during a relatively short time
of contact [24]. However, the diffusion theory does not explain the variation of autohesion
with the temperature of measurement, or the increase in autohesion with increase in
contact pressure.
148
The thermodynamic requirement of the interdiffusion is the compatibility or miscibility

of the contacting rubbers, which is a measure of the ability of the two substances to mix.
The condition for compatibility is that the Gibbs free energy for mixing is negative. The
Gibbs free energy of mixing (Gm) is related to the enthalpy (heat) of mixing (Hm) and the
entropy of mixing (Sm) by the equation
Gm = Hm - T Sm
Where T is the absolute temperature. As mixing always increases disorder, Sm is positive,

so the TSm term is always negative and therefore favours mixing. Hence it is the enthalpy
of mixing term, which actually decides whether mixing might occur. The most favourable
situation is for the enthalpy of mixing to be large and negative or for a large amount of
heat to be evolved on mixing. In molecular terms this means that there should be specific
stabilising interactions between the components, such as hydrogen bonding and dipole-
dipole interactions. While such interactions can be advantageously used in fairly low
molecular weight rubbers, their applicability is limited in commercial rubbers since such
specific interactions lead to increased viscosity.
Another group of miscible blends involves polymers of great similarity. The cause for
miscibility in this case is the similarity in the physical parameters of the components. An
example is NR and 1, 2 polybutadiene (1,2 BR) which are miscible even at higher molecular
weights [25]. As a result when NR is brought into contact with 1,2 BR, they interdiffuse
spontaneously.
In the case of regular rubbers (those in which component 1 and component 2 do not
form specific interactions) the enthalpy of mixing can be written as
Hm = V 1 2 (1 - 2)2
where V is the molar volume, 1 and 2 the volume fractions and 1 and 2 the solubility
parameters. This equation shows the significance of the solubility parameter: the closer
the solubility values for the substrates are, the more likely they are to be compatible.
Compositions of copolymer rubbers, e.g., EPR and SBR, can usually be adjusted to match
the solubility parameters.
How fast the process of interdiffusion takes place may be measured from the diffusion
coefficients (D) of rubbers measured as a function of their MW. For typical industrial
polymers with a MW of 200 300 x 103, D is 10 13 cm2/s. With this value of D it is
estimated that within one second after contact is achieved an rubber chain would
interdiffuse about 45 - enough for substantial interpenetration.
The mechanical theory of adhesion predicts mechanical interlocking as the driving force
for all adhesion, and is especially useful for materials with rough surfaces, and/or porous
149
materials. While mechanical interlocking cannot explain all adhesion there are instances
where such interlocking does play a major role, such as adhesion between textile cords
and rubber casing in automobile tyres where the only significant factor contributing to
adhesion is the penetration of the fibre ends into the rubber [26, 27]. The bond strength
between rubber and cord depends solely on the number of fibre ends involved, and the
depth to which they are embedded. In the case of tack or autohesion, the significant role
of mechanical interlocking is evidenced by the increase in tack with the roughness of the
rubber surface, even though other factors such as removal of a thin surface layer, and
improved interfacial contacts, are also involved in this case. For example, in precured
retreading, proper bonding between the casing and the precured tread is established only
when both the surfaces are roughened by buffing.
Rubber surfaces experience varying degrees of adhesion when brought into contact. The
physical forces of adhesion are generally thought to arise from two main sources: one
electrostatic and the other van der Waals type short range attraction. The adsorption theory
attributes bond strength to the formation of intermolecular forces of attraction or van der
Waals forces between the surface molecules. According to this theory tack or autohesion is
purely a surface phenomenon and there is a direct correlation between the energy of
adsorption and the autohesive bond strength and as polarity increases there should be a
proportional increase in the bond strength. However, in practice, such a correlation does
not exist [28] and highly polar rubbers tend to have less autohesion [29].
No two surfaces are absolutely identical and there will be some contact electrification.
The electrostatic theory considers the two surfaces to be bonded as the two plates of an
electrostatic condenser, and is due to Deryaguin [30]. According to this theory adhesion
occurs due to the electrostatic forces formed by interaction between the substrates. This
theory explains the pressure dependence of tack/autohesion very well but it does not
explain why raw and compounded rubbers lose most tack/autohesion as they are cured
and brought into molecular contact under pressure. Further this theory is also not
successful in explaining the time and temperature dependence of the tack/autohesion. By
using potential contrast scanning electron microscopy the existence of an electric double
layer at the polymer interface has been demonstrated [31].
5.2 Bonding of Vulcanised Rubbers to Unvulcanised Rubbers
In the conventional retreading process an unvulcanised tread compound is extruded as

a thick strip and a thin layer of a calendered cushion compound is bonded to this strip
by passing between a pair of rollers. Then the compound strip with cushion is fixed on
to the buffed casing of a tyre, after applying a solution of the cushion compound in
naphtha, and vulcanised in a tyre mould. Since the assembly has to be kept in the
150
mould for a long time, some deterioration in the quality of the rubber/reinforcement is
inevitable and hence precured retreading is becoming more popular these days. Further,
the actual retreading process in the case of the conventional retreading may take place
only after a few days of preparing the tread compound and hence the compounding
ingredients have to be properly selected. Chances of blooming are high if any ingredient
is added above its solubility limit at room temperature. Here the bonding between the
vulcanised casing and the unvulcanised tread takes place in the tyre mould. Roughening
the casing surface or wiping the surfaces by solvent naphtha improves bonding. A
typical formulation for the tread compound and the cushion compound are given in
Table 5.1a and Table 5.1b.
Table 5.1a Formulation for the tread compound

Ingredients Parts by weight
NR 60
BR 40
Zinc oxide 4.5
Stearic acid 2.0
HAF (N 330) 30
ISAF (N 220) 25
Aromatic oil 12.5
MOR 1.0
Accinox ZC 1.0
Vulkanox HS 0.5
Soluble sulphur 1.0
Insoluble sulphur 1.25
Accitard RE 0.15
HAF = High abrasion furnace
ISAF = Intermediate super abrasion furnace
MOR = 2-(4-morpholinyl mercapto)-benzthiazole
Accinox ZC = N-(1,3 Dimethyl butyl)-N-phenyl-p-phenylenediamine
Vulkanox HS = Polymerised 1,2 dihydro-2,2,4-trimethylquinoline
Accitard RE = N-cyclohexyl thiophthalimide
151
Table 5.1b Formulation for the cushion compound

Ingredients Parts by weight
NR 100
Pepton 44 0.2
Zinc oxide 6.0
Stearic acid 1.0
GPF (N 660) 40
Pine tar 4.0
CI resin 1.25
Aromatic oil 4.0
Wood rosin 1.5
Vulkanox HS 1.0
MOR 0.95
Pepton 44: Activated di(o-benzamidophenyl) disulphide
CI resin: Coumarone-indene resin
GPF: General purpose furnace
5.3 Bonding of Vulcanised Rubbers
The bonding of vulcanised rubber to vulcanised rubber is important in the fabrication of

large structures such as hovercraft loop and finger assemblies (skirt components) and
inflatable objects. It is also important in the precured retreading process, where a
vulcanised tread is bonded to the buffed casing of a tyre. The bond must possess adequate
strength, and must be capable of withstanding harsh environmental conditions such as
extended periods of water immersion, severe tyre running conditions, etc.
5.3.1 Strip Bonding of Tyre Retreading Components
The most common method of bonding vulcanised rubber components is by applying a

rubber compound strip in between them after applying a rubber compound solution to
the vulcanised surfaces. The compound solution and the strip compound usually contain
a high dosage of tackifying resins for improving the bonding. NR and polychloroprene
152
rubber are commonly used for preparing both the strip and the solution due to their high
degree of inherent tack. In certain cases, especially for bonding thin pieces, the rubber
strip may be avoided and the bond may be developed solely from the rubber solution. A
two component NR-based adhesive solution, one containing sulphur and the other
containing accelerator, may be used as 10% solution in toluene or solvent naphtha. They
are mixed in equal proportions immediately before use. Table 5.2 shows a typical
formulation of a NR-based adhesive solution.
Neoprene-based adhesive is also found to be effective in bonding vulcanised pieces and a

typical formulation is given in Table 5.3. It is used as a 15 20% solution in toluene.
Table 5.2 Two component NR-based solutions for bonding thin vulcanised
rubber pieces
Components Parts by weight
NR 10 0 100
Zinc oxide 5.0 5.0
Stearic acid 0.5 0.5
Vulkanox HS 1.0 1.0
Wood rosin 2.0 2.0
CI resin 2.0 2.0
Sulphur 5.0
Zinc isopropyl xanthate 5.0
Table 5.3 Neoprene-based adhesive solution for bonding thin vulcanised

rubber pieces
Neoprene AC 100
Light magnesium oxide 4.0
Zinc oxide 5.0
Vulkanox HS 2.0
Phenol formaldehyde resin 30.0
AC: adhesive grade
153
In this case the solution can induce bonding even without an accelerator and thus has
only a moderate shelf life. However by using a very low concentration of zinc oxide and
magnesium oxide, the shelf life can be enhanced. A few drops of water also improve the
shelf life. Grades of CR that have a high crystalline rate have been developed for adhesion
applications requiring quick and strong bonding. Mixing with an appropriate amount
of polyisocyanate, such as Desmodur R, prior to application can increase the bonding of
neoprene adhesive. Before applying the rubber solution the surfaces of the vulcanised
sheets are roughened, then the adhesive solution is applied over the surfaces and allowed
to dry until tacky and finally the sheets are held together under light pressure to expel
entrapped air and for bonding. In precured retreading, as the thickness of the components
to be held together are high, the strip bonding process is used. In this process the bonding
is provided by vulcanising a rubber strip compound kept in between the tread and casing.
A typical formulation of the strip compound is given in Table 5.4.
The accelerator dosage can be adjusted according to the temperature and time given
for retreading.
Table 5.4 Formulation of a NR-based bonding strip compound for bonding

vulcanised rubber pieces
NR 100
Pepton 44 0.2
Zinc oxide 5.0
Stearic acid 1.5
GPF (N 660) 40.0
Pine tar 4.0
Wood rosin 2.0
Aromatic oil 3.0
MOR 0.8
TMTM 0.7
Vulkanox HS 1.0
Accitard RE 0.15
TMTM: Tetramethyl thiuram monosulphide
154
In strip bonding the properties of the compound strip are significant for attaining good
bond strength. The cure rate of the strip compound also plays an important role as the
vulcanisation of the adhesive strip takes place by the heat conducted through the
adherends, which are already vulcanised. The strip compound should not contain any
ingredient which may bloom to the surface during storage.
5.3.2 Effects of Strip Thickness

The thickness of the rubber compound strip has a profound effect on the vulcanised
rubber vulcanised rubber bonding. In the case of NR/NR and NR-BR/NR-BR blends
bonding the peel strength increases with the increase in the thickness of the strip, reaches
a maximum and thereafter decreases [32] (see Figure 5.4) when the bonding time and
bonding temperature are kept constant. This shows that there is an optimum thickness
of the compound strip below which it cannot keep the two thick substrates intact.
Figure 5.4 Variation of the peel strenth with the thickness of adhesive strip at 140 C
for NR/NR () and NR-BR/NR-BR blend (o) test pieces
(Reproduced with permission from L. Job and R. Joseph, Journal of Adhesion Science
and Technology, 1995, 9, 11, 1427, Figure 1, p.1431. 1995 VSP BV)
155
However, at higher thickness the strip remains under-cured as the time of bonding is
kept constant resulting in a reduction in bond strength.
The adhesive strip can also be made from thermoplastic rubbers. The effect of adhesive
strip thickness was found to be quite different for two thermoplastic rubber strips used
for bonding Mylar film to a flat rubber layer from that of the rubber strip. In the case of
a stiff material like Kraton 1101, the peel strength was found to be virtually independent
of thickness over a range of 0.1 to 6.0 mm. For a softer, extensible material like Kraton
3202, the peel strength depended strongly upon the thickness, increasing by a factor of
about 20 over the range of thickness studied [33]. This behaviour is attributed to the
rheological behaviour of the adhesive strips. In the case of Kraton 1101, the effective
thickness of the adhesive layer remains the same even when its actual thickness is varied,
because only the surface layer gets deformed plastically on peeling.
5.3.3 Effects of Surface Roughness
The roughness of the substrates is also a significant factor in the bonding of vulcanised
rubbers. In the bonding of vulcanised SBR to SBR using polyurethane adhesives, a mechanical
roughening of the rubber surfaces using sandpaper was found to improve bonding. It is
well known that the roughening creates heterogenities on the surface, which will favour its
interaction with the adhesive and will eliminate some mould release products present on
the rubber surface. Also surface roughening improves mechanical interlocking.
5.3.4 Effects of Temperature on Bonding
Another important variable, which determines the bond strength, is the temperature of
bonding. NR based sheets had maximum peel strength at a bonding temperature of
130 C whereas NR-BR blend based sheets had a maximum peel strength at a bonding
temperature of 140 C (see Figure 5.5) [32].
5.3.5 Effects of the Chemical Nature of Polymers/Polymeric Additives/

Surface Roughness
Material properties such as the chemical nature of the polymers, their polarity, and
MW, are also important in determining the bond strength. A non-polar rubber like a
polybutadiene has poor adhesion to plasticised PVC, whereas introduction of a polar
group like a nitrile group into BR (as in NBR) enhances the joint strength. This may be
attributed to the strong dipolar interactions between the two polymers. In the case of
156
Figure 5.5 Peel strength as a function of the bonding temperature for NR/NR () and
NR-BR/NR-BR blend (o) test pieces using adhesive strip
(Reproduced with permission from L. Job and R. Joseph, Journal of Adhesion Science
and Technology, 1995, 9, 11, 1427, Figure 2, p.1432. 1995, VSP BV)
carboxylated nitrile rubber the bond strength was found to be still higher [22]. Plasticised
PVC shows higher bonding compared to rigid PVC since the former can easily deform
at low temperatures to the surface irregularities of the adherend. Samples bonded at
30 C failed at the interface irrespective of the contact time. A joint made at 100 C
failed at the interface at short contact times whereas all the samples failed cohesively
when bonded at 150 C. As the contact temperature is increased, the degree of wetting
also increases and interdiffusion is faster, leading to the formation of a strong interface
within a short contact time.
157
The addition of thermoplastics like high density polyethylene (HDPE) to NR can improve
its self-adhesion [34]. The improvement in bonding reached a maximum when the HDPE
content was 30 phr. The surface roughness also plays an important role and enhanced
the bond strength by a factor of seven when the surfaces are buffed. The temperature of
bonding was kept at 150 C and pressure of bonding 45 kg/cm2. At 30 phr HDPE the
adhesion strength was very high and instead of interfacial failure, cohesive failure occurred.
But at an increased concentration of 50 phr, interfacial failure occurred and bond strength
was found to be very low.
5.3.6 Urethane Adhesive Systems
Polyurethane and CR adhesives are widely used for bonding vulcanised rubber. Urethane
adhesives perform better in some respects compared to neoprene adhesives on greasy
leather as excessive grease and fatty acid present can affect neoprene adhesives more
adversely [35]. Vulcanised SBR can be bonded satisfactorily using neoprene adhesive if
the surface is freshly prepared. Urethane adhesives used are of three types:
1) single part - which contains no free isocyanate
2) two part - this is single part urethane to which free isocyanate is added immediately
prior to use
3) pre-reacted - this is a mixed urethane/isocyanate system (the isocyanate is not

sufficiently quick reacting to cause gelling).
Single part urethane is not efficient in the bonding of rubber. The addition of isocyanate
improves bonding as it can act as a bridge between rubber and urethane. However, it is
necessary to use polyfunctional isocyanate, as it has to react with polyurethane and rubber.
5.3.7 Surface Treatments to Improve Bonding (see also Section 1.2.4.1)
The chlorination of the rubber surface can improve bonding to urethanes [36]. It was
found that in the case of NR, chlorination produced an eight-fold increase in bonding
while for SBR it produced a four-fold increase in peel strength when two vulcanised NR
pieces or SBR pieces were bonded together using urethane adhesive. The chlorination of
rubber can be brought about by sodium hypochlorite, chlorine in carbon tetrachloride,
and hydrochloric acid in organic solvents. However the toxicity of these agents has
restricted their use and less hazardous trichloroisocyanuric acid (TIC) solution has been
found to be successful in the chlorination. Chlorination produces surface cracks which
favour mechanical interlocking of the adhesive in the pores, a surface oxidation and the
158
reaction of chlorine at the double bond of butadiene both favouring chemical adhesion.
The surface chlorination also prevents blooming of other chemicals to the surface. The
contact angle of ethylene glycol on a rubber surface was found to be lowered after
chlorination resulting in increased wettability of the rubber surface.
5.3.8 Effects of Contact Time/Surface Bloom
In the case of sulphur vulcanised NR, the contact time markedly influences the level of
adhesion. It is commonly observed that an increase in contact time improves bonding.
The surface condition of the vulcanisate has direct bearing on the contact time effect.
When sulphur vulcanised NR is boiled in isopropyl alcohol for 3.5 hours there is a
considerable reduction in the range of adhesion values with the contact time compared
with the original sample. It is observed that after three days of storage bloom can
reappear and the sample shows contact time effect. Alcohol washing restored shine.
This shows that bloom, which is continually re-established by migration of free
ingredients from the rubber interior, is an important component of surface
contamination, and isopropyl alcohol is unable to extract free compounding ingredients
from the bulk of the rubber. Acetone is found to be more effective than isopropyl
alcohol. Bloom on a rubber surface consists of a mixture of materials, antioxidants
being the major component. Heavily bloomed surfaces show no adhesion on initial
contact for about 20 seconds.
5.4. The Mechanism of Adhesion of Fully Cured Rubbers
The mechanism of adhesion of fully cured rubbers may be different from that of uncured
rubbers. The contribution from interdiffusion will be less significant. However, the
application of the compound solution and the compound strip may provide some
interdiffusion. The contribution to adhesion may arise principally from factors of
interfacial surface energy and rubber hysteresis (the percentage energy loss for cycle of
deformation). Bonding arises from several kinds of interactions that may be physical/or
chemical in nature.
References
1. W. C. Wake, Adhesion and Formulation of Adhesives, 2nd Edition, Applied

Science Publishers Ltd., Barking, Essex, UK ,1976.
2. G. R. Hamed, Rubber Chemistry and Technology, 1981, 54, 3, 577.
159
3. G. R. Hamed and C-H. Shieh, Rubber Chemistry and Technology, 1984, 57, 1, 227.
4. B. G. Crowther and R. E. Melley, Journal of the Institution of the Rubber

Industry, 1974, 8, 5, 197.
5. C. K. Rhee and J. C. Andries, Rubber Chemistry and Technology, 1981, 54, 1, 101.
6. B. A. Dogadkin, Rubber Chemistry and Technology, 1960, 33, 2, p.545.
7. A. K. Bhowmick and A. N. Gent, Rubber Chemistry and Technology, 1984, 57,

2, 216.
8. A. K. Bhowmick, P. Loha and S. N. Chakravarty, International Journal of

Adhesion and Adhesives, 1989, 9, 2, 95.
9. J. R. Beatty, Presented at the 104th ACS Rubber Division Meeting, Denver,

Colorado, Fall 1973, Paper No.14.
10. R. E. Drake and J. M. Labriola, Presented at the 139th Meeting of the ACS
Rubber Division, Toronto, Canada, Spring 1991, Paper No.48.
11. M. Sugimoto, T. Okumoto, T. Kurosaki, M. Ichikawa and K. Terashima,

presented at the International Rubber Conference (IRC 85), 1985, Kyoto, Japan,
Paper No.16B16.
12. M. D. Ellul and D. R. Hazelton, Rubber Chemistry and Technology, 1994, 67,
4, 583.
13. R. E. Tarney and J. J. Verbanc, inventors; E.I. Du Pont de Nemours and

Company, assignee; US Patent 3,657,203, 1972.
14. A. C. Soldatos, inventor; Union Carbide Corporation, assignee; US Patent,

3,616,362, 1971.
15. A. N. Gent and S. M. Lai, Rubber Chemistry and Technology, 1995, 68, 1, 13.
16. A. N. Gent and H. J. Kim, Rubber Chemistry and Technology, 1990, 63, 4, 613.
17. K. N. G. Fuller and G. J. Lake, Poster presented at the 3rd International

Conference on Adhesion, Adhesion 87, York, UK, 1987.
18. A. D. Roberts and A. B. Othman, Wear, 1977, 42, 1, 119.
19. P. J. Corish, Presented at the PRI Conference, Polymers in Extreme Environments,

Nottingham, UK, 1991, Paper No.3.
160
20. ASTM D413-98

Standard Test Methods for Rubber Property - Adhesion to Flexible Substrate, 2002.
21. G. R. Hamed and C. H. Shieh, Rubber Chemistry and Technology, 1986, 59,
5, 883.
22. N. R. Manoj and P. P. De, Journal of Elastomers and Plastics, 1994, 26, 3, 265.
23. S. S. Voyutskii and V. L. Vakula, Journal of Applied Polymer Science, 1963, 7,

2, 475.
24. J. D. Skewis, Rubber Chemistry and Technology, 1966, 39, 2, 217.
25. C. M. Roland, Rubber Chemistry and Technology, 1988, 61, 5, 866.
26. E. M. Borroff and W. C. Wake, Transactions of the Institution of the Rubber

Industry, 1949, 25, 3, 199.
27. E. M. Borroff and W. C. Wake, Transactions of the Institute of the Rubber

Industry, 1949, 25, 3, 210.
28. B. V. Deryaguin, Vestnik Akadnauk, 1963, 7, 10.
29. S. S. Voyutskii, Autohesion and Adhesion of High Polymers, Inter Science, New
York, 1963, Chapter V.
30. B. V. Deryaguin and V. P. Smilga, Minutes of Technology, Adhesion:

Fundamentals and Practice, Elsevier, Amsterdam, 1969, p.152.
31. W. Possart, International Journal of Adhesion and Adhesives, 1988, 8, 2, 77.
32. L. Job and R. Joseph, Journal of Adhesion Science and Technology, 1995, 9,
11, 1427.
33. A. N. Gent and G. R. Hamed, Rubber Chemistry and Technology, 1982, 55, 2, 483.
34. J. Kurian, S. K. De and G. B. Nando, Journal of Adhesion Science and

Technology, 1991, 5, 2, 109.
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161
162
6
RubberBrass Bonding
W. J. van Ooij
This chapter will discuss the state-of-the-art of bonding rubber compounds to brass, a
technology primarily used on steel tyre cords. The literature is reviewed since 1991 when
the previous review was published [1]. An updated mechanism for the rubber adhesion
mechanism of brass is presented. Some new developments, such as proposed alternatives
to brass, are also discussed.
6.1 Introduction
One of the oldest and most widely practised methods for bonding rubber to metals is by
coating steel with a layer of brass of nominally 70% copper. Alternatively, solid brass
can also be used as a substrate. It has been established that a strong bond is formed
between the brass surface and the rubber during the vulcanisation process of the rubber
[2-4]. This bond is very durable, and resistant to high temperature and dynamic loading.
For these reasons, this bonding process is used to promote adhesion between steel tyre
cords and rubber in radial tyres. The brass plating process is not used much in other
areas of technology where rubbermetal bonding is used, such as engine mounts,
suspension bushings, transmission and axle seals, and many others. For these areas,
discussed in different chapters in this book, the required rubber properties vary widely
and the brass plating technique has some limitations that make it unsuitable. In these
critical applications brass has been replaced with solvent-based or waterborne adhesives
which can cover a much wider range of metalrubber combinations.
The limitations of the brass plating technique are:
1. Brass only bonds by a unique, self-catalysed process (details are discussed later in this
chapter), if the rubber has a high degree of unsaturation; in practice, this limits its use
to natural rubber (NR), synthetic isoprene rubber (IR), styrene-butadiene-rubber (SBR)
and butadiene-rubber (BR).
2. A strong bond is only formed with sulphur-vulcanised compounds. Additionally these

compounds need to have a high sulphur level (4 phr) and a certain type of accelerator,
i.e., delayed-action sulphenamides. Systems containing lower sulphur levels, semi-
163
efficient vulcanisation systems (semi-EV) or EV systems and peroxide-cured systems,

all fail to bond to brass directly, i.e., without using an adhesive.
3. The brass composition and also its surface composition are important, and adhesion
is only obtained within rather narrow limits of copper percentages (roughly 65
75%) and oxide film thickness. In other words, the surface preparation of the brass
is very important.
4. An important additive to NR compounds used for bonding rubber to brass is a

cobalt salt, such as cobalt naphthenate. While this additive improves the stability of
the rubber-brass bond, especially in a corrosive environment, it exerts a negative
effect on the stability of the rubber network, in that it accelerates reversion
phenomena especially in the presence of oxygen and at elevated temperatures.
5. Since brass is not a highly corrosion-resistant metal, the rubberbrass bond is sensitive
to attack in a corrosive environment, e.g., by water, steam, high humidity, salt, and
so forth. In general, brass containing copper and zinc only, i.e., electrodeposited
brass, is prone to uniform corrosion, dezincification (in chloride and/or acid), stress
corrosion cracking (especially by ammonia and amines) and intergranular corrosion.
These effects are aggravated by the fact that brass in electrical contact with steel
forms a galvanic couple, with brass being cathodic and steel the anode. The situation
results in accelerated corrosion of the steel if the brass is porous, e.g., on tyre cords,
where corrosion can eventually result in wire breakage.
However, the advantages of the rubberbrass bonding process still outweigh these
limitations and the important properties, namely thermal stability, dynamic loading
resistance, crack growth resistance of NR and others, cannot be matched by adhesives.
Thus, the NR-brass bond is still exclusively used in tyres. It should be pointed out,
though, that the NR used in tyre belt and carcass areas is optimised for bonding
properties to the brass-plated tyre cord rather than for the thermal ageing oxidation
and crack growth resistance. If a new bonding agent could be developed that would be
less sensitive to NR compound formulations, tyre durability could be significantly
improved by reformulating the NR skim stock compound. It has taken more than
forty years before such new agents are slowly becoming available. They will briefly be
summarised in this chapter, but the emphasis will be on the properties of the rubber
brass bond and new developments in terms of brass coatings, compounding and
advances in understanding of the bonding mechanisms. Although this mechanism has
been studied and published [3, 5-11], there is still controversy over some aspects of it.
Some recent studies have shed more light on the nature of the brass-rubber interaction
and will, therefore, be discussed.
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RubberBrass Bonding
6.2 Mechanism of Rubber-Brass Bonding
6.2.1 Reviews
This topic was last reviewed by Van Ooij in 1991 [1]. Prior to that date, review articles
were published in 1979 and 1984 [3, 4]. All published papers on the mechanism of
bonding, brass requirements, compounding for optimum bonding and some patents were
reviewed. A paper describing some recent developments in rubbermetal bonding for
tyre applications was recently published by Van Ooij [12]. An updated adhesion model
was described based on the use of time-of-flight secondary ion mass spectrometry
(TOFSIMS) analysis of brass treated in squalene containing rubber chemicals. Some
details are given in the following sections. Other novelties are the use of organic plasma-
polymerised films as primers for bonding steel to rubber and, for the first time, bonding
of rubber to steel by using organofunctional silanes [12]. The rubber compounds were
peroxide-vulcanised only and silane processes for bonding to sulphur-vulcanised
compounds were announced but have not yet been shown.
6.2.2 Recent Mechanistic Studies
The mechanism of rubberbrass adhesion is described in several papers, cited earlier.

Although there still is a debate in the literature over the presence of covalent CuS bonding
across the rubberbrass interface, it is now generally accepted that during the initial
stage of the cure, a layer of interfacial sulphides are formed with predominantly non-
stoichiometric copper sulphide and smaller amounts of zinc sulphide. The copper sulphide
grows as dendrites into the liquid rubber which is still viscoelastic at that stage. When
the sulphide growth levels off, crosslinking through the delayed action sulphenamide
accelerator occurs and the result is a strong interlocking of the cured network and the
rubber compound. This mechanism is summarised in Figure 6.1 [4].
In this model, the adhesive strength and interfacial strength between the sulphide layers
are obviously of paramount importance. The type of sulphide, dendrite size, growth
rate, defect structure, etc., are dependent on the rubber formulation, such as accelerators,
sulphur/accelerator ratio, certain additives, e.g., cobalt or others, and also on the brass
parameters (surface cleanliness, oxide thickness, etc.), and thus, each compound must be
carefully optimised for bonding characteristics to a particular type of cord. Covalent
bonds between the metal and the rubber or between the copper sulphide and the
crosslinked rubber have never been demonstrated. However, it has been shown that the
only reaction occurring between copper and organic sulphides is the formation of copper
sulphides, i.e., that is the stable product [13]. Ageing of the rubber-brass bond in a
corrosive environment has been demonstrated to be the result of corrosion of the remaining
165
a)
b)
Figure 6.1 Mechanism of rubber-brass bonding after van Ooij [4]. Shown are a) the
original brass surface composition and, b) the interfacial copper sulphide dendrites
interlocked with the crosslinked rubber compound
(Reprinted with permission, from W. J. van Ooij, Rubber Chemistry and Technology, 1984, 57,
3, 426, Figure 1 and 445, Figure 11. 1984, Rubber Division, American Chemical Society, Inc.)
166
RubberBrass Bonding
brass layer under the sulphide film, primarily by dezincification. This process results in
the formation of copious amounts of zinc oxide and hydroxide and a weakening of the
interfacial strength. Thus, aged adhesion retention depends on how well the existing
sulphide film protects the underlying metal against corrosive attack and how stable the
sulphide film itself is against the attack by moisture and salt. Important variables are the
type of accelerator, the sulphur/accelerator ratio and the presence of cobalt-organic
complexes. These factors all have an effect on the type, structure, composition and
coarseness of the copper sulphide film, as is summarised in Figure 6.2.
Figure 6.2 Schematic of effects of rubber compound variations on rubberbrass

interface, and effects during ageing of the interface in conditions of high humidity
(Reprinted with permission, from W. J. van Ooij and M. E. F. Biemond, Rubber Chemistry
and Technology, 1984, 57, 4, 686. 1984, Rubber Division, American Chemical Society, Inc.)
167
Recent studies aimed at unravelling the bonding mechanism all support this summarised
model and provide some detail on aspects such as film composition or thickness. The
work summarised next was all of a fundamental nature, using either model brass samples
(polished coupons), or liquid squalene systems to simulate rubber compounds, [14] or
both. Ball [15] compared sulphide films formed on brass coupons from squalene baths
containing different cobalt adhesion promoters. The films were analysed by surface
analytical tools including secondary ion mass spectrometry (SIMS) which has a greater
sensitivity for cobalt. The model in Figure 6.1b based on dendritic copper sulphide growth
interlocked with organic polymer was confirmed. The films contained cobalt, which
increased the resistance to steam ageing, especially boroacylate salt which deposited
more cobalt in the film. The form of cobalt in the film was postulated to be cobalt-
sulphur-rubber rather than cobalt sulphide. Similar studies using transmission electron
microscopy (TEM) and secondary neutral mass spectrometry (SNMS) were performed
by Pieroth [16], who added cobalt naphthenate with and without a boric acid ester to
rubber which was contacted with sputtered brass films. A pronounced effect of the boric
acid ester on the retention of adhesion was found. Without cobalt, a strong growth of
ZnO/Zn(OH)2 occurred during steam ageing, resulting in a weakening of the interface.
This effect was effectively suppressed by the combination of the cobalt salt and the boric
acid ester, but not by the cobalt salt alone.
Different types of commercial bonding agents were compared, again in a squalene liquid
model system approach, by Hamed [17]. They investigated the rate of sulphide formation
on brass-plated tyre cords and their morphology using scanning electron microscopy
(SEM) and energy dispersive x-ray analysis (EDX). The commercial bonding agents
(including a cobalt salt) all initially formed a copper sulphide film with a high surface
area prior to the scorch of the squalene. The high-surface area sulphide was considered
favourable for penetrating into the viscoelastic rubber, thus resulting in tight interlocking
after rubber cure had occurred. The bonding agents also slowed down the growth of the
sulphide film during ageing in high humidity at 70% for 10 days. This copper sulphide
growth is normally a consequence of the dezincification (corrosion) reaction. These results,
as well as the previous ones, indicate that good adhesion promoters are primarily corrosion
inhibitors for the dezincification reaction.
Prokofev [18] studied the effects of oligomeric polysulphides on the rate of sulphidation
of copper foil in m-xylene. These oligomers contained linear polysulphide chains. It
was reported that the polysulphides themselves did not sulphidise the copper at an
appreciable rate. However, when used together with elemental sulphur, sulphidation
occurred and the sulphide was more homogeneous and finer than by sulphur alone.
These results were used to explain the more stable bonding to rubber containing
polysulphides. Apparently, linear sulphides are not reactive but they insert sulphide
and then become active for sulphidation.
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RubberBrass Bonding
Chandra [19] evaluated the effect of an adhesion promoter by investigating the failed
interfaces between NR skim stocks and tyre cords to determine the effect of a cobalt
adhesion promoter on the mode of failure. The main conclusions were that the model by
Van Ooij was confirmed. The cobalt strengthened and stabilised the interface, but had a
negative effect on the compound properties in the interface region, as expected. As a
result, the failure mode became more cohesive.
The following research deals with a detailed description of the sulphide film and the
dependence between the sulphide make-up and compound formulation. Potapov [20]
reported detailed analyses of the sulphide film and interfacial zones, their degree of
crosslinking and oxidation, by spectral and analytical procedures on thin sections. Many
parameters were measured, including the cohesive strength of the various copper sulphide
films. Oxidation of the compounds was explained on the basis of a catalytic effect exerted
by copper or cobalt in the compound. The overall conclusion of this work was that a
high degree of non-stoichiometry of the CuxS film results in better adhesion to the metal
because of a better match of the lattice parameters. Further, this degree of non-
stoichiometry is attained at a specific Cu+/S8 ratio which is specific for each accelerator
(three accelerators were compared). Cobalt strengthens the film mechanically and forms
cobalt sulphide. Optimised compound formulations were reported which gave the highest
mechanical strength of the sulphide film and the interfacial region.
Researchers from Graz, Austria [21-26], developed procedures for determining the
thickness, structure and composition of the interface formed between thin brass foils
reacted with simple rubber compounds. Analytical TEM, EDX, wavelength dispersive x-ray
analysis (WDS), and electron energy loss spectrometry (EELS) were used combined with
cryomicrotomy. Their results uniquely identified that copper sulphide is the bonding
agent. Its thickness should be no more than 250 nm and increases with sulphur content
in the compound. Thicker films were more brittle. The locus of adhesion failure is
frequently in the interface between the copper sulphide and substrate. Of several brass
pre-treatments that were compared, an alkaline treatment optimally activated the brass
for bonding.
As an overall conclusion, these detailed studies by this group, using highly

sophisticated equipment, all confirmed the validity of the model described earlier in
this section. The important issue is that all these studies confirmed a tight interlocking
between the polymer (rubber) and the sulphide film, i.e., organic material was actually
occluded inside the film and no sharp boundary was detected. Giridhar, in a
development of a novel tyre coating that could possibly replace brass (to be discussed
later) performed a detailed study of the interaction between brass-plated and other
alloy-plated tyre cords and squalene mixtures formulated as rubber for the study of
the organic chemistry at the metal surface [27]. This technique was instrumental in
169
detecting the absorption of the cobalt complex on the metal. Other rubber
compounding ingredients that were found to be absorbed were the accelerator N, N-
dicylohexyl benzothiazole sulphenamide (DCBS) and stearic acid. The implications
of these findings for the overall mechanism are given in an update of the model of
Figures 6.1 and 6.2 (see Section 6.2.3).
6.2.3 Updated RubberBrass Adhesion Model
Taking the various recent studies into consideration and with the model of Figures 6.1
and 6.2 as a starting point we can now refine the model as follows. It is important to
refer to the recent study by Chaler [28] who revisited the mechanism of rubber
vulcanisation using the liquid model system approach [14]. These studies shed new
light on the mechanism of sulphur vulcanisation and some of the conclusions by Chaler
are used in the model, which is shown in Figure 6.3. Five stages are distinguished,
which cover the initial periods of the cure, i.e., until the compound begins to crosslink.
For the sake of simplicity, cyclohexyl benzothiazole sulphenamide (CBS) is assumed to
be the accelerator here, but other sulphenamides would react similarly, albeit at a
different rate.
Stage I:
Formation of active intermediate products from the accelerator takes place here. Because
of the electronegativity of sulphur and the tendency of nitrogen to form positive ions,
the ions shown are preferred over radicals. Further, there is strong evidence that the
double bonds in NR (or squalene) accelerate the formation of these products. An effect
of the double bonds via the formation of a charge transfer complex as shown in
Figure 6.3 is proposed. Such a complex polarises the bond because of the high electron
density of the C=C bond.
Stage I: Formation of active intermediate products from the accelerator:
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RubberBrass Bonding
Evidence for this interaction are the observations that
a) the accelerator fragments seen in the TOFSIMS spectrum of the metal surface hung
in squalene are not seen if the squalene is replaced with squalane, its saturated
counterpart [27].
b) the sulphidation rate of brass is much lower when squalane is used as a model system
for rubber than when squalene is the vehicle [4, 5, 12]. As is shown below, the
sulphidation rate is a function of the concentration of the intermediate.
c) it has recently been found that in sulphur vulcanisation of squalene, the formation
of mercaptobenzothiazole sulphenamide (MBTS) from CBS is decisive for the onset
of the crosslinking reaction [28]. Mercaptobenzothiazole (MBT) catalyses the
decomposition of CBS, with the formation of MBTS (Figure 6.3 1-c). This
compound then forms the active sulphurating species by reacting with ZnO/S8
(ring opening):
The rate-determining step in this sequence is reaction 1a, the slow scission of CBS. It was
found that in squalene, the induction period was as follows:
1. mixture of squalene, ZnO, S8, CBS: 25 min
2. as 1, but without ZnO: 35 min
3. as 1, but without squalene: 85 min
4. as 1, but without squalene and ZnO: infinite
The data indicate that the CBS decomposition is catalysed by the double bonds of squalene
thus confirming the observations in a).
171
Figure 6.3 Schematic of updated mechanism for bonding rubber to brass
172
RubberBrass Bonding
Figure 6.3 Continued
173
Stage II:
The MBT or MBTS (both form the same complex shown in stage II) is absorbed on the
metal surface where it forms complexes of the type:
Prior to this absorption, the brass surface has been activated by stearic acid which dissolves
some of the surface oxide (mainly ZnO).
Stage III: The metal-sulphur (Me-S) bonds formed in stage II are active ring openers for
S8 molecules and sulphur insertion occurs. It has been postulated that rubber-soluble
zinc plays a role in these insertion reactions by forming a chelate with the nitrogen and
sulphur atoms of the MBT [28]. The net result is the formation of surface molecules of
the type (see Figure 6.3, stage III):
ISy- is inductively ionised sulphur
If the compound contains an active cobalt-containing adhesion promoter, metallic cobalt

precipitates onto the brass surface and also forms the Me-S bond, in addition to copper.
Zinc can also form this bond, but does not bond to rubber, as the zinc sulphide growth
rate is low (see stage IV). The role of cobalt in NR skim stocks is thus to activate (or
174
RubberBrass Bonding
depassivate) the brass surface. The result is a higher growth rate and less dependence on
oxide thickness and copper content of the brass.
Stage IV:
The absorption and insertion reactions of stage III occur very early on in the vulcanisation
process as the temperature is still low (140 C). At higher temperatures, the absorbed
Me-Sy-X complexes decompose and form Me-S and Sy-1X, an active radical for NR
crosslinking, where X is an accelerator fragment. Meanwhile, copper has diffused to the
surface (it is a p-type semiconductor) and has absorbed more accelerator fragments. By
this mechanism, the brass surface is sulphidised rapidly with the formation of CuxS and
not ZnS. This mechanism, based on sulphidation by the accelerator and not by elemental
sulphur, explains, for the first time, why brass sulphidises more rapidly in squalene than
squalane, as has been observed [4, 5, 12].
Stage V: This process will continue until fresh accelerator or MBT is no longer
available. Sulphidation then stops and the viscoelastic rubber, entrapped in the CuxS
dendrites, will crosslink. This process occurs after the sulphidation reaction, as the
decomposition of the rubber-bound intermediate (accelerator fragment dangling on
a rubber molecule) to form crosslinks, is a much slower reaction. The result is a tight
interlocking of the rubber in the copper sulphide dendrites. An important aspect of
this mechanism is that the concentration of Sy and X-Sy species in the immediate
vicinity of the interface is much higher than in the bulk of the compound. Both
species are active components in the reactions that result in rubber crosslinking.
Hence, the crosslink density of the rubber adjacent to the metal surface will be
increased. This factor contributes to the high adhesion attainable to brass. Other
bonding agents (including organofunctional silanes, to be discussed later) do not
increase the compounds mechanical properties in the interface, hence their adhesion
(pull-out or pull-off force) tends to be lower.
175
In summary, in this updated model a covalent bond of the type Cu-Sx-accelerator is

formed initially but decomposes at a later stage with the formation of sulphide and a
higher modulus of the interface region. This bond is formed with the accelerator and not
with the rubber. The net result is that only inorganic sulphides are formed that become
entangled in the crosslinked rubber. This model predicts that all metals that can react
with the accelerator as in Stage II, should, in principle, bond to rubber. These metals
include the transition metals: cobalt, copper, iron, nickel and zinc. Of these metals, only
copper and cobalt are very active and indeed, form strong bonds. The other metals do
not bond in practice because the sulphide growth (see Stage IV) is slow (in the case of
iron or zinc), or the metal is passive (nickel), or the sulphide does not form the dendrites
that copper and cobalt do. It is obvious from this model that, in addition to the metal
surface conditions, the accelerator, sulphur and S8/accelerator ratio have a strong effect,
as is observed experimentally.
The following additives affect the bond formation:
Stearic acid: some stearic acid is required for the formation of zinc ions which
appear to assist the sulphur insertion reaction. It also activates the brass surface in
Stage I. If too much stearic acid is present, the brass surface is actually attacked.
Some zinc is dissolved from the brass and an excess of copper sulphide is formed.
The adhesion level will drop. A higher Zn2+ concentration will accelerate the S8
insertion (Stage III). Acceleration of the S8 insertion is good but the excess of copper
sulphide is undesirable.
Type of accelerator: the decomposition rate of the accelerator depends on its structure.
DCBS, which is often used, is less reactive than CBS shown in Figure 6.3, possibly
176
RubberBrass Bonding
because stearic effects will slow down the formation of the charge transfer complex.
The necessity to use a delayed-action sulphenamide accelerator is now obvious. In the
induction period the accelerator absorption and sulphide formation need to develop
prior to the rubber crosslinking process. Only this sequence results in a tight
interlocking of high surface-area copper sulphide dendrites and the crosslinked rubber.
The amine fragment released by the accelerator is an important factor as well, as it is
also absorbed at the metal surface [27]. There it can block the absorption of accelerator
and inhibit sulphide growth, and it can also accelerate brass or steel corrosion, for
instance if N-oxydiethylene benzothiazole sulphenamide (OBTS) is used. This
morpholinothio molecule appears to accelerate corrosion [29].
Accelerator-to-sulphur level: according to our model, if the number of MBT or

MBTS molecules that is absorbed is high, then there will be many nuclei for
sulphide formation, and hence a fine-grained film is formed. If the S 8
concentration is also high, the rate of insertion and decomposition is high, and
a dense, compact film is formed which is highly non-stoichiometric. If the
accelerator concentration is low and the sulphur/accelerator is low as well, a
coarse film with larger dendrites and higher stoichiometry is formed. Such a
film is of poorer quality, as described before.
As a conclusion to this section, it can be stated that optimal adhesion requires a careful
optimisation of rubber formulation in terms of choice of components and their levels, in
order to balance the rates of brass activation, accelerator activation, accelerator absorption
(nucleation), and sulphur insertion into the absorbed accelerator fragment.
6.2.4 New Evidence for Ageing of the Interfacial Sulphide Film
The ageing of the rubber-brass bond in a corrosive environment or under thermal ageing
conditions has been well documented. It is generally accepted that loss of adhesion is
primarily caused by corrosion of the part of the brass layer that has not been converted
to a sulphide film [1, 3, 4]. The corrosion process is dezincification, although in some
cases stress corrosion cracking cannot be excluded. Van Ooij has shown that in intact
tyres the adhesion degradation in the belt of the truck tyres is not the result of corrosive
attack, but of initiation and propagation of cracks in the rubber between the individual
tyre cord filaments [29]. These aspects are clearly caused by rubber properties (flexural
fatigue) and by the type of cord construction used. They will not be discussed further in
this chapter.
Apart from these two mechanisms, a new one has recently been proposed [13]. An investigation
was made of the rubber-brass interface in a cured tyre sample. The rubber was separated
177
from the tyre cord by cryogenic techniques [29], as described earlier. The cord, still covered
with the sulphide film, was analysed and depth profiled by TOFSIMS. An identical sample
was kept for several months at elevated temperature. The results are shown in Figure 6.4.
The TOFSIMS results show the following phenomena:
The film in the fresh samples consists of mainly of copper sulphide; the exact
composition of this sulphide cannot be determined by this technique.
The profile of the aged interface shows that the film has changed; the copper sulphide
is no longer the dominant sulphide, but more ZnS has been formed. This is not only
concluded from the profiles, but from the reconstructed spectra as well.
Cobalt is clearly detected in the film and it seems to be more associated with the ZnS
than with the CuxS component of the film. A new observation is that some cobalt is
actually detected in the metal under the sulphide film. Since ternary CuZnCo alloys
are more corrosion resistant than pure brass [1, 3, 4], this finding is an alternative
explanation for the improved stability of the interface using certain cobalt compounds;
the cobalt is reduced to metallic cobalt by the brass, and diffuses into the metal, thus
reducing its dezincification sensitivity.
Figure 6.4a Depth profiles by TOFSIMS of the interfacial film between NR and brass-
plated tyre cords in tyres; a) new tyre
178
RubberBrass Bonding
Figure 6.4b Depth profiles by TOFSIMS of the interfacial film between NR and brass-
plated tyre cords in tyres; b) after ageing for 6 months at 70 C in air
Figure 6.4c Depth profiles by TOFSIMS of the interfacial film between NR and brass-
plated tyre cords in tyres; c) reconstructed TOFSIMS spectra. The rubber was
separated from the cord by the method described by Ahn [29]
179
The carbon depth profile illustrates clearly the interlocking effect of the organic material
in the sulphide film. This has not changed much in the aged film, so the conversion
from CuxS to ZnS does not necessarily destroy the bond, at least initially.
The overall conclusion from this work is that the CuxS sulphide film on brass is inherently
unstable, as has been concluded before [4]. It is formed because it has a higher growth
rate (higher than by reacting with free sulphur) in the presence of the sulphurating agents.
However, when heated in a environment without sulphurating species, the underlying
brass reduces the copper sulphide to zinc sulphide, which is more stable than copper
sulphide. This conclusion has been reached earlier by Van Ooij based on model work
with squalene model systems [9], but it is now reported for the first time in actual tyre
cords. In the older work, the rate of overgrowth of CuxS by ZnS was observed to be
strongly dependent on the accelerator level and the sulphur/accelerator level which, in
turn, affected the coarseness of the CuxS film.
In the next section the recent literature (1990 to date) will be reviewed and discussed in
light of the updated model presented above.
6.2.5 Compounding for Brass Adhesion
Very few recent compound optimisation studies can be found in literature, as they are
normally kept proprietary. It has been published that the type of sulphur has little
effect on adhesion (pull-out) value. On the other hand, the adhesion increased with
ZnO level and with the high-structure carbon black, the former because of the brass
activation, the latter most likely because of the increased rubber modulus. Other factors
that were identified as affecting the pull-out force were the mixing method and the
cure time [30].
The effect of silica in compounds for brass adhesion was studied recently [31].
Incorporation of small amounts of precipitated silica can itself improve adhesion of
rubber to metals [32], including brass. However, a loss in adhesion after ageing in humidity
is then observed. The mechanism is not well understood. It is possible to offset this effect
by replacing part of the carbon black with silica and also by adding a cobalt complex
containing boron. If compounded to the same physical characteristics, i.e., modulus level,
the adhesion retention after salt water ageing was improved. By choosing certain low
specific surface area silicas it was also possible to improve the tear resistance and keep
the hysteresis low. It should be pointed out that the silica was treated with the silane
coupling agent bis-[triethoxysilylpropyl]tetrasulphide. In general, this sulphur silane had
a positive effect on rubber properties (through an increased bonding effect) but a somewhat
negative effect on humid and heat aged adhesion retention.
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RubberBrass Bonding
6.2.6 Additives to Compounds for Brass Adhesion
It has been demonstrated that many additives can be used to improve initial and/or aged
adhesion of rubber to brass. Most of the recent studies involve the use of cobalt salts.
Other additives that have been studied include organic resin formers, metal salts other
than cobalt, silica, organic sulphide and miscellaneous chemicals. The most widely used
and studied additive is a metal-organic cobalt salt, such as cobalt-naphthenate,
neodecanoate, stearate, boroacylate, and others. Inorganic cobalt salts consisting of cobalt
metaborate absorbed and calcined on precipitated silica have been proposed by Van
Ooij [33], but they were never commercialised. The idea behind this cobalt-borosilicate
approach was to separate the corrosion-inhibiting effect that inorganic cobalt ions have
on brass dezincification [10, 33] from the effect that metal-organic rubber-soluble cobalt
salts exert on rubber cure (acceleration), crosslink density, crosslink types, reversion,
and increased sensitivity to oxidative ageing [33].
In addition to these generally negative effects, cobalt salts are expensive and not always
readily available. Thus, it is understandable that research efforts have been aimed at
reducing the negative effect of cobalt, either by optimising the anion, or combining salts
in which the anion is optimised so that it decomposes readily during the stage of the cure
process where the interfacial sulphide layer is formed. The cobalt salt stability and rubber
stability are critical parameters, as was demonstrated in the above-mentioned experiments
with totally inorganic cobalt. If the stability (the reactivity to produce inorganic cobalt
ions), is optimised and tuned to the rubber cure and sulphide formation, the required
cobalt level can be reduced, thus alleviating the negative effects on rubber properties.
A reduced cobalt level, using optimised metal-organic cobalt salts, was also proposed by
Labarre, who introduced new adhesion promoter systems [34]. A systematic comparison
of metal-organic salts on the cord-rubber adhesion and rubber vulcanisation kinetics was
published by Chandra [35]. Both the cation (cobalt, nickel, zinc) and anion (stearate,
naphthenate, boroacylate, neodecanoate) were varied. Among the major results obtained
were those concerning the cations. Cobalt always exerted the maximum effect on the cure
and the rubber adhesion, followed by nickel and zinc. The effect of the anion was
considerably less and could be explained on the basis of the stability of the metal-organic
complex, but also, to a certain extent, their direct involvement in the cure reaction. The
same group also reported on the adhesion performance of the cobalt, nickel or zinc salts of
boroacylates [36]. Addition of hexamethylenemelamine-resorcinol-hydrated silica (HRH)
resin former systems to a standard rubber compound for brass adhesion was also considered.
It was reported that the cord pull-out force and the ageing resistance in a variety of hostile
environments was enhanced by the HRH system, the metal organic salt and, especially, the
combination of the two. The cobalt salt improved the adhesion energy more than other
salts. It was again found that the performance of the promoter was enhanced by the ease of
181
dissociation of the interfacial film. The supremacy of cobalt among all cations was confirmed,
considering its overall performance and resistance against various ageing conditions. Cobalt
was especially effective against salt and steam ageing in this study.
A low cobalt and boron-containing additive was also described by Bobrov [37], although
their materials were not specified. It was shown that the effect of a resorcinol derivative
(aminolysis of the brass coating), could be negated by the cobalt-boron additive, resulting
in a high-modulus belt compound with a high corrosion resistance of the steel cord.
The merits of combining cobalt salts and resin agents (for example hexamethylene
melamine and resorcinol-formaldehyde resin, RFR) to promote bonding and enhance
durability were investigated by Hamed [38]. Several black-filled vulcanisates were bonded
to a standard brass-plated steel cord using the tyre cord adhesion test (TCAT) pullout
geometry [38]. The highest pull-out forces, both initially and especially after ageing,
were obtained when the cobalt and the HR additives were used together. Attenuated
Total Reflection (ATR) infrared analysis showed that the RFR migrated to the brass
surface, providing a barrier to attack by moisture of the interfacial region. Moisture
uptake was, indeed, reduced for compositions containing the HR system. In addition to
this effect, sulphidation of brass in the presence of cobalt naphthenate gave a surface
topology of substantially higher surface area than without this agent. The high surface
area will promote interlocking between the rubber and growing sulphide film. These
effects were studied using a squalene model system. A new phenomenon reported in this
paper was that the RFR resin was found to be able to remove both cobalt and zinc from
the squalene mixtures by an as yet unknown action, possibly by complexing. This occurs
after the sulphide formation stage. This subsequent removal of cobalt from the rubber
phase by the resin may prevent cobalt from promoting degradation of the rubber during
ageing, as is indeed observed in compounds containing these combined bonding agents.
Hoff reported on the use of certain melamine resins that were able to function as stand-
alone or one-component systems when used in steel wire belt applications [39]. One-
component melamine resins were described that were capable of forming a network in
the rubber without the need for a co-reactant such as resorcinol. The performance of
these new resins was compared to that of some classic two-component methylene donor-
methylene acceptor systems. The new, one-component systems gave good initial and
aged adhesion, equivalent tensile and dynamic mechanical properties and superior crack
growth resistance than the currently used two component systems.
Whereas the observations described in Section 6.2.6 can easily be accommodated by the
adhesion model described earlier, this poses more problems with a series of papers
published on the effect of precipitated silica [31, 40, 41]. Partial replacement of carbon
black with precipitated fine particle size silica resulted in improved bond fatigue life of
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RubberBrass Bonding
brass-coated wire to sulphur-cured NR. The bond fatigue life of the wire bonded to
rubber was greatly improved by reducing the concentration of zinc oxide. This research,
therefore, clearly identified the relationship between silica and zinc oxide. The zinc oxide,
after initial solubilisation, leads to the formation of excess zinc sulphide or zinc oxide at
the interface. The mechanism of adhesion enhancement by silica may thus involve a
reduction of the amount of interfacial zinc oxide when soluble zinc is removed from the
system by attachment to silica surface silanol groups.
The positive effect of replacement of some carbon black by precipitated silica was further
evaluated in a compound for wire adhesion that also contained an organocobalt adhesion
promoter. Up to 20 phr of different types of silicas with widely varying surface areas was
added. It was found that the energy of adhesion, which increased linearly with the phr of
silica, did not correlate with any of the silica properties. Thus, the observed improvement
of wire adhesion was not a physical effect due to increased compound tear strength, but
was again related to changes in the interfacial layer formed on the wire [40].
Waddell did some work on the changes in the interfacial layers [41]. A wide range of
surface-analytical tools were used: Auger electron spectroscopy (AES), x-ray photoelectron
spectroscopy (XPS), SEM, EDX, and particle induced x-ray emission (PIXE), which
indicated that silica use reduced the thickness of the interfacial film, and particularly
promoted zinc oxide formation and lowered the amount of sulphide formed.
Prokofev described the use of polysulphides, oligomers and polymers containing

polysulphide fragments of the following structure in the main chain [42]:
HS-(R-S-S-)n-R-SH
with R = CH2-CH2-O-CH2-O-CH2-CH2
It has been demonstrated previously that such additions can increase the strength of
rubber-brass adhesion considerably. In this research it was established that polysulphides
are only weak crosslinking agents for unsaturated rubber by themselves. In the presence
of sulphenamide accelerators, such as OBTS, polysulphides, in amounts of 0.5 1 phr,
activate the sulphur vulcanisation. However, the reversion process (crosslink breakdown)
is not accelerated. A favourable effect on the physicomechanical properties of the
vulcanisate was also reported.
Although no mechanistic details are given, it can be assumed that the polysulphides, in
the presence of soluble zinc, result in Sx formation, similar to the reaction with MBTS
shown in Figure 6.3. These persulphurated polysulphides will then activate rubber cure
and possibly also sulphidise the brass surface effectively.
183
The final rubber additive recently used for brass adhesion is tetrachlorobenzoquinone
(TCBQ) [43]. Low loading into a cobalt-free but otherwise standard compound
increased initial adhesion and rubber coverage of the pulled wire markedly. However,
higher loading resulted in a decline of the adhesion. Also, aged adhesion was negatively
affected by the addition. It was demonstrated that the copper diffusion into the rubber
occurred as a result of the presence of TCBQ. These results indicated that a strong
activation of the brass can result in improved initial unaged adhesion, but aged adhesion
becomes poor as active cobalt metal ions catalyse oxidation and thus degradation.
These results are important as they confirm that the bonding to brass is in fact a
controlled corrosion process. TCBQ is not a corrosion inhibitor but a corrosion
accelerator for brass, especially for the copper component of it. Such additions will
not be able to replace the ubiquitous cobalt salt in the compound, as cobalt promotes
the formation of sulphides but at the same time inhibits the dezincification reaction of
the brass. This is the reason why cobalt is so effective. The search for cobalt replacement
still goes on, as the problem with this metal (oxidative ageing catalysis) has not yet
been completely solved. However, it has now been shown that the cobalt ions, after
having performed their task, can be effectively removed by the addition of certain
resin systems and/or silica, thus largely alleviating cobalts negative effects. However,
it is strongly recommended to search for rubber additives that promote the formation
of fine-grained, high-surface area copper sulphides and at the same time inhibit the
dezincification effect, while exerting no influence on rubber crosslinking. Model studies
using squalene could be useful here.
6.2.7 Developments in Metal Pre-treatments
Only very few recent papers have been published in which new development of substrate
treatments were reported. Krone reported on the optimum brass copper content and
plating weight for rubber adhesion [44] and confirmed data that were known previously.
A more detailed study was published by Goryaev [45]. Several steel cords were prepared
and their overall thickness, homogeneity and surface composition altered. The adhesion
to a standard NR compound was determined. Among the findings were that:
1. There should be no area on the cord with a low brass thickness, in other words less
than 100 nm, because these areas will affect the thickness of the ZnO layer, which
controls the brass reactivity.
2. A barrier layer of non-stoichiometric ZnO is necessary having certain zinc and oxygen
concentration limits.
3. The overall thickness of the ZnO layer must be 40 50 nm.
184
RubberBrass Bonding
4. The concentration of Cu atoms within the ZnO layer must exceed the concentration
of Zn and O atoms.
Although these requirements may seem difficult to control in an industrial environment,

they do indicate that the reactivity of the brass is a decisive factor and further, this
reactivity depends strongly on the properties of the oxide film. In this sense, this work
confirms the model proposed by Van Ooij in 1984 [4].
6.2.7.1 Organofunctional Silanes in RubberBrass Bonding
A new development in rubber-brass bonding appears to be in organofunctional silanes.

Such molecules are commonly of the type Y-CH2CH2CH2-Si(OX)3 where Y is an
organofunctional group and OX is an ethoxy or methoxy group. Such silanes are all
stable, colourless liquids. They can be hydrolysed in water or water/alcohol mixtures to
yield Y-CH2CH2CH2-Si(OH)3. The silanol groups are active to hydroxyl groups on glass,
silica and metal oxides and can form MeOSi bonds of the type:
Me-O-Si-CH2CH2CH2Y [46] (6.1)
The remaining silanol groups in the film can react with each other and form siloxane units:
Since the Me-O-Si bonds are relatively stable, and because the Si-O-Si bonds are highly
hydrophobic, the interphase polymer-silane-substrate has become highly resistant to
moisture, or in other words, to corrosive attack. The functional group X can be selected
from a wide range of available molecules, so that it interacts with functional groups in
the polymer. In this way, an extremely stable interface can be obtained that is completely
covalently bonded and resistant to water. Such silane technology has been very successful
185
and is widely used in polymer, paint, adhesives and other industries [46]. Van Ooij and
others have recently demonstrated that silanes, in addition to acting as coupling agents,
can also be used very effectively as corrosion inhibiting metal treatments [47-52]. In
their work the use of so-called bis-silanes of the following types were particularly featured:
(XO)3Si-CH2CH2-Si-(OX)3 (6.2)
(XO)3Si-CH2CH2CH2-Sx-CH2CH2CH2-Si-(OX)3 (6.3)
(XO)3Si-CH2CH2CH2-NH-CH2CH2CH2-Si-(OX)3 (6.4)
where OX= methoxy or ethoxy and Sx = tetrasulphide (average x = 3.8 [53]). It was
demonstrated that such silanes, alone or in combination with the standard single silanes,
can prevent corrosion of the metals of stainless steel, carbon steel, zinc, aluminium,
brass, aluminium alloys and magnesium alloys from various forms of corrosion, even
without paint coating. Adhesion to paint systems and adhesives was also improved.
Several silane-based metal pre-treatment systems are now commercially used successfully
in metal finishing processes where they replace chromate metal pre-treatments.
Despite this success of silanes, which are easy to use and apply, their use as metal
pre-treatments for bonding metals to rubber has been lacking. The only rubber-related
use is as a treatment of rubber-grade silica [32, 33]. This process improves the adhesion
of the silica to the rubber and therefore the mechanical rubber properties. There is
only one patent that describes the use of a silane to bond bare steel cord (in other
words not plated with brass) to sulphur-vulcanised tyre cord skim stocks, published
by Sharma in 1982 [54]. Good adhesion was reported but only if the compound
contained a certain resin. Apparently, the silane reacted more with the resin than
with the rubber compound.
Van Ooij recently published a series of papers in which it was shown that excellent
bonding could be obtained between stainless steel, carbon steel, aluminium or brass and
peroxide-cured silica-filled ethylene-propylene diene monomer (EPDM), silicone rubber,
fluorosilicone rubber and fluorocarbon rubber [55, 56]. The rubbers were transfer-
moulded and the silane treatment was a two-step treatment consisting of a brief rinse in
bis-[triethoxysilyl] ethane (BTSE) followed by a brief rinse in a vinyl silane (VS) solution.
The treatments were identical for the four metals. In addition to 100% cohesive failure
in the rubber in initial adhesion tests, very good adhesion, in other words 100% cohesive
retention of the bond was reported after ageing in synthetic fuel, boiling acid, boiling
alkali, thermal ageing, salt spray exposure and other ageing conditions [57]. This process
outperformed all commercially available products, especially in ageing performance. Since
peroxide-cured rubber is not used in tyres, the Van Ooij group reported separately on
silane processes for bonding metals to sulphur-vulcanised rubber compounds [58].
186
RubberBrass Bonding
It was demonstrated that the BTSE/VS process developed for peroxide-cured rubbers did
not work for sulphur compounds with a high or low sulphur level. The tetrasulphide
silane that is used for modifying silica did not work either. However, a powerful new
silane bonding agent was reported that can bond several metals to a wide range of
compounds [58]. The treatment consisted of applying a mixture of silanes to the surface
of steel, galvanised steel, tin, aluminium, stainless steel or brass. The compounds were
based on NR, EPDM, NBR and SBR. The vulcanisation systems used were high sulphur
with cobalt, high sulphur without cobalt, low sulphur, peroxide and also mixed peroxide/
sulphur systems. Even cured vulcanisates could be bonded to these metals. The bonds
were extremely resistant to humidity, for example, in pressure cookers at 150 C. The
silanes used were formulae 6.3 and 6.4. A mixture of formulae 6.3:6.4 = 3:1 performed
best, whereas the two individual silanes did not bond at all.
The mechanism of this phenomenal system is still under investigation, but it has been
shown that the bis-amino silanes have the capability to form a dry film upon heating,
even without hydrolysing the silane. The polysulphur silane does not dry upon heating
by itself, but does so if it is heated in a mixture with the bis-amino silane. Thus, the bis-
amino silane may form a mechanically strong film, with the polysulphur silane providing
the reactivity of the film required to bond to the rubber compound.
Overall this new process is very attractive and has several environmental advantages, if
it could replace brass on steel tyre cords. Tests with silane-treated tyre cords are in progress.
The authors proposed use of a new tyre cord without brass coating but with a zinc
coating instead, as tyre cords without brass coating are difficult to manufacture (the
brass lubricates the die in the final wire drawing process). The final zinc-plated cord is
then passed through a silane bath and dried. Quite remarkable in this system is that the
silane-based film does not impair the adhesion of brass to sulphur-cured compound. If
the adhesion of a brass plated cord is mediocre, the silane process actually improves its
performance, as shown in Table 6.1 [58].
In summary, this silane-based adhesion process is a major development due to its simplicity,
broad applicability and performance. Among the advantages are:
1. One silane system can bond a wide range of metals to sulphur-cured compounds,
including steel, which would not bond by itself, and brass which would bond by
itself. The metals used in tyre cords are, thus, no longer limited to brass on steel.
2. The process can be used on regular existing steel tyre cords and would then improve
the bonding of brass and would also bond the cut edges of cords, which are frequently
the locus of crack initiation leading to belt edge separation.
3. The ubiquitous cobalt can be eliminated from tyre cord skim stocks. In fact, the
silane systems work slightly better with compounds not containing cobalt.
187
Table 6.1 Adhesion performance of silane-treated metals to high and low

sulphur NR compounds
Initial adhesion1 (rubber coverage)
Metal Compound
N/mm
CRS I2 0
70/30 brass I 10.2 3.6 (50)
Alloy 360 brass I 0
CRS + silane4 I 11. 7 1.5 (100)
70/30 brass + silane I 11. 1 1.4 (100)
Alloy 360 brass + silane I 10.5 1.6 (90)
CRS II 3 0
CRS + silane II 10. 2 2.3 (80)
1 ASTM D429-02 Method B + metal coupons
2 High sulphur, no-cobalt tyre cord skim stock
3 Low sulphur engine mount compound
4 All silanes treatments are by 1:3 volume mixtures of bis-[trimethoxysilylpropyl]amine
and bis-[triethoxysilylpropyl]tetrasulphide
4. The bonding characteristics of the silane films are not strongly dependent on the
compound formulation, as distinct from the performance of brass. Even low sulphur
and semi-EV systems work well. Hence, with this system, the compound of the skim
stock can be optimised for mechanical, fatigue and tear resistance properties rather
than for adhesion, as is currently done. This reformulation can, therefore, lead to
improved tyre performance.
5. The silane film provides excellent corrosion protection to the steel, in addition to
adhesion performance. Thus, rusting of tyre cords during the lifetime of the tyre cord,
especially if there are cuts and punctures, will be reduced.
6. The same (or a very similar) silane process can be used for many other automotive
and non-automotive bonding applications, such as engine mounts.
Obviously, much developmental work will have to be done on this new system, such as
the evaluation of dynamic adhesion properties, cost analysis, and so on. Important factors
in favour of the new systems are their ease of application, simple bath make-up and their
188
RubberBrass Bonding
environmental compliance. Both silanes used have no toxicity problems, and they can
replace environmentally problematic processes such as brass plating and the use of solvent-
based adhesives in various automotive non-tyre applications.
6.2.8 Developments of Novel Alloys for Bonding to Rubber
There have only been a very few attempts at research aimed at developing modified
brass or alternative alloys for bonding to rubber compounds. After the failure of the
ternary alloys of the type CuZnX (X = Co or Ni) around 1980, the focus of the tyre cord
and rubber industries has been on the development of better compounds or tyre cord
constructions.
Only two developments are worth mentioning here. Giridhar developed a dual layer
coating on steel wires consisting of a ZnCo base layer (1% Co) followed by a NiZn
(30% Zn) top layer [27, 59-62]. Both alloys were deposited from simple acid sulphate
baths. The advantages of this system are:
superior adhesion to standard NR compounds is obtained,
the cobalt content of the compound can be reduced by 50-75%, but not completely
eliminated,
the aged adhesion retention is much improved over brass,
the plating baths are simple and contain no toxic chemicals, and they can be used at
high plating speed.
A drawback was that these cords were more difficult to draw than brass because the -
NiZn phase is harder than -brass. The form is a crystalline, single phase state with up
to 37% zinc present.
The mechanism of adhesion of this cord has not been studied in great detail [27]. However,
the limited work that was done indicated that the amount of the interfacial reaction
products formed was considerably less than in the case of brass, and it cannot simply be
assumed that NixSy would replace the function of CuxS. The corrosion resistance of this
cord is much higher than of brass because Zn1%Co has much better resistance than
brass or even pure zinc.
In a recent publication, the Pirelli group reported that the NiZn top layer had been
dropped from the system and a new tyre had successfully been developed with the
Zn1%Co coating only [63]. By modifying the crystal orientation of the deposit and by
developing an optimised lubricant, a cord could be obtained with equal drawing behaviour,
189
adhesion performance on par with brass but much superior aged adhesion. Actual tyres
built with this cord showed less rust. What was remarkable though, was that the fatigue
of the rubber in the cord region, in other words, inter-belt separation, was worse for the
new cord, as compared with brass. It is expected that the problem can be solved by
modifying the skim stock formulation.
For this cord, too, the adhesion mechanism has not been unravelled uniquely. It was
theorised that the cobalt in the compound (a required additive) activates the zinc surface.
More work in this field is anticipated.
A Japanese group has developed a plating alloy consisting of Ni/Cu/P deposit [64]. Good
adhesion of NR and SBR was reported. With no more than 20% Cu, cohesive rubber
failure was observed. At 50% Cu or higher, failure became largely adhesive. The adhesion
seems to depend on the formation of a thin interfacial sulphide film, as can be expected.
6.2.9 Miscellaneous
Some miscellaneous publications are summarised here. It was reported by Matyukhin

that the bond between brass-plated tyre cord and rubber can be broken electrochemically
[65]. The process results in a growth in the interfacial layer of zinc hydroxide which
dislodges the sulphide film. The method appears useful for recycling purposes, but it was
also reported to be useful for assessing the strength of the cord-rubber bond.
Mori reported on a method to increase the cord-rubber bond strength [66]. By

intermittently ageing the samples in water at a temperature of 95 C, the pull-out strengths
increased. Their data suggested that strengthening occurred in both the cord and
compound sides of the interface. Intermittent ageing gave better results than continuous
ageing. A mechanism for this effect was not given.
Panchuk proposed a new test for measuring the bond strength between the cord and the
rubber under dynamic loading, which was especially useful for large size tyres and thick
cords [67]. The method is based on the idea of pulsed cyclic loading of small test specimens.
Results can be obtained within 48 hours.
6.2.10 Summary
The main emphasis of the work on rubber-brass bonding published in the last 10 years
has been on elucidating mechanisms further. The adhesion model accepted since 1984 in
which the formation of a film of non-stoichiometric copper sulphide has been confirmed
in all studies. It has now become clearer how to obtain a thin copper sulphide film with
190
RubberBrass Bonding
a high surface area. The ageing effect occurring in the film in the absence of corrosive
attack, was found to be due to the decomposition of the copper sulphide with the formation
of zinc sulphide. This effect was predicted in 1984 and has now been confirmed. No real
alternatives for cobalt have been announced. The effect of the type of cobalt is now
better understood, but no alternatives exist. However, the negative effects of these additives
can be controlled by using certain additives.
In terms of materials, one new tyre cord coating other than brass has been proposed that
has actually made it to the tyre testing stage. This cord has shown some unexpected
deficiencies, but if they can be overcome, this cord may have a bright future in view of its
ease of manufacture and, especially, its much better corrosion resistance and environmental
advantages.
The other major development that needs to be recapped here is that of silane systems for
bonding a wide range of metals to a wide range of compound types and formulations.
This process may become a panacea for bonding in many industries, but much more
work will have to be done before the process can replace the brass-coating process for
bonding rubber steel to tyre cords.
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7
Review of Tyre Cord Adhesion
W. S. Fulton and J. C. Wilson
7.1 Introduction
Steel cord has been the main reinforcing material for tyres, hoses and conveyor belts
for many decades, indeed the first steel reinforced tyres appeared over ninety years
ago. However, it was not until the emergence of radial tyres that steel cord became a
common form of reinforcement and understandably the adhesion between brass-coated
steel cord and rubber compound became a significant factor governing the performance
and durability of car and truck tyres. Therefore, it is necessary to achieve a high level
of adhesion and sustain this level throughout the service history of the tyre.
Brass-coated steel cords are widely used for tyre reinforcement because they allow the
manufacturer to optimise many physical parameters of the tyre, such as strength,
stiffness, modulus, durability, stability and uniformity [1]. Currently in Europe, there
is great environmental pressure to reduce car emissions, particularly levels of carbon
dioxide, and so address certain commitments agreed at Kyoto in the context of the
United Nations Framework on Climate Change [2]. The innovation of the so-called
green tyre [3], with substantially lower rolling resistance, has in some way met this
need. Further developments of steel cord with higher tensile strength and higher stiffness/
weight ratio allow the construction of lighter tyres that will also contribute to the
reduction of fuel consumption.
It is well known that good adhesion between brass-coated steel cord and rubber
compound is essential for the long-term performance of tyres. However, the rubber-
metal interface is prone to deterioration, particularly under conditions of high humidity
and salt, and so reinforcement by the steel cord is reduced, with a concomitant reduction
in the life of the tyre. Consequently, various organic cobalt salts are used, alone or in
combination with resin systems, to improve and maintain good bonding at the rubber-
metal interface. At present, organic cobalt salts appear to be the most efficient adhesion
promoter and could be considered as a bench-mark by which the tyre industry assesses
rubber-metal bond strength.
197
Commercial rubbers
7.2 Accepted Mechanisms of RubberBrass Bonding
Over the last 20 years the mechanism by which brass-coated steel cord and rubber bond
has been the subject of much investigation [4, 5, 6, 7, 8, 9] and review articles [10, 11].
Despite such extensive efforts the absolute mechanism of adhesion has not yet been clarified.
As the bonding layer between rubber and brass-coated steel cord is of the order of 20-50
nm thick, specialised techniques must be adopted for analysis, and the use of these techniques
is well-documented [12, 13, 14, 15]. Accordingly, the use of surface analytical tools such
as X-ray photoelectron spectroscopy (XPS or ESCA), Auger electron spectroscopy (AES),
energy-dispersive X-rays (EDX) and secondary ion mass spectroscopy (SIMS) have helped
to elucidate chemical structure and morphology at the rubber-metal interface. Analytical
electron microscopy (AEM), coupled with electron diffraction has been used to determine
the different crystallographic forms of copper sulphide, present in the bonding layers [16].
When forming a tyre cord, copper and zinc are electro-deposited sequentially on to drawn
steel wire and treated by a thermal diffusion process to produce a brass alloy coating.
Further drawing of the wire eventually produces a steel cord filament coated with a
brass layer, approximately 0.2 m thick. The method of drawing the wire through the
forming die creates a surface texture as well as influencing the composition, distribution
and thickness of the brass layer [17]. When the metal filaments are drawn, it is possible
that organic residues from the lubricant baths are deposited on the brass surface and
these may affect the adhesion of the rubber to metal after vulcanisation. Typically, a
brass layer is composed of 63.5% copper and it has been shown [18, 19] that the adhesion
force tends to a maximum value with a copper content between 67% and 72%, but
better retention of adhesion after ageing under humid conditions is achieved at a lower
copper content. Adhesion can also be affected by differences in the concentration of zinc
and copper in the surface compared to the composition of bulk brass. If the brass coating
is insufficient then corrosion resistance is lowered and poor adhesion can occur after
ageing. This is due to delamination of the brass by dissolution of iron in exposed areas
that can eventually result in cord breakage.
When brass-coated wire is drawn during the forming process, Zn2+ ions diffuse to the
surface and are oxidised to form a ZnO layer. A thin CuO skin can form, but it is usually
present in very small amounts. The enriched ZnO layer also contains metallic copper
inclusions formed as a result of the internal oxidation mechanism of zinc (see Figure 7.1).
Wire drawing conditions may vary and these can affect the thickness and distribution of
ZnO, as well as the number of copper inclusions.
During vulcanisation, the brass surface is exposed to active sulphur-containing molecules

present in the rubber compound and a strong bond is formed between the rubber compound
and the tyre cord by the action of an interfacial, non-stoichiometric CuxS layer (x 1.8)
198
Figure 7.1 Diagram of brass-coated steel cord surface

(Reproduced with permission from W. J. Van Ooij, Rubber Chemistry and Technology,
1984, 57, 421, Figure 10. 1984, Rubber Division, American Chemical Society, Inc.)
that grows before the rubber is fully cross-linked. At an early stage of vulcanisation, Cu+
and Zn+ ions and free electrons move to the surface of the brass wire via cationic diffusion
and a CuxS layer, with some ZnS inclusions, is formed by a process called sulphidation.
ZnS is formed initially, but is overgrown by CuxS at a later stage and the rate at which the
critical thickness of CuxS is reached depends upon several factors, including copper content
of the ZnO layer and curing conditions. The different growth rates have been attributed
[19] to the much faster rate of oxide formation of a P-type semiconductor (CuxS) to that of
a N-type semiconductor (ZnS). During the first stages of sulphidation, ZnS forms slowly
and diffusion of copper ions through this layer is hindered because ions migrate by interstitial
diffusion and copper ions migrate more slowly than zinc ions because of the different ionic
radii. The CuxS thickens as copper ions diffuse into this layer via lattice defects and the
diffusion rate is relatively high because of the non-stoichiometric nature of the CuxS. The
rate of CuxS formation is sufficient to allow growth to a thickness that is essential for good
bond formation and the amount of CuxS formed depends primarily on the number of
copper inclusions in the ZnO layer. Sulphidation will cease when all the inclusions are
depleted (see Chapter 6.2.2, Figure 6.1b).
A previous mechanistic model [19] proposed a synchronisation of sulphidation and

network formation. However, this is not necessarily the case and it is now generally
accepted that it is essential to delay the cross-linking process long enough to build a CuxS
199
layer of critical thickness. The amount of CuxS present in the layer is directly related to
the degree of sulphidation. It is still not well demonstrated how the CuxS layer interacts
with the rubber and it is thought that because the CuxS layer is dendritic in form, a high
bond strength is obtained primarily by a tight, physical interlocking between this layer
and the vulcanised rubber. If chemical crosslinking of CuxS to the rubber by CuxS-Sy-NR
bonds occurs then it is very much a minor factor. Such a physical bonding mechanism
has been supported by the fact that a reduction in pressure during vulcanisation results
in a loss of adhesion at the CuxS-NR interface [5]. However, in recent studies by Persoone
[20] in which AES was combined with Maximum Likelihood Common Factor Analysis
(MLCFA), a CS component was shown to exist at the CuxS-NR interface, a fact
that was also noted previously by Van Ooij [21].
For unaged systems, adhesion between rubber and brass usually exceeds the tear strength
of the rubber [4] and therefore bond failure never occurs at the CuxS-rubber interface [6].
The initial chemical composition and surface structure of the brass influence the bonding
mechanism by virtue of limiting the amount of CuxS that is formed during vulcanisation
[22, 23]. There is an optimum thickness for the CuxS layer that imparts maximum adhesion
and if the layer becomes too thick, then it will readily detach from the brass resulting in
low bond strength. According to Van Ooij [5], one of the major prerequisites is that growth
of the CuxS layer has been completed before cross-linking begins.
7.3 Ageing of the Rubber-Brass Bond
Rubber-brass bond degradation may be due to several processes, including thermal

ageing and electrochemical corrosion. During heat ageing, degradation of the rubber
as well as deterioration of the interface may occur [24]. Copper migrates, by cationic
diffusion, through the ZnS and CuxS to thicken the existing CuxS layer [4, 5] which
eventually cracks and weakens the rubber-metal bond. When the CuxS layer stops
growing, Zn2+ ions diffuse through the entire interfacial layer to create ZnO/Zn(OH)2.
The diffusion of Zn2+ ions can be a slow process under dry conditions, but eventually,
ZnO/Zn(OH)2 will develop at the metal surface to weaken the bond. In humid
conditions, an increase of moisture and oxygen content will accelerate this process by
altering the rate of diffusion of the Zn2+ ions. According to Van Ooij [9], the rate-
determining step is the formation of Zn2+ ions at the anode which then diffuse through
to the surface layer and thus the CuxS layer is overgrown by ZnS and Zn(OH)2.
Moreover, the conductivity of the ZnO and CuxS layers plays an important role in
governing the rate of formation of Zn(OH)2 layer.
In due course, the formation of ZnO/Zn(OH)2 from the precipitation of Zn2+ destroys
the integrity of the CuxS layer and debonding occurs [25]. Such processes are generally
200
called dezincification [5] and are assumed to be the major, underlying effects that cause
bond failure (see Figure 7.2).
Brass plated steel cord that contains low levels of copper is not so sensitive to decohesion
caused by moisture. Initial adhesion may be lower because of fewer copper inclusions,
but a more coherent ZnO is formed which reduces the amount of Zn2+ ions diffusing
through the CuxS layer and so less ZnO/Zn(OH)2 is formed at the interface. Compounding
with high levels of ZnO also helps to inhibit the dezincification process by reducing the
diffusion rate of Zn2+ ions to the cord surface.
Tyre cords are liable to corrosion under wet and saline conditions by various routes,
including dezincification and electrochemical reactions [26, 27]. The major reactions,
determined by the effect on brass of a 3% NaCl solution, are the preferential diffusion of
Zn2+ ions from the bulk of the brass to the ZnO/Zn(OH)2 layer and the partial dissolution
of copper ions with some ZnO. As the concentration of ZnO increases, a surface layer of
Zn(OH)2 forms which is then slowly dissolved.
7.4 Metal Organic Cobalt Salts
There are two main advantages to be gained by the addition of cobalt adhesion
promoters. Firstly, is the effect that cobalt has upon sulphidation during the scorch
period to ameliorate CuxS growth and dramatically increase the subsequent rubber-
Figure 7.2 A schematic illustration of the interfacial structures formed after ageing of
the rubber-metal bond (see also Chapter 6.2.2, Figure 6.2)
(Reproduced with permission from W. J. Van Ooij and M. E. F. Biemond, Rubber
Chemistry and Technology, 1984, 57, 4, 686, Figure 2 Aged. 1984, Rubber
Division, American Chemical Society, Inc.)
201
metal bond strength. Secondly, is the advantage of protection and increased durability
of the bond afforded by cobalt during ageing, particularly at high temperature and
high humidity. Moreover, under humid conditions, cobalt boron complexes have been
shown to improve the levels of adhesion more than simple di-soaps [28].
During the curing process, cobalt inhibits the formation of ZnS at the cord surface by
acting as a selective diffusion barrier [29, 30] to allow the rapid formation of CuxS.
For systems containing a thin layer of cobalt, copper migrates via grain boundary
diffusion to the rubber-metal interface to react to form CuxS. However, zinc cannot
diffuse by the same mechanism because cobalt acts as a selective diffusion barrier, and
so promotes the growth of CuxS at the expense of surface ZnS.
Scanning electron microscopic studies [31] on brass cords immersed at elevated

temperatures in squalene mixtures containing a cure system and various bonding agents
have revealed the extent of sulphidation. Figure 7.3a shows the micrograph obtained
from a wire immersed in a control mixture, containing curatives but no bonding agents
and Figure 7.3b shows the micrograph obtained from a wire immersed in a mixture
containing cobalt naphthenate. It would appear that sulphidation is preferentially
nucleated along the drawing lines of the wire surface. The control reveals a small
amount of surface nodules, whereas the cobalt wire gives a more dense and irregular
nodules of CuxS. These nodules could be interpreted as the dendritic morphology
described earlier and thus it can be envisaged how unvulcanised rubber compound will
intermesh with the growing Cu xS layer, eventually being locked in place after
vulcanisation. Further analysis by EDX of the cobalt naphthenate wire system has
revealed a sulphur content approximately three times greater than that without any
cobalt, corroborating the fact that the presence of cobalt promotes sulphidation.
As well as mitigating the formation of CuxS, cobalt salts will significantly accelerate
the cure rate and the cross-link density (or state of cure) is also increased in compounds
containing high levels of sulphur [4, 5]. An example of this effect is illustrated by
comparing the cure characteristics of three compounds (see Figure 7.4); one without
cobalt (blank), one with 0.1 phr cobalt boroacylate (Manobond 680C) and one with
0.1 phr cobalt stearate (Manobond CS95) concentration based on cobalt metal content.
The effect of cobalt is evident, whereas the anion has comparatively less effect, indeed
the stearate has slightly more influence than the boroacylate and this has been interpreted
[32] as an accelerator activating effect in the presence of ZnO. Studies by Chandra
[33], revealed the effect of different anions on the cure characteristics and he was able
to rank them, with stearate showing the largest effect followed by naphthenate,
neodecanoate and boroacylate. Such an effect may be related to the ease by which
cobalt salts dissociate to form their constituent ions [10].
202
Figure 7.3a Scanning electron micrograph obtained from a brass-coated tyre cord
immersed in a squalene mixture without cobalt (magnification x300 left; x400 right)
(Reproduced with permission from G. R. Hamed and R. Paul, Rubber Chemistry
and Technology, 1997, 70, 4, 541, Figure 4. 1997, Rubber Division, American
Chemical Society, Inc.)
Figure 7.3b Scanning electron micrograph obtained from a brass-coated tyre cord
immersed in a squalene mixture with cobalt naphthenate
(magnification x300 left; x400 right)
(Reproduced with permission from G. R. Hamed and R. Paul, Rubber Chemistry
and Technology, 1997, 70, 541, Figure 7. 1997, Rubber Division, American
203
Figure 7.4 Cure characteristics of belt compounds that contain cobalt

adhesion promoters
In studies of model systems based on squalene [34], it was shown that cobalt salts undergo
a dissociation reaction to form Co2+ ions at the interface and the relative rate of formation
and amount of cobalt deposited on the surface depends on the nature of the organic
anion. It was also shown how the type of anion affects ageing properties by influencing
cure and complex stability and hence the amount of cobalt available to maintain bond
strength during ageing. Therefore by judicial choice of the anionic complex, optimum
performance was achieved.
One of the other benefits of adding cobalt salts is the improved retention of adhesion
after ageing at high humidity [35]. Cobalt salts dissociate to form cobalt ions that are
incorporated into the ZnO layer and during subsequent vulcanisation, the formation of
ZnS is suppressed and CuxS growth is stimulated. Cobalt accumulates at the interface
(see Figure 7.5) but not in the ZnO layer. Interestingly, when cobalt boroacylates are
used as adhesion promoters, significantly higher concentrations of cobalt were detected
than other cobalt salts [36]. As stated previously, decohesion is caused by the build-up of
ZnO and Zn(OH)2 during the process of dezincification and that, according to Van Ooij
[9], the formation of Zn2+ is the rate determining step. Cobalt affects dezincification by
reducing the conductivity of the ZnO layer to slow down the migration of zinc ions and
so reduce the rate of dezincification.
It has been reported [37] that a combination of cobalt and boron improve the retention
of adhesion after steam-ageing and that boric esters increase the mobility of cobalt so
that increased concentrations of cobalt were detected at the rubber-metal interface.
204
Figure 7.5 Diagrammatic representation of cobalt promoted adhesion

(Reproduced with permission from W. J. Van Ooij, Rubber Chemistry and Technology,
1984, 57, 3, 421, Figure 13 (middle diagram). 1984, Rubber Division, American
However, boron also accumulated at the interface and borates are known to act also as
corrosion inhibitors, particularly with steel and so there is a possible dual effect. It has
also been postulated that borates may act by buffering the environment at the rubber
metal interface and so help to inhibit corrosion mechanisms.
It is important to have an optimum concentration of cobalt at the interface and if the

concentration is too high, then metallic cobalt can be precipitated and this will accelerate
dezincification and thus degrade interfacial adhesion.
7.5 The Role of Resins and Silica/Resin Systems (see also Chapter 9.2.3)
Resin systems have been employed extensively for many years in applications such as the
bonding of textiles to rubber, in hoses and belts where they have been used as tackifiers,
reinforcers, curing agents and adhesion promoters. The addition of resin and/or cobalt
depends upon the application and performance requirements of the rubber article that is
to be bonded. Traditionally, resorcinol in combination with a methylene donor such as
hexamethylene tetramine (HMT; Figure 7.6) was utilised either alone or in compounds
containing cobalt salts. On heating, HMT decomposes to produce ammonia and
formaldehyde that reacts with the resorcinol to produce a stable, highly crosslinked
polymeric network.
At present, the tyre industry generally uses alternatives to resorcinol and HMT because
of health and safety concerns over their toxicity. Resorcinol has a tendency to fume
at elevated temperatures, whilst formaldehyde generated from HMT is toxic and
may cause irreversible effects. A second generation of resins includes resorcinol/
205
Figure 7.6 Structure of resorcinol and hexamethylene tetramine
formaldehyde condensation products such as Penacolite B-18S [38] or phenol/

resorcinol resins such as the Ribenol range [39]. These resins have low free resorcinol
contents but still require a methylene donor. The use of HMT was superceded in the
tyre industry by modified melamine compounds such as hexamethoxymethylmelamine
(HMMM) on silica carriers, e.g., Cyrez 964LF [40]. The latest generation of resins
includes modified resorcinol/formaldehyde resins, such as Penacolite B-20S [41],
cresol-cashew modified phenol/formaldehyde resins (Ribetak 14588A) [39] and
urethane modified novolak resins [42].
As stated previously, precipitated silica is being used to replace the carbon black
filler in so-called green tyres where it has been shown to reduce rolling resistance
[43-46], and so help to reduce fuel consumption. Since the late 1960s, silica has been
used in combination with resin systems and at that time PPG introduced a system
that consisted of HI-SIL hydrated silica, resorcinol and hexamethylene tetramine
(HRH). Initially it was used chiefly for bonding various rubbers to textiles, but such
systems have found increasing use in wire coat and belt compounds.
Much work has been done describing the benefits to tyre steel cord adhesion by using
resins and precipitated silica in conjunction with cobalt adhesion. Tate [28] compared
various adhesion promoter systems in a belt compound and concluded that at low
addition levels, a combination of cobalt salt, resorcinol, formaldehyde donor and silica
gave good physical properties and good adhesion even under the most severe ageing
conditions. Wagner [46-50] showed that the addition of silica improved rubber tear
strength, abrasion resistance, hardness, modulus and adhesion. More recently, Cochet
[51] examined the use of low specific surface area silicas in conjunction with a coupling
agent and cobalt salt and found improved retention of adhesion after heat, humidity
and salt-water ageing. Evans [52] showed that both compound tear strength and
206
adhesion increased when silica was used with a cobalt salt. It has also been shown that
the energy of adhesion values [53] increased linearly with increasing silica content [52]
which suggested a direct effect that silica had on the rubber/wire interfacial layer.
Adhesion data for two methylene/formaldehyde donors, HMT and HMMM, were
compared with resorcinol and subsequent analysis revealed that initial adhesion levels
were generally higher for the HMT systems [54]. Whilst both donors performed well
after thermal ageing, it was shown that addition of HMMM to be advantageous over
HMT after humidity and steam ageing. Recent studies [55] by Hoff compared traditional
HMT/resin/cobalt systems and HMMM/resin/cobalt systems against a new generation
of one component resin systems that did not require a resorcinol acceptor. Hoff claimed
that compounds containing new one component resins and no cobalt salt had better
adhesion retention after salt ageing than the traditional resin/cobalt systems. Similar
single component resins were found to give good rubber-to-steel cord adhesion when
used in combination with a triazine and a cobalt salt [56], with the added advantage of
easier processing than resin/formaldehyde systems.
As stated previously, cobalt salts can be used with or without a resin/silica system and
for the latter a combination of all three is required to obtain the desired adhesion and
rubber physical properties under all ageing conditions. The concentration of resin is
variable but it generally falls in the range of one to four parts per hundred rubber and
the methylene donor level is approximately in the same range. For optimum compound
properties, it is usual for the resin/donor ratio to be greater than one. Cobalt metal
levels generally fall in the range 0.1 to 0.3 parts, whilst silica may used at levels from 0
to 55 parts.
When using resin systems, the resin can be mixed in the initial stage with rubber,
carbon black and/or silica, cobalt salt and other ingredients, whilst the methylene donor
is mixed in the final stage with the curatives at a lower temperature. This ensures that
no crosslinking occurs before vulcanisation to cause processing difficulties and also
diminish the mode of action by which the resin improves rubber to metal bonding.
With the correct choice of curing system, the resin and silica have no discernible effect
on cure, and by careful selection of batch ingredients and concentrations, compound
properties are not adversely affected.
Despite their widespread use in rubber formulations, few mechanistic studies have
been performed to determine the role of silica and resin in the adhesion process. The
effect that resorcinol/formaldehyde resin had upon the adhesion interface between
rubber and a brass film has been investigated [57, 58] using AES in an attempt to
correlate spectroscopic data with actual adhesion values. In the unaged state, the
structure of the interface was essentially the same for compounds containing resin as
those without. Differences became apparent after ageing at high humidity when the
207
interface remained relatively unchanged in the case of the resin-containing sample (at
3 phr) and it was thought that the resorcinol/formaldehyde resin reacted with HMMM
to produce a protective barrier at the interface. Hamed and Huang [57] proposed such
a barrier that would prevent attack by moisture and also prevent migration of copper
and zinc towards the bulk rubber. Equally, the migration of sulphur and oxygen to the
interface would be hindered under humid conditions and consequently degradation of
the interface would be suppressed. Alternative theories [10] suggest that HMMM may
complex with cobalt in the rubber and thus prevent degradation by retarding the pro-
oxidative effects of cobalt.
The role of silica-only systems on adhesion has been studied using model compounds
with squalene [59]. It was shown that the mechanism for increased adhesion to brass-
coated wire-to-rubber was not just a simple improvement of the physical properties of
the rubber, but that silica moderated the thickness and composition of the interfacial
layer by a chemical interaction. SEM-EDX (scanning electron microscopy with energy
dispersive analysis of X-rays), XPS, AES and PIXE (proton induced X-ray emission
spectroscopy) revealed that silica affected the relative concentrations of compounds
present in the interfacial layer, promoting zinc oxide formation in particular.
7.6 Summary
The main purpose of this chapter has been to describe the predominant bonding systems
that are presently used in tyres. These are cobalt salts used either alone or in combination
with resin/silica systems. They have become very well established and are used by many,
if not all, the major tyre companies. Nevertheless, other experimental bonding systems
are being investigated and tested. These include metal complexes other than cobalt and
other non-metal bonding systems.
One of the most recent innovations for bonding tyre cord to rubber has been the use of
silanes to promote adhesion and to protect the interface [60, 61]. Other non-metallic
systems, such as tetrachlorobenzoquinone [62] and chloropyrimidines and chlorotriazines
[63] have also been studied. Regarding copper free coating of steel, alloy systems
containing Zn/Ni/Co [64], Zn/Co [65, 66] and other zinc alloys [67] have been proposed.
Traditionally, the tyre industry has been conservative when considering changes to the
belt region of a tyre because this is such an important and critical part of the tyre. Currently,
cobalt systems perform well and failures in the breaker are rare, in fact the tyre is more
likely to fail by catastrophic damage, e.g., puncture or just wearing away. Trends towards
tyres with longer life and with the capability to be retreaded will mean that tyre cord
adhesion systems will have to be designed to meet this need.
208
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Patent 4,519,430, 1985.
45. S. Wolff, Tire Science Technology, 15, 4, 276.
46. R. Rauline, inventor; Compagnie Generale des Etablissments Michelin - Michelin

& Cie, assignee; US Patent 5,227,425, 1993.
47. M. P. Wagner, Rubber Chemistry and Technology, 1976, 49, 3, 703.
48. M. P. Wagner, Elastomerics,1981, 113, 8, 40.
49. M. P. Wagner and N. L. Hewitt, Rubber Chemistry and Technology, 1979,

52, 4, 805.
50. M. P. Wagner and N. L. Hewitt, Rubber and Plastics News, 1984, 13, 23, 20.
51. P. Cochet, D. Butcher and Y. Bomal, Kautschuk Gummi Kunststoffe, 1995, 48,
5, 353.
52. L. R. Evans, J. C. Hope, T. A. Okel and W. H. Waddell, Presented at the 147th

ACS Rubber Division Meeting, Philadelphia, PA, Spring 1995, Paper No.16.
211
53. R. A. Ridha, J. F. Roach, D. E. Erickson and T. F. Reed, Rubber Chemistry and

Technology, 1981, 54, 4, 835.
54. P. Combette and F. Alarcon-Lorca, Revue Generale des Caoutchoucs et

Plastiques, 1988, 65, 683, 103.
55. C. M. Hoff, Presented at the 152nd ACS Rubber Division Meeting, Cleveland,
OH, Fall 1997, Paper No.21.
56. M. L. Engelhardt and K-K. Kang, inventors; Hanook Tire Manufacturing Co.,
Ltd., assignee; US Patent 5,723,523, 1998.
57. G. R. Hamed and J. Huang, Rubber Chemistry and Technology, 1991, 64, 2, 285.
58. G. Seo, Journal of Adhesion Science and Technology, 1997, 11, 11, 1433.
59. W. H. Waddell, L. R. Evans, E.G. Goralski and L. J. Snodgrass, Presented at the

148th ACS Rubber Division Meeting, Cleveland, OH, Fall 1995, Paper No.65.
60. W. J. Van Ooij and T. Child, Chemtech, 1998, February, 26.
61. W. J. Van Ooij, L. Shijian and S. Jayaseelan, Presented at IRC99, Seoul, Korea,
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Chemical Company Inc., assignee; US Patent 5,126,385, 1992.
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212
8
Rubber to Metal Bonding Using
Metallic Coagents
R. Costin
Editors Note
Metallic Coagents for Peroxide Vulcanisation
Metallic coagents are reactive substances, which improve the effectiveness of peroxide
crosslinking. Most of them belong to the group of methacrylates or derivatives containing
allyls, but polymeric materials with a high content of vinyl groups are also known to
react in a similar way.
The crosslinking efficiency of many peroxide-initiated free radicals is low. These labile
radicals can be converted to more stable radicals by contact in situ in the rubber mix
with polyfunctional monomers to form a three-dimensional network. Crosslinking
efficiency is thus increased by some 20%.
In addition these materials act as plasticisers during processing and in some cases also
act as hardening agents. The following chapter discusses the use of such agents in bonding
applications for a variety of rubbers.
Titanate and Zirconate Coupling Agents
Coupling agents are molecular bridges at the interface between two dissimilar substrates,
usually but not limited to, an organic filler and an organic polymer matrix.
Organometallic titanates and zirconate coupling agents form monomolecular layers on

the substrate of most materials, such as metals, metal oxides, carbonates, sulphides,
sulphates, siliceous materials, carbon black, some synthetic fibres such as Kevlar, dispersed
dyes and organic pigments to name a few. They render the substrate hydrophobic (moisture
free), organophilic (rubber compatible and reactive), organofunctional (such as phosphato
flame retardant functionality to provide controlled intumesence) and catalytically reactive
with the polymer phase.
They may also act as reactive super plasticisers to increase rubber flow while increasing
the mechanical properties of the rubber - even above the Tg. Viscosity reduction or polymer
213
Commercial rubbers
solvation and higher filler loading can be accomplished with less plasticiser. Flow is
achieved through molecular rearrangement and not average molecular weight reduction
of the rubber.
Neoalkoxy zirconates also provide novel opportunities for the adhesion of fluorinated
polymers to metal substrates because the introduction of a zirconate at the interface
results in a metal oxygen zirconium (VI) organofluoride.
8.1 Introduction
The use of coagents in conjunction with peroxides to cure rubbers has been common
practice in the rubber industry for many years. Coagents are typically multifunctional
monomers that are highly reactive in the presence of free radicals and readily graft to
rubber chains to form a polymeric crosslink network. They are used in peroxide-cured
systems to increase the crosslinking efficiency of the vulcanisation process and to increase
the crosslink density of the rubber. The increase in crosslink density is directly related to
the coagent concentration and has a major effect on the mechanical and physical properties
of the cured rubber. Some of the most common coagents in use today are esters of methacrylic
acid [1, 2]. Trimethylolpropane trimethacrylate (TRIM) and 1,3-butyleneglycol
dimethacrylate (BGDMA) are typical examples of the methacrylate ester class of coagents.
Metallic salts of acrylic acid and methacrylic acid also function as coagents in the same
way as the methacrylate esters do. They are also highly reactive in the presence of free
radicals and readily form a polymeric crosslink network with rubbers. Several examples
are reported where they have been used as coagents in peroxide-cure formulations for
both saturated and unsaturated rubbers.
In a patent issued to the US Army in the late 1980s, the zinc salts of acrylic acid and
methacrylic acid were used to upgrade the properties of hydrogenated nitrile rubber
(HNBR) [3]. The goal of this work was to develop abrasion-resistant materials that
could be used to extend the service life of tank treads. Zinc dimethacrylate (ZDMA)
proved to be the best material in the study for improving the tear strength, abrasion
resistance, and high temperature performance of HNBR.
Also, during this period, Zeon Chemicals discovered that curing HNBR which contained
a mixture of zinc oxide and methacrylic acid, resulted in rubber products possessing very
high tensile strength and excellent abrasion resistance [4, 5 and 6]. In this case, the zinc
oxide and methacrylic acid reacted in situ to form ZDMA prior to curing. This approach
requires careful control of the methacrylic acid-zinc oxide stoichiometry, to minimise
residual methacrylic acid that could cause corrosion of the mixing equipment.
214
Rubber to Metal Bonding Using Metallic Coagents
Metallic salts of acrylic acid and methacrylic acid have also been used for many years
with polybutadiene to form the rubber cores for two-piece golf balls [7, 8 and 9].
Crosslinking polybutadiene with metal salts of either acrylic acid or methacrylic acid
results in a very strong rubber compound with high compression and a high coefficient
of restitution (COR). The COR is a measurement of velocity for golf balls. In the test,
the ball is propelled against a backboard, and the inlet and exit velocities are measured.
The COR is the exit velocity/inlet velocity. Zinc salts have proved to be the most effective
of the metal salts and are used extensively in the manufacture of golf ball cores today.
Several papers have been published that describe the use of zinc diacrylate (ZDA) and
ZDMA as coagents to improve the physical properties of rubbers [10, 11, 12, 13 and
14]. In this context, they are referred to as metallic coagents. They differ from
conventional rubber coagents, like triallyl cyanurate (TAC) and TRIM, in that they
have ionic bonds that become part of the crosslink network. The ionic bonds allow for
a flexible and more forgiving network, particularly at high crosslink levels. This can
lead to rubber products with good dynamic properties and a good combination of
physical properties.
It has been found that, in addition to improving the mechanical properties of rubber,
metallic coagents also increase the adhesion of rubber to untreated metals and synthetic
fibres during vulcanisation [15, 16]. They offer a way of bonding rubber to metal that
is far less intensive and time consuming than the procedure required for conventional
adhesives [17, 18]. There are several ways metallic coagents can be used with rubber
compounds to improve adhesion. The most straightforward way is to simply mix them
with the rubber compound, where they function as internal adhesion promoters upon
curing. They can also be mixed with a rubber compound to form an adhesive strip that
can be used as a tie layer between various rubber compounds and metals. This technique
can be applied to either sulphur- or peroxide-cured stock. And finally, they may be
used to form reactive dispersions, which can be applied as pastes to either the rubber
or metal surface prior to curing. This chapter reviews these techniques along with
some of the physical properties that can be obtained using metallic coagents.
8.2 Metallic Coagents
Metallic coagents are defined as the metal salts of acrylic and methacrylic acids. The two
products discussed, Saret 633 and Saret 634, are the difunctional zinc salts of acrylic
acid and methacrylic acid, as shown in Figure 8.1.
They are free flowing, 100% reactive solids, and can be readily compounded with a
variety of rubbers. Additional characteristics include low odour, scorch protection
215
Figure 8.1 Saret metallic coagents
with a non-nitroso scorch retarder, and improved physical properties. They also
provide excellent high temperature stability and good dynamic properties, as well as
outstanding fluid resistance.
Many of the unique properties associated with the metallic coagents come from the
ionic bonds that are formed between the zinc cations and the corresponding
carboxylate anions. Metal cations, particularly zinc, are known to increase the strength
and the mechanical properties of polymers containing metal-neutralised ionic
crosslinks. These products are known as ionomers and their properties are well-
documented [18]. The same ionic crosslink mechanism is believed to occur with
rubbers that are cured with Saret 633 and Saret 634. Crosslinking with peroxide
results in the formation of a covalent bond. This carbon-carbon bond is quite rigid
and stable and accounts for the lower tensile and tear strength of peroxide-cured
stocks compared with sulphur vulcanisates. The good heat stability of this covalent
bond also explains the superior heat aged characteristics of peroxide cured systems.
In contrast, polysulphide crosslinks formed with sulphur curing are thermally weak,
but are mobile under stress and can slip along the hydrocarbon chain. This mobility
has been used to explain the superior tensile and tear strength in sulphur-cured stocks.
The crosslinks formed with metallic coagent in peroxide cured rubbers are ionic due
to the zinc carboxylate bonds (see Figure 8.2). These ionic bonds exhibit both good
heat aged stability and the ability to slip along, characteristics of both the peroxide
and sulphur crosslink systems, giving high tensile and tear strength and excellent
heat aged properties.
When metallic coagents are used in rubber compounds to increase bonding to metals
and reinforcing materials, they also change the physical properties of the rubber
compound. Therefore, their use as coagents and their effect on the properties of the
rubber compound will be discussed in Sections 8.2.2 and 8.2.3.
216
Figure 8.2 Ionic crosslinks formed with metallic coagents
8.2.1 Scorch Safety
ZDA and ZDMA increase both the cure state and the cure rate of the rubber compound
and, therefore, are classified as Type I coagents. Type I coagents are highly reactive
in free radical reactions and tend to produce both rubber crosslinks and
homopolymerisation [19]. This will lead to high hardness and high tensile strength,
but may also accelerate crosslinking that could reduce scorch safety during mixing.
An example of this is shown in Figure 8.3 for ZDA in nitrile rubber. The rheometer
curves show the cure characteristics of ZDA with peroxide relative to peroxide alone.
It can be seen that the scorch time is significantly less for ZDA with peroxide than
Figure 8.3 Torque versus time for various coagents
217
for peroxide alone. Also, the cure rate is significantly faster with the ZDA/peroxide
combination, which allows for more rapid processing where scorch is not a concern.
It should also be noted that the maximum torque is much higher with ZDA and
peroxide, which indicates a greater crosslink density and, therefore, higher mechanical
properties.
To overcome scorch behaviour during processing, scorch retarded versions of ZDA

and ZDMA were developed and are recommended for rubber applications [11, 12,
13]. Both Saret 633 and Saret 634 contain non-nitroso scorch retarders, which are
safe and effective for rubber compounding. The effect of the scorch retarder on ZDA
is also shown in Figure 8.3. In this example, Saret 633 (ZDA with scorch retarder) is
compared to ZDA and to peroxide alone. The scorch time of Saret 633 has increased
significantly relative to ZDA and is about the same as that obtained with the peroxide
alone. This indicates that mixing can be achieved more safely with less chance of
premature vulcanisation. Also, the maximum torque obtained with Saret 633 is
essentially the same as that obtained with ZDA, indicating that no significant change
in crosslink density occurred.
The same behaviour occurs with the scorch-retarded version of ZDMA and is
illustrated in Table 8.1 with EPDM rubber. In this example, a 40% increase in TS2 is
obtained with Saret 634, the scorch-retarded version of ZDMA, without any
significant loss in maximum torque (MHF). MHF is the difference between the
minimum torque (ML) and the maximum torque (MH) obtained for a rubber compound
by oscillating disk rheometer (ODR). It is a measure of the crosslink density of a
compound and is part of the curing characteristics of a compound.
Thus, with the Saret metallic coagents it is possible to gain the benefit of increased crosslink
density and faster cure rates, while maintaining good scorch safety.
Table 8.1 Effect of Saret retarder on scorch safety

No Coagent ZDMA Saret 634
TS2, min 1.5 2. 1
TS5, min 5.5 3.5 4. 0
MHF, N-m 1.24 2.15 2.30
TS2 is the time taken for a 2 unit increase in torque
TS5 is the time taken for a 5 unit increase in torque
218
scorch safety
8.2.2 Tensile Properties
The increase in modulus obtained with coagents in the peroxide curing of rubber
compounds is always accompanied by a corresponding decrease in elongation. This
behaviour is noted for all coagents in commercial use today. One surprising
characteristic of metallic coagents is that they increase the hardness and modulus of
rubbers like other coagents do, but with much greater retention of elongation. This
characteristic is compared in Figure 8.4, with Saret 633 and Saret 634 versus TRIM,
all in EPDM. In all cases, as the coagent concentration was increased from 0 to 20
phr, the modulus increased and the elongation decreased. However, the metallic
coagents, Saret 633 and Saret 634, gave much higher elongation than TRIM for a
specific modulus value. Saret 634 gave a slightly better balance of modulus and
elongation at low modulus values and Saret 633 gave the highest modulus for a
given concentration and the highest modulus overall.
Peroxide and coagents normally have very little beneficial effect on the tensile strength
of rubbers. Sulphur vulcanisation, on the other hand, normally increases the tensile
strength of rubbers. However, it has been found that metallic coagents increase the
tensile strength of rubbers such as EPDM and NBR in a manner similar to that
obtained with sulphur vulcanisation. This effect is shown in Table 8.2 for Saret 633
and Saret 634 versus TRIM, all in NBR. Saret 633 gave the highest tensile strength
at each concentration. It is interesting to note that, with Saret 633, the increase in
tensile strength is linear, suggesting that higher tensile strengths could be obtained at
Figure 8.4 Modulus versus elongation values for various coagents
219
Table 8.2 Tensile strength versus coagent concentration

phr TRIM (MPa) Saret 633 (MPa) Saret 634 (MPa)
0 15.8 15.8 15.8
10 15.2 18.8 16.0
20 15.4 21.4 18. 2
higher coagent concentrations. The tensile strength also increased with Saret 634,
but not as dramatically. And, as expected with TRIM, the tensile strength remained
essentially unchanged.
Similar results were obtained with EPDM.
8.2.3 Tear Strength
The effect of metallic coagents on the tear strength of EPDM is displayed graphically in
Figure 8.5. With both Saret 633 and Saret 634, the tear strength increased as the coagent
Figure 8.5 Tear strength obtained with metallic coagents
220
was increased. However, tear strength decreased when TRIM was used as the coagent.
This is typical behaviour for both Type I and Type II coagents. Type I coagents are more
reactive and increase both the cure rate and the cure state of a rubber compound. Type II
coagents are less reactive and increase only the cure state.
With both Saret 633 and Saret 634 the tear strength increased as the concentration was
increased, reaching maximum strength at concentrations near 10 to 15 phr. This is in
contrast to the behaviour of conventional coagents, where tear strength normally declines
as the crosslink density is increased. An example of normal coagents is shown with
TRIM in Figure 8.5. In this case, the tear strength decreased sharply with 5 phr TRIM
and then gradually levelled-off at about 10 phr.
8.3 Experimental
8.3.1 Materials
8.3.1.1 Solid Rubbers
A nitrile masterbatch, see Table 8.3, was used in all experiments pertaining to nitrile
rubbers. Hycar 1042 (Zeon Chemicals) is a general purpose NBR (acrylonitrile content
is 33%) with good processing characteristics and high physical properties.
An EPDM masterbatch, see Table 8.4, was used in all experiments relating to EPDM
rubbers.
Table 8.3 Formulation for a nitrile Table 8.4 Formulation for an

masterbatch EPDM masterbatch
Material ph r Material phr
Hycar 1042 100 Nordel 1040 100
Carbon black N365 65 Carbon black N762 100
Dioctyl phthalate 15 Sunpar oil 2280 50
Zinc oxide 5 Zinc oxide 5
Stearic acid 1 Stearic acid 1
221
The chlorosulphonated PE compound, see Table 8.5, was used with or without (control)
Saret 633. Saret 633 is ZDA containing a non-nitroso scorch retarder to provide scorch
safety during processing.
The ethylene vinyl acetate copolymer (EVA) compound is given in Table 8.6.
The silicone rubber formulation is given in Table 8.7. This formulation was used with or
without (control), Saret 633.
The natural rubber formulation is given in Table 8.8 and was used with or without
(control), Saret 633.
8.3.1.2 Formulation Preparation
The rubbers were compounded according to the formulations described in Section 8.3.1.1,
using a laboratory 15.2 cm two-roll mill. All masterbatches were masticated on a two-
Table 8.5 Formulation for a

Hypalon compound
Table 8.6 Formulation for an
Material ph r
EVA compound
Hypalon 40 100
Material phr
Poly-Dispersion T
44 Elvax 240 100
(HRL) D-90
Carbon black N550 5 HI SIL 230 25
Whitex clay 40 Zinc oxide 3
Kerflex A 20 Stearic acid 3
Sundex oil 790 15 Trioctyl trimellitate

3
(TOTM)
Paraffin Wax 6
Perkadox 1440 2
DiCup 40KE 5
Saret 633 3
Saret 633 5
Elvax 240 (DuPont) is 28% vinyl
Hypalon 40 is made by DuPont acetate with a melt index of 43
Poly-Dispersion T (HRL) D-90 is made
by Rhein Chemie
HRL: heat resistant lithage
222
Table 8.8 Formulation for natural

rubber
Material phr
Table 8.7 Formulation for SMR CV 60 100

silicone rubber Carbon black 22
Material ph r HI SIL 230 5
Silicone 6140 100 Zinc oxide 4
6916 HA 1 TOTM 3
Triganox 10145 2 Resin D 2
Saret 633 10 Stearic acid 1
Silicone 6140 and 6916 HA (stabiliser) DiCup 40KE 5
are made by General Electric
Saret 633 10
SMR: Standard Malaysian Rubber
(Malaysian Rubber Bureau)
roll mill until a flux was created at the nip of the rollers. At this point, the Agerite Resin
D, DiCup and coagent were slowly added to the flux roll. The band was then sheeted
and folded and then rebanded for mixing. This process was repeated many times to
ensure thorough mixing. The coagent concentration was varied as noted in the individual
formulations. The compounded rubbers were then cured in a compression mould for
twenty minutes at 160 166 C.
8.3.1.3 Compounding and Curing
The Saret 633 and 634 coagents can be mixed with most rubbers using a two-roll mill or
a Banbury internal mixer. Curing the resulting rubber compound against the metal
substrate creates the adhesive bond as well as the mechanical properties of the rubber.
The rubber formulations used in most adhesive tests were mixed on a two-roll mill and
sheeted out to a thickness of 0.08 mm. Strips of the rubber sheeting were then placed
between the appropriate metal panels and cured in a compression mould for 20 minutes
at 165 C. The shear adhesion values and the mechanical properties were determined
according to ASTM test methods D816-82 [20] and D412-98a [21], respectively.
223
8.3.1.4 Measurement
Physical tests were conducted for all moulded compounds after moulding, and again
after heat ageing at 100 C for 70 hours. Tensile strength, modulus and elongation were
determined according to ASTM method D412 using a Thwing Albert model 1451-42
tensile tester at a crosshead speed of 51 cm/minute. Shore A hardness tests were determined
for samples after moulding using a hand-held Shore A durometer.
Cure characteristics, which include scorch time, cure rate and torque values, were
measured over a 20 minute period at 160 C using a Monsanto oscillating-disk rheometer
according to ASTM method D1084 [22].
Compression set was determined by compressing a 2.5 cm diameter specimen built up

with four plies to 50% original thickness for 22 hours at 100 C. The specimen was then
removed and the permanent set measured as a percentage of original thickness, using the
method in ASTM D395 [23].
Rubber-to-metal adhesion was determined by tensile testing a rubber specimen cured

between two metal coupons as illustrated in Figure 8.6. The tensile test was run at
2.5 cm/minute crosshead speed and the force in kg to break the lap joint in shear was
measured. The rubber specimen, approximately 0.08 cm thick, was cured at 160 166 C
for 30 minutes between two 2.5 x 7.6 x 0.08 cm metal coupons overlapped 2.5 cm in a
plaque mould under 207 MPa pressure (Figure 8.6). The metal coupons were methanol
washed and dried before curing.
Adhesion peel tests were run by curing a 0.64 cm thick rubber specimen against a metal
coupon and then tensile testing at 180 angle of pull with 2.5 cm/minute crosshead
speed. The rubber specimen was hand pressed against the metal coupon.
Figure 8.6 Test specimen - side view
224
8.3.2.1 Liquid Rubbers for Sealants
The liquid rubbers that were used in the sealant applications are listed in Table 8.9.
Test formulations for pumpable sealants based on liquid natural rubber, liquid polybutadiene
and liquid nitrile rubber are shown in Tables 8.10, 8.11, and 8.12, respectively.
Table 8.9 Liquid rubbers used for sealant applications and their suppliers
Trade name Company Formulation
Trilene 56 EPDM Uniroyal 13% DCPD in 49% ethylene
51% propylene
MW 5,200
DPR 40 NR Hardman 36,000-55000 Pa-s
viscosity at 38 C
MW 40,000
R45 HT PB Elf Atochem Hydroxyl terminated
PB
MW 2,800
NBR 1312LV Zeon 33% ACN
low MW liquid rubber
ACN: acrylonitrile; DCPD: dicyclopentadiene; MW: molecular weight; PB: polybutadiene
Table 8.10 NR sealant formulation Table 8.11 PB sealant formulation

Material phr Material phr
DPR 40 NR 10 0 R45 HT PB 100
Calcium carbonate 50 Calcium carbonate 50
Zinc oxide 7.5 Zinc oxide 7.5
Stearic acid 1.0 Stearic acid 1.0
Maglite D 2.0 Maglite D 2.0
Agente resin D 0.5 Agerite resin D 0.5
t-Butyl perbenzoate 7.7 t-Butyl perbenzoate 7.7
Saret 633 30.0 Saret 633 30.0
DPR 40 NR is supplied by Hardman
PB NR 225
Table 8.12 Nitrile sealant formulation

Material phr
NBR 1312LV 100
Calcium carbonate 50
Zinc oxide 7.5
Stearic acid 1.0
Maglite D 2.0
Agerite resin D 0.5
t-Butyl perbenzoate 7.7
Saret 633 30.0
NBR 1312 LV is produced by Zeon Chemicals
The pumpable sealants were prepared according to the above formulations and were
cured at 160 C for 25 minutes.
Saret 633 and Saret 634 (Sartomer Company) are the scorch-retarded versions of zinc
diacrylate and zinc dimethacrylate, respectively. The Saret metallic coagents are used in
rubber compounding to avoid premature curing during mixing.
The reactive dispersions (CD-627, CD-628, PRO 1825) are experimental materials
developed by Sartomer Company for evaluation in this study. They are proprietary products
that consist of a metallic coagent dispersed at various concentrations in different acrylic
monomers. A viscous solution or paste is formed which can be used in place of an adhesive
to form adhesive bonds during the curing step of the rubber compound (peroxide cure
only). They contain no solvents and are 100% reactive. The metallic coagent is a small
particle-size powder that is not soluble in monomers, but does form a stable dispersion.
A practical use of Saret 633 as an internal adhesion promoter is shown in Table 8.13
which gives a formulation for a pumpable sealant based on liquid EPDM [24]. This
formulation not only gives excellent adhesion to steel, but bonds strongly to oily steel as
well. In this example, lap shear adhesion was determined using steel coupons, overlapped
2.5 cm, with a spacer to form a uniform sealant thickness of 0.18 cm. Light pressure was
applied so that the upper coupon would be pressed against the spacer. The sealant was
then cured at 160 C for 25 minutes. To test for bonding to an oily surface, the steel
226
EPDM
Table 8.13 A typical formulation of an EPDM sealant

Formulation Saret 633 Control
Trilene 56 EPDM 100 100
CaCO3 50 50
Zinc oxide 7.5 7.5
Stearic acid 1.0 1.0
Maglite D 2.0 2.0
Agerite resin D 0.5 0.5
t-Butyl perbenzoate 7.7 7.7
Saret 633 20 0
Lap shear adhesion
To steel, MPa 4.88 (C) 0.14 (C)
To oily steel, MPa 4.26 (C) 0.21 (50% C)
C = Cohesive Failure
coupons were coated with ASTM oil No. 3, the excess oil was removed, and then the
sealant was applied and cured as above. This type of performance is particularly attractive
for automotive applications where oily surfaces and oil contamination are prevalent.
Normally, extensive cleaning is required to prepare the metal surface for adhesion with
conventional adhesives and sealants.
Table 8.14 shows the benefit of adding Saret 633 to several liquid rubberic sealant
formulations. Formulations and cure conditions are described in Section 8.3.2. In each
case, a control without Saret 633 was also tested for comparison and found to have
adhesive values ranging from 0 to 0.27 MPa.
Lap shear adhesion was measured using steel coupons overlapped 2.5 cm. Spacers were
used between the coupons to obtain a uniform sealant thickness of 0.18 cm. Light pressure
was applied so the upper coupon would bear evenly on the spacers. The sealant compounds
were then cured at 160 C for 25 minutes and then tested at room temperature.
When liquid natural rubber is used as the sealant base, shear adhesion increased from
0 for the control to 4.55 MPa with 30 phr Saret 633. Heat ageing at 130 C for 14 days
increased the shear adhesion to 4.90 MPa.
227
pumpable
Table 8.14 Pumpable sealants based on liquid rubbers

Liquid rubber Saret 633 (phr) Adhesion* (MPa)
Trilene 56 EPDM 20 4.90 (C)
DPR natural rubber 30 4.55 (C)
NBR 1312LV 30 3.45 (C)
R45HT polybutadiene 30 5.24 (A/C)
* Shear Adhesion to Steel
A = Adhesive Failure
Saret 633 also was evaluated in a liquid polybutadiene sealant as shown in Table 8.15.
Again, shear adhesion increased from 0.28 MPa for the control to 5.24 MPa for Saret
633 at a concentration of 30 phr. Shear adhesion decreased to 3.51 MPa when the
sealant was exposed to 5% sodium hydroxide solution for 70 hours at 70 C. A separate
test specimen heat aged at 130 C for 14 days increased the shear strength to over
6.90 MPa.
The liquid nitrile rubber was evaluated at 30 phr Saret 633 as shown in Table 8.12.
Shear adhesion to steel was 3.45 MPa for the Saret 633 formulation versus 0 MPa for
the control. Heat ageing at 130 C for 14 days also showed an increase with this
formulation, with the value increasing to 6.55 MPa.
In all cases, Saret 633 increased adhesion to oily and clean steel relative to the control.
The failure mode was predominantly cohesive with the Saret 633 in all sealant
formulations. The sealant viscosity for each formulation was approximately 1500 MPa.
No attempt was made to optimise the cure conditions or the formulations for
performance.
Liquid polybutadiene formulated with Saret 633 was also evaluated as a glass sealant
as shown in Table 8.15. As the data show, adhesive values of 1.03 MPa and 1.72 MPa
were obtained for bonding glass to steel and glass to E-Coat (electrostatic phosphate
coating applied to metal to aid corrosion resistance and surface uniformity), respectively.
Cohesive failure occurred in all cases, suggesting higher values could be obtained with
higher strength formulations. The controls, without Saret 633, did not adhere to the
glass substrate.
228
polybutadiene glass
Table 8.15 Polybutadiene glass sealant

Formulation (Cure at 160 C) phr
R45HT polybutadiene 100
HiSil 230 50
Zinc oxide 7.5
Stearic acid 1.0
Maglite D 2.0
Resin D 0.5
Saret 633 30
CADOX BS 10
Shear adhesion, MPa
Glass to steel 1.03 (C)
Glass to E-coat steel 1.72 (C)
CADOX = 50% Benzoyl Peroxide on a silicone carrier
8.4 Results and Discussion
8.4.1 Adhesion to Metals
Conventional metal reinforced rubber products require both an adhesive to bond the
metal to the rubber and a separate curing system to increase the mechanical properties
of the rubber. This entails an intensive, time-consuming series of procedures: first the
metal surface has to be prepared, then the adhesive has to be applied and dried. After
this step, the rubber compound has to be prepared, moulded and then cured in contact
with adhesive treated metal. In most cases a post-cure step also is required. The metallic
coagents offer several alternative ways of bonding rubber to metal that are far less
intensive and time consuming. This is due in part to the fact that they form strong
rubber-to-metal bonds without the use of external adhesives or a separate curing step.
Any procedure that places the metallic coagents and peroxide between the metal surface
and rubber with applied pressure may be used.
229
Three techniques to bond rubber to metal and synthetic fibres using metallic coagents
have been developed [25]. They are:
1) in the uncured rubber compound as an internal adhesion promoter,
2) in a thin adhesive strip that functions as a tie layer upon curing,
3) in a reactive dispersion that can be applied as a viscous liquid or paste to either the
metal or rubber prior to curing.
Although the metallic coagents are not adhesives by themselves, there are applications
where these techniques may be applied to improve the adhesion of rubber to metals and
synthetic fibres.
8.4.1.1 Internal Adhesion Promoter
When using Saret 633 and Saret 634 as internal adhesion promoters, it is important to
remember that they do crosslink with the rubber during curing and, therefore, change
the physical properties of the rubber. An example of this is shown in Table 8.16 for the
Nordel EPDM formulation containing 2 phr of the metallic coagents. In this example,
both the modulus and tensile strength increased significantly, even at a concentration of
2 phr. Shear adhesion also increased significantly at the 2 phr concentration, especially
with Saret 633.
Saret 634, while not as effective as Saret 633, also increased adhesion in the example
described in Table 8.16. In applications where high tear strength, abrasion resistance,
exceptional scorch safety and slow cure are needed, Saret 634 may be the best choice.
Metallic coagents based on other metal salts, such as calcium and magnesium, also increase
rubber-to-metal adhesion, but not as effectively as Saret 633 and Saret 634.
Table 8.16 Tensile properties obtained with metallic coagents in EPDM

Modulus Tensile strength Adhesion to steel
Coagent (2 phr)
(MPa) (MPa) (MPa)
None 0.55 3.83 0.5 0
Saret 633 1.10 9.14 3.4 4
Saret 634 1.03 8.66 2.1 4
230
The strength of the adhesive bond increases as the concentration of the metallic coagent
is increased. The effect of Saret 633 concentration on the adhesion of EPDM to steel is
shown in Table 8.17. Shear adhesion increased from 0.5 MPa to 11.34 MPa as the Saret
633 concentration was increased from 2 phr to 20 phr. In all cases, cohesive failure, i.e.,
failure within the rubber, is the primary mode of failure for the adhesive bond. It should
also be noted that as the Saret 633 concentration is increased from 2 phr to 20 phr, the
modulus and hardness of the rubber also increases. As a result, Saret 633 cannot be
simply added to a currently used rubber compound to replace an adhesive without
modifying the formulation. It would be necessary to adjust the Saret 633 and/or filler
concentrations to get the best balance of adhesion and physical properties.
As shown in Figure 8.7, strong rubber-to-metal bonding can be obtained with Saret 633
as an internal adhesion promoter for a variety of rubbers such as silicone rubber, EVA,
EPDM, NR and Hypalon. All of the compounds contained 5 phr of Saret 633 and were
cured with peroxide. In each case, shear adhesion was significantly increased with the
Saret 633 cure system over the peroxide control.
Table 8.17 Adhesion to steel obtained with Saret 633 in EPDM

Saret 633 2 phr 20 phr
Adhesion, MPa 0.50 11.34
Modulus, MPa 1.1 2.13
Shore A hardness 55 80
Figure 8.7 Adhesion of various rubber to steel
231
Cohesive failure was found to be the predominant mode of failure for each rubber
compound containing Saret 633 (Figure 8.7). Therefore, it would be expected that as the
Saret 633 concentration is increased, the rubber compound would become stronger due
to additional crosslinking, which would result in an increase in adhesive strength at the
interface between rubber and substrate. This proved to be the case and is shown in
Figure 8.8 for EPDM bonded to untreated steel. As the Saret 633 concentration was
increased from 0 to 20 phr, the shear adhesion increased from approximately 0.55 MPa
for the control to over 11.0 MPa. Cohesive failure was the predominant mode of failure
at each concentration. Similar performance was observed for other rubbers, such as
nitrile, natural, polybutadiene, silicone and hydrogenated nitrile.
The Saret 633/peroxide-cure system also promotes good adhesion to other untreated
metals, including aluminium, zinc, brass, and stainless steel. This is illustrated in Figure 8.9
for EPDM containing 10 phr Saret 633. In each case, shear adhesion increased with the
addition of Saret 633, compared with peroxide alone.
8.4.1.2 Adhesive Tie Layer
A further technique is to form an adhesive strip containing the metallic coagent. The
adhesive strip may then be used to bond another rubber to a metal surface. When the
adhesive strip approach is used, the metallic coagents are milled into the rubber compound.
The uncured compound is then formed into sheets by calendaring and then cut into
stable, thin strips that contain the metallic coagent, peroxide and other rubber additives.
The rubber strip can then be applied between the uncured rubber compound and the
Figure 8.8 The effect of Saret 633 concentration on the shear adhesion of EPDM to steel
232
Figure 8.9 EPDM adhesion to various metals
metal surface and cured to form an adhesive bond. In this way, the rubber strip is
functioning as a tie layer between the metal and rubber. Figure 8.10 illustrates the test
method that was used to evaluate this approach for various rubber compounds. Although
other rubbers could have been used, the adhesive strips used in this study were prepared
using the EPDM masterbatch containing 10 phr Saret 633 as described in Section 8.3.1.1.
The EPDM compound was calendared to form thin strips approximately 0.8 mm thick.
The strips were placed between the uncured rubber and the metal coupons as shown in
Figure 8.10. After curing, the test specimen was cooled and tested for lap shear adhesion.
This technique works for bonding both peroxide and sulphur cured stock to various
metals. An example of this technique is illustrated in Table 8.18 with a strip containing
Saret 633 in EPDM that is bonding sulphur cured EPDM to steel.
Figure 8.10 Adhesive strip - test specimen side view
233
Table 8.19 Bonding peroxide

cured elastomers to steel with the
EPDM Saret 633 adhesive strip
Table 8.18 Bonding sulphur cured
EPDM to steel Shear adhesion
Rubber
(MPa)
Shear adhesion
(MPa) EPDM 8.53 (C)
No adhesive 0.58 NBR 5.98 (C)
Commercial adhesive 4.68 CPE 7.22 (C)
EPDM Saret 633 strip 5.78 NR 8.53 (C)

C = cohesive failure
CPE = Chlorinated polyethylene
The EPDM Saret 633 strip also may be used to bond other rubbers to various metals.
Several examples of peroxide cured rubbers are shown in Table 8.19. In each case,
0.8 mm of the EPDM Saret 633 strip was placed between the rubber compound before
curing. After curing at 160 C for 20 minutes, the test specimen was cooled and tested
for shear adhesion.
8.4.1.3 Reactive Adhesive Dispersions
The third approach involves applying a dispersion of the metallic coagent as a reactive
adhesive between the metal and the rubber stock. The reactive dispersions, as described
in Section 8.3.1.1, are made by mixing the metallic coagent in a liquid coagent to form
a viscous liquid or paste. They may then be applied in place of an adhesive to the
surface of the metal or the uncured rubber stock. The only requirement is that the
rubber being bonded must contain peroxide as the curative. When the rubber is cured,
peroxide in the rubber stock activates the reactive dispersion, forming adhesive bonds
between the rubber and the metal surface. Results obtained using this technique are
summarised in Table 8.20 for several reactive dispersions, versus a conventional solvent-
based adhesive, for bonding peroxide-cured EPDM to steel.
sulphur
234
peroxide reactive dispersions
Table 8.20 Bonding peroxide-cured EPDM

to steel with reactive dispersions
Shear adhesion
(MPa)
No adhesive 0.4 8
Solvent adhesive 5.5 0
Reactive dispersion 3.44 5.5 0
8.4.2 Adhesion to Fibres and Fabrics
Many rubber products are reinforced with metallic or synthetic fibres to increase the strength
of the product. Effective adhesion of the rubber to the reinforcing material is critical for
good service life and safe performance. If the adhesive bond fails, a weak point will result,
causing premature failure. In belts, fabric reinforcement is used to support the wear area
for improved abrasion resistance. Again, good adhesion is necessary for the fabric to function
effectively in this capacity.
Saret 633 and Saret 634 were found to increase the adhesion of rubber to most polar surfaces,
including synthetic fibres and fabrics [26]. Examples of this are shown in the next section.
8.4.2.1 Monofilament/Braided Wire Adhesion
Saret 633 was evaluated in a T-pull adhesion test using the EPDM formulation described in
the materials section (see Section 8.3.1.1). The T-pull test measures the adhesion between
rubber and a fibre. The fibre is placed in a mould and rubber is then added and cured. The
fibre is then pulled in a perpendicular direction from the rubber and the force to break the
adhesive bond is measured. The T-pull test is accomplished by using a special mould with a
grid of trenches into which can be laid rubber and perpendicular to the rubber a filament. By
filling the trench half way with the rubber the filament is embedded. After curing, the filament
and rubber resemble a cross. The tensile tester is used to strip the rubber from the filament.
Data for Saret 633 and several filaments and braid are shown in Figure 8.11 together
with data for the control without the Saret 633.
In each case, the Saret 633 significantly improves the T-pull adhesion over the control,
especially the metallic monofilaments, copper, aluminium and steel. The adhesive failure
235
Figure 8.11 T-pull adhesion of EPDM to fibres and wires
in each case was cohesive, including the polyester and the Nylon, wherein rubber remained
on the monofilament after the test.
8.4.2.2. Nylon Braid
A comparison of Saret 633 versus conventional resorcinol formaldehyde (RFL) treatment

in a T-pull adhesion test with Nylon braid and EPDM is shown in Figure 8.12.
The control, which consists of Nylon braid without RFL treatment and EPDM rubber
without Saret 633, tested at 1.3 N force. The RFL sample, which is RFL treated braid that
is used commercially today, tested at 5.8 N with EPDM without Saret 633. With EPDM
containing 10 phr Saret 633, a value of 15.5 N was obtained with untreated Nylon braid.
This is more than double the value obtained with the commercially available Nylon braid.
Saret 633 clearly increases adhesion to synthetic fibres like Nylon and polyesters. Thus,
with Saret 633, it may not be necessary to RFL treat fibres and fabric for good adhesion.
This could simplify applications where rubber reinforcement is required.
8.4.2.3 Fabric Adhesion
The EPDM formulation described in Section 8.3.1.1, with and without 10 phr of metallic
using coagent, was cured in contact with Nylon/polyester warp fabric for 20 minutes at
160 C. RFL treated fabric was used in the control sample. Peel adhesion (180 angle)
236
Figure 8.12 T-pull adhesion of EPDM bonded to Nylon braid
was measured on a 1.27 cm wide specimen at a test speed of 2.5 cm/minute. The results
obtained with Saret 633 and Saret 634 versus the RFL control are shown in Figure 8.13.
Results shown in Figure 8.13 show the superior adhesion characteristics obtained with
the Saret 633 when cured against the fabric at 160 C for 20 minutes. Fabric was peeled
from the rubber at an angle of 180. Failure mode was cohesive with rubber remaining on
the fabric after the peel test.
Figure 8.13 The effect of metallic coagents on the peel strength of Nylon/polyester
fabric bonded to EPDM
237
In a separate but similar test, Saret 634 was compared with Saret 633. For situations
where either water sensitivity or abrasion resistance is an issue, Saret 634 can be substituted
for the Saret 633. Saret 634 is less sensitive to moisture then Saret 633.
8.5 Summary
Saret 633 and Saret 634 can be used to create strong adhesive bonds between a
variety of rubber compounds and untreated metals, synthetic fibres and fabrics. They
also function as coagents by increasing the crosslink density of the rubber compound.
Thus, they function as adhesion promoters as well as crosslinkers to enhance both
the adhesive and mechanical properties of the cured rubber. One requirement is that
they are used in peroxide cure compounds for optimum results. Metallic coagents
have been used with sulphur to improve adhesion but they do adversely affect the
cure state of a sulphur compound.
The most straightforward way of using the metallic coagents is to mix them directly
into the rubber compound before curing. This approach may be a good fit for rubber
rollers, sealants, adhesive tapes, extruded products and certain moulded goods. It
would have limited utility for moulded products where mould sticking or mould
fouling is a problem. However, using external mould release agents will minimise
mould sticking and mould fouling problems.
Two other techniques have been described for bonding rubber to metals, fibres and
fabrics with the metallic coagents. One involves using the metallic coagent in an
adhesive strip to bond another rubber compound to the metal, fibre or fabric upon
curing. This approach can be applied to both sulphur and peroxide cured compounds.
Another technique is to apply the metallic coagent, in the form of a dispersion, between
the rubber stock and the metal prior to curing. In this case, the metallic coagent
functions as a reactive adhesive, which is activated by peroxides.
Saret 633 is the best coagent for adhesion, but Saret 634 is a good alternative when
abrasion resistance, tear strength or moisture resistance are needed in addition to
adhesion.
Acknowledgements
The author would like to acknowledge the many contributions of Walt Nagel, Gary
Ceska and Al Tuccio in developing this technology.
238
References
1. R. Eirich, Science and Technology of Rubber, Academic Press, Inc., New York,
1978.
2. T. Howath, J. A. Cornell and L. R. Olson, Rubber World, 1963, 148, 5, 69.
3. P. Touchet, G. Rodriquez, P. E. Gatza, D. P. Butler, D. Crawford, A. R. Teets,

H. O. Feuer and P. Flanagan, inventors; USA, Secretary of the Army, assignee; US
Patent 4,843,114, 1989.
4. R. C. Klingender, M. Oyama and Y. Saito, Rubber World, 1990, 202, 3, 26.
5. R. C. Klingender, M. Oyama and Y. Saito, Presented at the 135th Meeting of the

ACS Rubber Division, Mexico City, Mexico, Spring 1989, Paper No.62.
6. A. Saito, A. Fujino and A. Ikeda, Elastomer Developments: Materials,

Applications, Processing and Performance, Society of Automotive Engineers,
Special Publication, USA, 1989, 890359.
7. S. Martin, T. Melvin and J. K. Pieroni, inventors; Uniroyal, Inc., assignee; US

Patent 4,266,772, 1981.
8. C. M. Roland, inventor; The Firestone Tire & Rubber Company, assignee; US

Patent 4,720,526, 1988.
9. P. Molitor, inventor; Spalding and Evenflo Companies, Inc., assignee; US Patent

4,726,590, 1988.
10. R. Costin, W. Nagel and R. Ekwall, Rubber Chemistry and Technology, 1991,
64, 2, 152.
11. R. Costin, R. Ekwall and W. Nagel, Presented at the International Rubber

Conference (IKT91), Deutsch Kautschuk Gesellschaft EV, Essen, Germany, 1991,
p.205.
12. R. Costin, W. Nagel and R. Ekwall, Kautschuk und Gummi Kunststoffe, 1992,
45, 8, 648.
13. R. Costin, W. Nagel and R. Ekwall, Rubber World, 1992, 206, 5, 27.
14. R. Costin and W. R. Nagel, Rubber & Plastics News, 1995, 24, 19, 19.
15. R. Costin and W. Nagel, Gummi Fasern Kunststoffe, 1995, 48, 5, 796.
239
17. R. Costin and W. R. Nagel, Rubber & Plastics News, 1996, 25, 17, 14.
18. H. Xie and Y. Feng, Polymer, 1988, 29, 7, 1216.
19. C. Keller, Presented at the 132nd Meeting of the ACS Rubber Division, Fall,
1987, Paper No.74.
20. ASTM D816-82

Standard Test Methods for Rubber Cements, 2001.
21. ASTM D412-98a

Standard Test Methods for Vulcanised Rubber and Thermoplastic Elastomers -
Tension, 2002.
22. ASTM D1084-97

Standard Test Methods for Viscosity of Adhesives, 1997.
23. ASTM D395-03

Standard Test Methods for Rubber Property - Compression Set, 2003.
24. W. R. Nagel, Adhesives & Sealants Industry, 1997, 4, 4, 36.
26. W. R. Nagel, Cure Concepts, 4 Volumes, Sartomer, Exton, PA, USA, 1999.
240
9
Rubber to Fabric Bonding
D. Wootton
9.1 Introduction
Many of the frequently encountered rubber articles are in fact rubber/textile composites.
In order to obtain the optimum performance from such products, it is essential that the
various components are adequately bonded together.
Generally, this adhesion is obtained by prior treatment of the fabric, although there are
other ways by which adequate adhesion can be obtained. Needless to say, the methods
used are largely dictated by the type of fibre being used, the polymer to which it is to be
bonded and final application of the composite product. The various methods of adhesion
are discussed in this chapter, together with other factors which can affect adhesion. Finally,
the environmental aspects of the various treatments are considered.
9.2 Adhesive Systems

9.2.1 Aqueous Fabric Treatments
The standard aqueous treatment for textile adhesion is based on resorcinol/formaldehyde
resin/latex (RFL) dip systems. A typical formulation for such an adhesive dip is given in
Table 9.1.
The actual ratios of resorcinol to formaldehyde and of resin to rubber solids may be
varied within reasonable limits, the generally accepted optimum ratios being between
1:1.5 and 1:2 for the resorcinol to formaldehyde and between 1:5 and 1:7 for the resin to
rubber ratio. Within these limits, it is possible to fine tune the RFL formulation to suit
the particular rubber compound with which it is to be used. Generally, however, it is
more convenient to use a standard dip formulation for most applications, to avoid
excessive complexity, while still maintaining perfectly adequate adhesion levels to a wide
range of rubber compounds. For most applications, the preferred latex used is a styrene/
butadiene/vinyl pyridine (VP) terpolymer latex.
The RFL adhesive dip is prepared by dissolving the resorcinol in water, adding the
formaldehyde and then the alkali as condensation catalyst, to produce the aqueous solution
of the resin condensate. This generally takes place at room temperature in about 6 hours.
241
Commercial rubbers

RFL system formulation
Table 9.1 Formulation of RFL system for rayon cord

Component Parts (wet) Parts (dry)
Resorcinol 9.4 9. 4
Formalin (37%) 13.8 5. 1
Sodium hydroxide (10%) 7.0 0. 7
Water 157.8
VP latex (40%) 212.0 84. 8
Water 100.0
TOTAL 500.0 100. 0
This resin solution is then added to the latex, with gentle stirring to ensure good mixing.
The completed dip is then allowed to mature for a further 24 hours before use.
Although this procedure has been used for many years, alternative methods can offer certain
advantages. In an alternative method, instead of allowing the resin precondensation to
occur prior to its addition to the latex, a single shot method may be used. The resorcinol
solution and formaldehyde are added to the latex before the addition of the alkali; the
addition of the alkali to the mixture then allows the resin to condense in the presence of the
latex. In so doing the resin partially replaces the stabilising surfactants on the latex particles
and gives a much more intimate dispersion of the resin throughout the rubber phase, in
effect forming an interpenetrating network of resin in rubber, as the two materials are not
greatly compatible [1]. With this method of preparation, there are two significant advantages.
Firstly, there is greater control over the condensation reaction of the resorcinol and
formaldehyde (when the condensation is carried out separately, the exothermic reaction
can proceed too rapidly, and it is not unknown for a resin batch to turn solid before the
normal condensation time has elapsed). Secondly, the completed dip has a much improved
shelf life compared with the two-stage mixing method. With the two-stage mix, optimum
adhesion is only obtained within 24 to 72 hours of mixing, while the single stage mix will
maintain its adhesion levels for two to three weeks after mixing.
Another variation to the standard formulation is to use a precondensed novolak resin.

These are high solids (70%) solutions of acid-catalysed resins in water. They are of high
viscosity and strongly acidic (pH of around 2.0). Accordingly, the resin requires diluting
to a lower solids concentration and neutralising to a pH of greater than 8.5, so as not to
coagulate the latex; this is usually achieved by the use of ammonia. A typical formulation
for a novolak-based system is given in Table 9.2.
242
novolak resin
Table 9.2 RFL adhesive dip, using a novolak resin

Water 163.0
Novolak resin (70%) 19.1 13.4
Ammonia (SG 0.88) 3.5 1.2
Water 100.0
Formaldehyde (37%) 9.4 3.5
VP latex (40%) 202.4 81.0
Ammonia 2.6 0.9
TOTAL 500.0 100.0
This formulation is prepared by dissolving the resin in the aqueous ammonia solution
and then adding this to the ammoniated latex. The formaldehyde is then diluted and
added, slowly and with stirring, to the latex/resin solution. This completed dip is then
allowed to mature for at least 18 hours before use. In common with the single shot
mixture previously described, this formulation also has a very good shelf life after mixing.
In the formulations given in Tables 9.1 and 9.2, both sodium hydroxide and ammonia
have been used as the alkali catalyst for the resin condensation reaction. Both are suitable
for this, but work by Rijpkema and Weening [2] has shown that in the final dried and
cured RFL film, the two alkalis give somewhat different properties to the resultant film.
In particular, the use of ammonia gives a film with a much higher elongation than that
obtained by using sodium hydroxide; this gives greater flexibility to the film, resulting in
improved dynamic fatigue of the bonded composite.
The application of the RFL adhesive dips to the textile substrate is generally carried out
by immersion in a bath of the dip, followed by removal of excess dip by squeezing,
suction, air-knife, etc. The impregnated fabric is then dried, and finally baked to fully
cure the RFL dip film. The baking, to complete the crosslinking of the resin component
of the adhesive, can take place at temperatures between around 130 C and 225 C, with
the time varying from 15 to 20 seconds up to 2 minutes, depending on the nature and
weight of the substrate fabric being treated. The selection of curing conditions is mainly
dictated by the type of yarn used in the textile substrate, and certain modifications to the
formulations and processes may be needed for optimum adhesion with some yarn types,
as discussed in the following sections.
243
Cotton
Generally cotton fabrics do not require any adhesive treatment, as adhesion is largely
obtained by mechanical methods, due to the embedding of the free fibre ends into the
polymer matrix to which the fabric is being bonded. This mechanism has been studied
[3] and a relationship found between the number of protruding fibre ends and the level
of adhesion obtained.
If, for particular reasons, additional treatments are used, particularly aqueous based
ones, there can be difficulties in obtaining satisfactory wetting of the fabric, on account
of the naturally occurring waxes on the fibres.
Rayon (regenerated cellulose)
The standard system used for adhesion to these artificial continuous filament fibres is an
RFL; however, with the lower tenacity rayon yarns, it is possible to use a mixture of
latices, substituting up to 70% of the styrene/butadiene/VP latex with a standard styrene/
butadiene (SBR) latex. With the higher tenacity polynosic yarns (high tenacity, high wet
strength viscose rayon), it is preferable to use a higher proportion of VP latex (with the
necessary adjustment of water addition to maintain the required solids content), increasing
to between 60 and 80% VP latex content.
The rayon textile is then dipped through the RFL dip and the impregnated fabric dried
and baked, to cure the deposited dip solids. With these fabrics, exposures of 1 2 minutes
at between 130 C and 150 oC are sufficient to achieve good adhesion levels, the time
and temperatures being to some extent controlled by the weight of the fabric.
Polyamide (Nylon 66 and Nylon 6)
Again the standard RFL system is ideal for use with polyamide yarns and fabrics. With
these fibres, however, it is necessary to use higher levels of VP latex than with rayon, a
minimum of 80% VP latex being required to obtain the optimum levels of adhesion.
This is illustrated in Table 9.3.
Generally with polyamides, higher curing temperatures are required, compared with the
corresponding rayon treatments. Minimum temperatures of around 160 oC are needed.
It is also suggested that higher temperatures and lower exposure times can be used with
advantage with the single shot type dips [5], employing temperatures of 190 200 oC
but with exposure times of only 20 to 30 seconds instead of 100 to 120 seconds. Again,
244
Table 9.3 Effect of VP:SBR ratio on Nylon 66 adhesion

Latex % SBR Solids % VP Peel Adhesion kN/m
100 0 5.8
80 20 11.9
60 40 16.8
40 60 19.6
20 80 21.5
0 100 22.0
Test: 2-ply peel test using NR/carbon black compound see ASTM D4393-02 [4]
the practical drying and baking times tend to be dictated by the structure, weight and
final application of the substrate, rather than those shown to be possible in theory.
Polyester (polyethylene terephthalate)
Polyester yarns are generally much less reactive than the cellulosic or polyamide yarns,
and so require additional treatments to achieve adequate levels of adhesion.
While solvent pre-treatment with an isocyanate solution has been used, more commonly,
aqueous systems have been developed for the first stage of a two dip system, using standard
RFL systems for the second stage.
One of the earlier but very successful systems was the DuPont D417 or Shoaf system [6],
using an epoxy product with a blocked isocyanate as a first stage, to react with the
polyester surface, giving improved adhesion when followed with the RFL second stage
dip. The basic formulation for this is given in Table 9.4.
The polyester fabric is passed through this dip, to give a solids pick-up of approximately
0.5%, and is then treated at a temperature of approximately 225 to 230 C, to activate
the blocked isocyanate and form the reactive film on the substrate. After this pre-treatment,
the fabric is then dipped again with a standard RFL dip and cured, again using higher
temperatures of at least 200 C. This system gives very good levels of adhesion, and is
quite widely used in the treatment of polyester tyre cord.
Other systems have been developed to achieve a single stage treatment, overcoming
the adhesion challenges of polyester. One of the more successful of these is the Vulcabond
245
Table 9.4 Formulation for polyester pre-dip, DuPont D 417

Blocked isocyanate (40% dispersion) a 180.0 72. 0
Epoxy resin b 27.2 27. 2
Gum tragacanth solution (2%) 25.0 0. 5
Dispersant (50%) 0.6 0. 3
Water 1767.2
TOTAL 2000.0 100. 0
a Such as Grilbond IL6, a caprolactam blocked methylene bis(phenyl di-isocyanate).
Grilbond is a registered trade name owned by EMS - American Grilon
b Such as Denacol NER 010a, a liquid epoxy derived from epichlorohydrin and glycerol.
Denacol is a registered trade name, owned by Nagase Co
E system, in which the RF resin component of the RFL system is modified by co-
condensation with chlorinated phenol [7]. The recommended formulation for this system
is given in Table 9. 5. Polyester Emserwerke Nagase Co. RFL adhesive system Vulnax
International Ltd.
Table 9.5 Vulcabond* E RFL adhesive system

Water 165.8
Resorcinol 9.8 9.8
Formaldehyde (37%) 5.9 2.2
VP latex (40%) 121.5 48.6
Vulcabond E (20% solution) 197.0 39.4
TOTAL 500.0 100.0
* Vulcabond is a registered trade mark owned by Vulnax International Ltd
246
This system requires just a single pass through this modified RFL dip, again with the
need for high temperature curing, around 215 C.
Another approach to improve the adhesion of polyester has been developed, by many of
the yarn producers, whereby an activation pre-treatment is applied to the yarn during
spinning. This pre-activation replaces the need for special dip formulations and allows
good adhesion levels to be achieved using standard RFL dips. Again, higher temperature
curing is required than is generally necessary for polyamide yarns. The pre-treated polyester
yarns are now very widely used, particularly for general mechanical rubber applications,
such as conveyor belting, hose, and V-belt cord.
Aramid
Although chemically closely related to the standard nylon yarns (aliphatic polyamides),
the aramids (aromatic polyamides) do not give satisfactory adhesion levels if treated
with the standard RFL systems, as the aromatic groups partially sterically shield the
reactive polyamide groups in the polymer chain. Again, a two-stage dipping process is
required, but in this case, the pre-dip can be somewhat simpler than with polyester, and
a solution of the epoxy-based product on its own is generally sufficient to give the necessary
adhesion levels, when followed by a standard RFL dip.
Also, fibres pre-treated at the spinning stage are now available, requiring only RFL
treatment, although as with polyester, high treatment temperatures are required to achieve
the full levels of adhesion.
One disadvantage of the high temperature processing of aramid and polyester (at least
200 C) is that the achieved adhesion levels are much more affected by relatively slight
variations in the adherend rubber compound [8].
Adhesion to other polymers
The various systems described above have been designed for adhesion between the various
textile fibres and the basic hydrocarbon polymers, natural rubber (NR), styrene/butadiene
rubbers (SBR), polybutadiene (BR) and polyisoprene (IR). With slight modification to
these systems, good adhesion levels can be achieved with other polymers.
Generally, for those polymers for which a corresponding latex is available, such as
polychloroprene (CR) and nitrile rubber (NBR), the VP latex component can be partly
(from around 50%) or completely substituted by the corresponding polymer latex. Apart
247
from this modification to the formulation, the processing and performance are very similar
to that already described.
For other polymers alternative methods must be used. For example, for butyl rubber
(IIR) it has been found that treatment of the textile with a resorcinol/formaldehyde
resin solution will give significant improvement to the adhesion levels. This is often
increased still further by the use of an interply of a halogenated butyl polymer
(particularly chlorobutyl).
Another similar polymer, chlorosulphonated polyethylene (Hypalon), also requires special

modifications to achieve adequate adhesion, but in this case it is the basic polymer
formulation that is modified, by the addition of from 20 to 40% of NR; this gives a good
increase in achieved adhesion without too great a loss of the outstanding weathering and
ageing properties of the polymer.
9.2.2 Solvent-Based Adhesive Systems
Solvent-based systems have been used for the rubber coating of textiles for many
years [9], and are still widely used for many applications. Initially solvent spreading
or coating, using a solvent solution or dough of the rubber compound, was primarily
a simple technique to achieve a thin coating of rubber on the surface of the fabric.
Nowadays, there is much greater attention given to achieving high levels of adhesion
between the textile.
The use of a solvent solution of an isocyanate as the predip for polyester textiles, followed
by an aqueous RFL dip has already been described. The main solvent systems employed
today involve the use of rubber cements or solutions, generally including adhesion
promoters such as isocyanates, to give the required levels of adhesion between the applied
coating and the textile substrate.
In a typical application, the rubber compound is dissolved in a mixture of suitable solvents

(usually a mixture of aliphatic, aromatic and chlorinated solvents) to give the desired
solids content and viscosity for spreading. This dough is then applied to the fabric by
spreading, using a knife system to control the thickness and evenness of the applied
coating. In this way the required final thickness of coating is achieved by a number of
passes, with solvent evaporation between coats. In order to achieve the required adhesion
levels, the chosen adhesion promoter is usually only necessary in the first one or two
applied coats, with the required final coating thickness being built up with only the base
compound dough.
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Another area where solvent treatment is generally required is in the treatment of heavy
cabled cords for cut-edge V-belts. Here complete penetration of the cord is required, in
order that on cutting the belt sections from the cured sleeve the integrity of the cord is
maintained and no fraying of the cord occurs. This requires cutting across the thickness
of the cord at a very low angle, possibly over a length of around 20 cm.
The major disadvantages associated with these solvent systems relate to the environmental
aspects, which will be considered later.
9.2.3 In Situ Bonding Systems
All the systems described in Sections 9.2.1 and 9.2.2 have been treatments applied to the
textile before its incorporation into the rubber matrix. However, systems also exist in
which certain additives can be included in the rubber formulation to promote adhesion
directly with the fabric, without the need for any textile pre-treatment. These are the in
situ or direct bonding systems.
These systems rely on the inclusion into the rubber matrix of resorcinol (or a resorcinol/
formaldehyde precondensate) together with a methylene donor. The addition of these
two components will give a moderate level of adhesion, this can be greatly enhanced by
the use of a fine particle size hydrated silica.
The original methylene donor used for this system was hexamethylene tetramine. While
this was perfectly adequate as a methylene donor from the adhesion standpoint, it also
significantly affected the cure system, and thus alternative materials have been used,
especially hexamethoxy methyl melamine.
These systems give good levels of adhesion with loomstate (untreated) rayon and polyamide
textiles, and can improve adhesion levels with cotton fabrics. However, in order to achieve
satisfactory levels with polyester, it is necessary to use a pre-treated polyester yarn. Also
with polyester, the amine residues from the methylene donor may cause significant
degradation of the polymer, giving loss of strength. Great care is therefore needed in selecting
the most appropriate methylene donor, if such systems are to be used with polyester fabrics.
These systems act by the formation, within the rubber matrix, of a resorcinol/formaldehyde
resin; this migrates to the rubber/textile interface and there reacts with the active groups in
the textile to give a chemical bond. On account of this migration to the surface of the
rubber, it is essential that there is sufficient of the precursors in the rubber to achieve the
necessary concentrations at the interface to achieve adequate adhesion. As the resin will
also migrate backwards, into the bulk of the rubber as well as to the surface, it is considered
249
necessary that the layer of compound, containing the adhesion promoters, be at least 0.25
mm in thickness, to achieve the required levels of adhesion. This consideration therefore
rules out the use of the direct bonding systems in spreading applications, as it would not be
possible to achieve the necessary concentration of adhesion promoters by this technique.
These systems can be used alone, with untreated fabrics. However, if they are used in
conjunction with adhesive dipped fabrics, both systems will contribute to the adhesion,
and achieved levels can be significantly higher than with either system alone.
9.3 Mechanisms of Adhesion
The mechanisms whereby adhesion is obtained between textiles and rubber can be
considered in two separate areas, namely the interfaces between the textile and the dip
layer, and between the dip and the rubber matrix.
With cotton-based fabrics, the basic adhesion is achieved purely by mechanical means,
due to the embedding of the individual fibre ends within the rubber matrix [3]. On
peeling the bond, it is necessary either to pull these fibre ends out of the rubber or, if this
force is greater than the tensile strength of the fibres, to break the fibres. This mechanical
adhesion applies basically to all staple fibre-based fabrics, where there is no additional
adhesive treatment. However, in the case of the synthetic staple fibres, the individual
fibres are smooth and cylindrical, compared with the rougher surface produced by the
scales on the cotton fibre surface. The adhesion levels obtained with these yarns are
significantly lower than with cotton.
9.3.1 Dip/rubber Interface
Considering the treated fabrics, the adhesion between the dip film and the rubber matrix
is derived mainly from the direct crosslinking of the latex polymer component with the
rubber in the matrix compound. There is also some slight contribution from purely
mechanical action, due to the penetration of the rubber matrix into the weave structure
of the fabric, but this is minimal with all but the most open weave structures. Similarly,
there is a small contribution from interaction between the resin component of the dip
and the rubber in the matrix compound.
In order to achieve the direct crosslinking between the dip latex rubber and the matrix
polymer, it is, of course, necessary for the curatives, sulphur and accelerator (or active
groupings derived from them), to migrate from the matrix into the dip film. Consequently,
the actual formulation of the curing system can have significant effects on the levels of
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adhesion achieved. In order for adequate proportions of the required substances to migrate,
it is desirable that the curing system has a long scorch time and relatively slow cure, to
allow time for the formation of the active species and migration into the dip layer. With
fast curing systems, or with short, high temperature cures, the final levels of adhesion
achieved are generally lower than with slower systems or longer, lower temperature cures.
In the extreme case of sulphurless cures, adhesion levels are very low, due to the lack of
suitable intermediates to migrate. These effects are shown in Table 9.6.
As can be seen from these results, the curing system exerts a significant effect on the
adhesion levels. As the speed of cure increases (as shown by decreasing cure time), so the
levels of adhesion fall; although the scorch time of CBS systems are greater than with
MBTS alone, the cure is faster and the adhesion achieved is reduced. With the activated
Table 9.6 Effect of curing system on adhesion

Adhesion Accelerator Accelerator dosage Sulphur level Cure
(Peel) (kN/m) (phr) (phr) (min at 153 C)
21.0 MBTS 0.6 2.5 15.0
19.1 NOBS 0.5 2.5 15.0
18.7 CBS 0. 5 2.5 12.5
18.0 MBTS 0.4 2.5 12.5
DPG 0.2
13.7 MBTS 0.4 2.5 10.0
TMTD 0.1
12.0 CBS 2.0 1.0 12.0
10.5 CB S 4.0 0.5 15.0
2.1 BDTPTS 1.0 Nil 12.0
TMTD 3.0
1.7 CBS 2.0 Nil 15.0
BDTPTS 3.0
BDTPTS: bis(di-ethyl thiophosphoryl) trisulphide
CBS: N-cyclo hexyl benzthiazyl sulphenamide
MBTS: mercaptobenzothiazole disulphide
NOBS: N-oxy di-ethylene benzthiazyl sulphenamide
TMTD: tetra-methyl thiuram disulphide
DPG: N, N diphenyl guanidine
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systems, MBTS/DPG and MBTS/TMTD, the greater the activation and the faster the
cure, so the levels of adhesion decrease and, with the sulphurless cure, TMTD alone,
there is virtually no adhesion other than the purely mechanical contribution.
9.3.2 Dip/textile Interface
In considering the other side of the adhesion equation, that is between the textile and the
dip, there is no simple explanation of the mechanisms involved. It is generally accepted
for rayon and nylon fibres, that the main contribution arises from chemical reaction
between the resin component of the dip and the textile polymer, but it is suggested that
mechanical and physical interactions also contribute significantly to the total adhesion
[10]. The contributions ascribed to these various effects are summarised in Table 9.7.
Such reactions between the resin and the fibre will also account for the effectiveness of
the in-situ bonding systems for nylon and rayon fabrics.
With polyester however the mechanisms are even less clearly understood. In the case of
the isocyanate-containing systems it has been suggested that there is a direct chemical
reaction between the isocyanate and the polyester groups. However, considering the
general low reactivity of the polyester linkages, as shown by the high stability of the
polymer generally, and the low level of hydroxyl groups in the polymer chain terminating
groups, it is unlikely that such reactions would contribute greatly to the overall levels of
adhesion achieved. Work with such systems [11] has suggested that the isocyanates react
Table 9.7 Mechanisms contributing to adhesion (After Schoon & Zierler) [10]
Mechanism Contribution to Adhesion %
Direct mechanical: 15
penetration of dip/rubber into the structure of the fabric
Diffusion: 5
microscopic or molecular diffusion into the yarn
filaments
Primary chemical bonds: 60
direct covalent chemical linkages between the resin and
textile fibre
Secondary chemical bonds: 20
mainly hydrogen bonding
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to give a polyurethane, which is much more thermodynamically compatible with the

surface of the polyester, and therefore in effect provides a different and more reactive
surface to the adhesive dip.
9.4 Other Factors Affecting Adhesion
In the ideal situation, a treated textile would immediately be incorporated into the polymer
matrix and the final product cured immediately. In practice this is rarely, if ever the case,
and therefore the treated textile must be stored (and often transported) before it is
incorporated into the polymer.
9.4.1 Storage of Treated Textiles
After treatment, the fabric or cord should be stored in a cool, dry and dark environment.
When stored under such conditions, the adhesion properties will be maintained for a
considerable period; often, a period of six months is recommended as the shelf life of
such products, but it has been found that even after periods of eighteen months to two
years, the adhesion levels have not been significantly degraded. It is always recommended,
however, that after a prolonged storage, the adhesion properties of the treated textile be
evaluated before committing it to production. In the event of some loss of adhesion, it is
usually possible to recover the required levels by redipping the fabric or cord before use
and regaining the original adhesion levels.
Of the three parameters, heat, moisture and light, the most critical of these is light.
Studies have shown that light, ozone and humidity all cause degradation of adhesion
[12], with the most significant effects occurring within the first few hours of exposure.
Other work [13] has shown that over 50% of the original adhesion can be lost by exposure
to daylight for just 48 hours, while storage open, (i.e., opened but not necessarily exposed
to direct light) will result in some 40% adhesion loss.
Other studies of these effects [14] have indicated that some protection against this degradation
can be obtained by incorporation of a wax emulsion into the RFL dip, which would give rise
to a protective film on the surface of the treated textile. This work also showed that
conventional anti-ozonants or UV absorbers did not give any significant protection, thereby
indicating that the loss of adhesion arose from the attack on the surface butadiene double
bonds in the dip film, reducing the co-curing of the dip rubber with the matrix polymer.
Moisture is generally less of a threat to adhesion; with the relatively low moisture regain
of Nylon (4.5% maximum and typically around only 2% in dipped fabrics) and of
253
polyester (0.5% maximum) the moisture content of the textile is not usually sufficient to
interfere with the adhesion or cure of the final composite. In the case of rayon, the high
regain of around 11% can give rise to problems, due to the creation of porosity in the
final product as the moisture is boiled off during cure. With such fabrics predrying before
calendering or spreading is usually necessary.
9.4.2 Adhesion in Service
Frequently, the final composites are subjected to various severe environments during
service. These can include heat, flexing and moisture.
On exposure to heat, there is a progressive loss of adhesion, with levels dropping to

around 30 to 40% of the original values after 7 days ageing at 100 C. Although this
may seem rather drastic, the retained adhesion is usually perfectly adequate for the
application: the original values obtained are generally significantly above the specified
levels for the application, and these specified levels usually include a built in safety margin.
Looking at the effects of moisture, or more drastically immersion in water, there is some
loss of adhesion with both nylon and polyester fabrics. These losses are usually of the
order of 10 20% of the original values, but on drying out the composite, the original
levels are regained, to within less than 5% loss. These effects are related to the direct
contact of the textile component with water, as is the case with cut edge conveyor belting.
In many other applications, there is no direct contact of the textile with water, as the
edges and joints are sealed to prevent such ingress. Without the direct contact it is most
unlikely that there is any affect on the adhesion levels.
9.5 Environmental Aspects
All of the systems described present certain environmental aspects, which require
consideration during the operation of the processes. These can conveniently be considered
for the different stages of production.
9.5.1 Storage and Handling
All liquid materials must be in secure vessels, which must be bunded to contain any
spillage or leakage from the primary storage vessel. With certain of the materials -
formaldehyde, ammonia and the various solvents - additional local exhaust ventilation
is required to restrict the possibility of exceeding the imposed safe exposure levels for the
254
product. Additionally, standard personal protective equipment - gloves, goggles and

breathing mask - should always be worn when handling such materials. In handling
isocyanates, additional personal protective equipment is mandatory, as the authorised
exposure limits are exceedingly tight (long term exposure limit 0.02 mg/m3).
9.5.2 In Process
The different systems each present different aspects for attention. In the case of the
aqueous systems, the major concerns are again local exhaust ventilation, to prevent build-
up of fumes in the work place.
From the process itself, the exhaust from the curing ovens requires monitoring, for the
presence of formaldehyde vapour, ammonia, volatile organic compounds (VOC) and
particulates. With many of the more recent installations, conformance with the regulating
limits should not present much problem, but on occasion, some form of abatement system
may have to be installed.
With solvent systems (in the UK), these will probably fall within the regulation of the
Integrated Pollution Control regulations (soon to become the Integrated Pollution
Prevention and Control regulations). Here it is necessary that some form of abatement
treatment be applied to the exhaust systems, to control the VOC emissions. This may be
achieved either by a solvent recovery system or by an incineration process, in which case,
suitable precautions must be taken to ensure that the temperatures achieved during
incineration are high enough to eliminate all solvents and to prevent the formation of
other noxious by-products of oxidation. Usually temperatures in excess of 700 C are
required to ensure this; the heat generated by such processes can be recovered for process
heating, etc.
In the case of the use of in-situ bonding systems, the main problems here arise from an
increase of rubber fume on mixing and on opening the curing presses, but much work is
being done [15, 16] to reduce the effects of resorcinol and the resins on increased fume.
9.5.3 Wastes and Disposal
From the aqueous processes, the main process wastes are the residues and washings
arising at the end of processing runs. These generally contain latex and resin, but are
usually much less concentrated than the normal dips. Such residues are sometimes accepted
by the Water Authorities for treatment, provided that the pH, total solids and chemical
oxygen demand fall within the limits of Consent to Discharge. Frequently, it is necessary
255
to install some form of pre-treatment system to remove the bulk of solid materials, by
coagulation, flocculation and filtration, before the clarified liquor can be discharged to
drain. This then presents the problem of the disposal of the resultant solid matter, which
requires disposal as special wastes, either to special landfill sites or by incineration.
With the solvent processes, again the disposal of waste solvents and spreading compound
doughs has to be handled as special wastes, although often, recovery of the solvents
themselves is feasible.
From all of these systems, there remains the disposal of the process waste treated fabric,
from seams, ends, etc. These can be used for certain applications, by shredding the treated
textile and using it as a semi-reinforcing and bulking filler in rubber products such as
dustbin lids, traffic cones, and so on.
References
1. D. D. Eley and L. B. J. Pawlowski, Journal of Colloid and Interface Science,

1969, 29, 222.
2. B. Rijpkema and W. E. Weening, Proceedings of the 144th ACS Rubber Division

Meeting (IRC 93), Orlando, FL, USA, 1993, Paper No.142.
3. E. M. Borroff and W. C. Wake, Transactions of the Institution of the Rubber

Industry, 1949, 25, 1, 39.
4. ASTM D4393-02
Test Method for Strap Peel Adhesion of Reinforcing Cords or Fabrics to Rubber
Compounds, 2002.
5. B. Mitchell, Journal of the Institution of the Rubber Industry, 1975, 5, 151.
6. C. J. Shoaf, inventor; E. I. du Pont de Nemours and Company, assignee; US

Patent 3,307,966, 1967.
7. R. A. Edington and D. H. Aldred, inventors; no assignee; GB Patent 1, 140,

528, 1969.
8. W. Weening and W. H. Hupje, Kautchuk und Gummi Kunststoffe, 1972, 7,

25, 324.
9. C. Macintosh, inventor; no assignee; GB Patent 4,804, 1823.
256
10. Th. G. F. Schoon and L. Zierler, Kautschuk und Gummi Kunststoffe, 1970, 23,
12, 615.
11. R. E. Hartz, Journal of Applied Polymer Science, 1975, 19, 3, 735.
12. H. M. Wenghoeffer, Rubber Chemistry and Technology, 1974, 47, 5, 1066.
13. M. Fahrig, Rubber Technology International 98, 1998, 139.
14. Y. Iyengar, Journal of Applied Polymer Science, 1975, 19, 3, 855.
15. K. Meier, U. Goerl and S. Wolff, inventors; Degussa AG, assignee; US Patent
5,321,070, 1994.
16. K. Meier, U. Goerl and S. Wolff, inventors; Degussa AG, assignee; US Patent
5,470,905, 1995.
257
258
10
Bonding Rubber with Cyanoacrylates
R. Goss
10.1 Introduction
Cyanoacrylates were first introduced commercially in the late 1960s and into the consumer
market in the 1970s. Since then super glues have been used and are continuing to be
used in both industry and around the home for a huge variety of applications. There is
now a bewildering range of cyanoacrylates available to both the home user and particularly
the industrial user.
Cyanoacrylates offer an unbeatable combination of speed, simplicity and strength

particularly when faced with the need to join widely different materials. They will
bond metals, plastics, ceramics, wood, leather, paper, cork and rubber in any
combination without heat treatment and for most applications without the need for
surface pre-treatment.
There are many types of rubber available but most can be bonded with cyanoacrylates.
Polychloroprene, nitrile, natural rubber (polyisoprene), styrene butadiene rubber (SBR)

and butyl are amongst the types of rubber that can be readily bonded with cyanoacrylates.
Ethylene propylene diene monomer (EPDM) and fluroelastomers (Viton, registered trade
mark of DuPont) can also be bonded, although only with specific grades of cyanoacrylate.
Silicone rubber and thermoplastic rubber (Santoprene, registered trade mark of Advanced
Elastomer Systems) can be bonded with the aid of a primer. Typical applications and
techniques for bonding different grades of rubber are discussed in Section 10.11.
10.2 Liquid Cyanoacrylates
In liquid form cyanoacrylates are soluble in most organic solvents and insoluble in water.
Most grades are of high volatility and thus are irritating to the eyes and nose; low odour
grades are discussed in Section 10.12.1.3. Cyanoacrylates are generally available as
colourless liquids in a wide viscosity range from 3 mPa.s (i.e., a thin liquid) to a thixotropic
gel consistency in a wide variety of pack sizes. They should be stored in a cool dry place,
preferably at a temperature between 5 C and 8 C for optimum shelf life. Toughened,
coloured, flexible, UV curable and low-odour versions are also available.
259
Commercial rubbers
10.3 Curing of Cyanoacrylates
Cyanoacrylate adhesives contain an acidic stabiliser, which prevents the adhesive from
polymerising. The acid stabiliser is neutralised when the product is in contact with the
surface moisture. In general, moisture, which is normally found on all surfaces exposed
to the atmosphere, is sufficient to initiate curing within a few seconds. The moisture
neutralises the stabiliser and thus initiates the cure. Figure 10.1 represents the
cyanoacrylate in liquid form:
The large spheres represent the adhesive monomer,
The smaller spheres represent the acidic stabiliser,
The dark spheres represent the surface moisture.
During polymerisation (solidification of the adhesive) chains of adhesive molecules build

up on the surfaces and interweave to bind the surfaces together, see Figure 10.2.
The cure speed of a cyanoacrylate, if left open on a surface, will be quite sluggish,
because there is insufficient moisture and the adhesive will remain liquid for several
hours (although the cyanoacrylate will cure at the surface interface). When the adhesive
is between two close fitting surfaces, where there is moisture on both surfaces, the
cyanoacrylate will cure rapidly. The gap between parts should ideally be less than
0.1 mm (see Figure 10.3).
Figure 10.1 A cyanoacrylate in liquid form
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Figure 10.2 The initial chains form rapidly, giving cyanoacrylate adhesives their
characteristic fast bonding (cure speed) times
Figure 10.3 When the adhesive is between two close fitting surfaces the cyanoacrylate
cures rapidly due to the surface moisture on both surfaces
10.3.1 Factors Affecting Cure
The curing of cyanoacrylate adhesives is affected by:
i) The relative humidity in the local area,

ii) The gap between the parts,
iii) Volume of the adhesive applied,
iv) The ambient temperature,
v) Acidic residues, e.g., residues from surface treatment.
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10.3.1.1 Relative humidity
The optimum cure condition for cyanoacrylates is when the relative humidity (RH) is
between 40% RH and 60% RH. Lower RH, i.e., 20% RH, will result in a slower cure,
and high RH (80% RH) result in a faster cure. A dry environment (low RH) often occurs
when the work area heating system is switched on in the autumn months, thus drying
out the local air adjacent to the work station.
High RH can also be detrimental as the cyanoacrylate can sometimes cure so fast that the
adhesive cures before it has properly adhered to the surface and the resulting bond is poor.
Figure 10.4 shows how RH can affect the cure speed for an ethyl cyanoacrylate.
Figure 10.4 Graph showing how tensile strength develops with time on nitrile rubber at
different levels of humidity. At 100% strength the rubber fails before the adhesive bond
10.3.1.2 Gap Between the Parts
Cyanoacrylates are best suited to parts with small gaps (<0.1 mm). Some grades will
cure through gaps up to 0.5 mm or even 1 mm using activators, but as a good rule of
thumb the thinner the bond line the stronger the joint and the faster the cure.
10.3.1.3 Volume of the Adhesive Applied
If excessive adhesive is applied, there is insufficient surface moisture and the cyanoacrylate
will be slow to cure and may bloom (see Section 10.12.1). The adhesive should be applied
262
such that there is just sufficient to cover the joint. Dispensing equipment (see Section 10.9)
is recommended for production applications.
10.3.1.4 Ambient Temperature
The ambient temperature does not contribute significantly to the cure speed of the
cyanoacrylate but as with all chemical reactions if the ambient temperature is low, i.e.,
less than 5 C, then the cure speed will be longer. This may occur for example in a
maintenance application where a cyanoacrylate is used outdoors in winter. An activator
may be required to ensure a reliable cure (see also Section 10.8).
10.3.1.5 Acidic Deposits
Cyanoacrylates contain an acidic stabiliser, so if they come into contact with an acidic
surface the stabiliser is not neutralised and the cyanoacrylate remains liquid. Some
materials are naturally slightly acidic, e.g., paper, cardboard, cork and leather, and a
standard cyanoacrylate will either be slow to cure or be completely inhibited from curing.
Modified cyanoacrylates are now available which overcome the surface acidity and cure
well on these surfaces (see Section 10.4.1). Acidic deposits may also be present as a result
of an incorrect cleaning or surface preparation process.
10.3.2 Cure Speed
Under the right conditions (see Section 10.3.1), cyanoacrylates will gain handling strength
within the first minute or so. The two major factors affecting cure speed are the RH and
the gap. The definition of handling strength will depend on the actual application but is
generally regarded as the time when parts can be picked up gently without the adhesive
joint failing.
The cyanoacrylate should not be disturbed during the critical time when it is changing
from a liquid to a solid as the product may never gain its full strength.
10.4 Types of Cyanoacrylate
There are three major chemical types of cyanoacrylate adhesives. The major distinguishing
feature between these three is the size of the molecule.
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Cyanoacrylate cure speed
Figure 10.5 Full cure is achieved after 1224 h (rubber to steel). Approximately 60%
strength is achieved within the first minute
Methyl cyanoacrylate, the original cyanoacrylate ester, has the smallest molecule of the
three adhesives. Thus a larger number of molecules can be applied over a given area.
Consequently, a larger number of polymer chains can be formed - resulting in bonds with
a high tensile strength. Methyl cyanoacrylates are thus particularly suited to bonding metals.
The ethyl cyanoacrylate ester molecule is slightly larger than the methyl ester molecule
although adhesive properties are very similar. However because of their larger size, the
number of molecules per given area is less than that for methyl adhesives. This results in
a less rigid adhesive and is more suited to bonding rubbers and plastics.
The alcoxethyl cyanoacrylate ester molecule is considerably larger than that of both the
methyl and ethyl esters and this results in a slower curing adhesive. Whilst a slower cure
speed has advantages when assembling intricate parts which have to be aligned after contact,
it is the low volatility which gives a butyl cyanoacrylate adhesive its major advantage. Its
larger heavier molecule is less volatile than those of the other two esters, hence odour is
less and the possibility of blooming (a white deposit adjacent to the bond line) is eliminated.
10.4.1 Bonding to Acidic and Porous Substrates
Some substrates, for example paper, cork, cardboard, leather, dichromated metals and
some fabrics can be slightly acidic, and since the cyanoacrylate contains an acidic stabiliser
the adhesive will be very slow curing or may not cure at all. For these substrates, a
264
surface activator or surface insensitive formula must be used to obtain short handling
times. The surface sensitive grade includes a special additive which can convert surface
contamination into an activating species towards cyanoacrylates and thus allow the
adhesive to continue curing in the usual way.
This additive is now used in some consumer cyanoacrylates because it reduces the
dependence on surface moisture to cure and ultimately leads to good bond strength
with many substrates.
Similarly because these surface insensitive cyanoacrylates are good general purpose
bonders, they are particularly suited to the maintenance sector where the condition of
the substrate is not well defined.
This family of cyanoacrylates are fast curing. However they may cure too quickly in
some applications, and fail to adhere properly to the surface.
10.4.2 Toughened Cyanoacrylates
Cyanoacrylates can be toughened by the addition of rubber particles. These modified ethyl
cyanoacrylates show superior peel strength and often high humidity resistance. The principle
of toughening the adhesive is that the rubber particles minimise the propagation of cracks
as the adhesive is subjected to high peel or cleavage loads (see Figure 10.6).
The rubber toughened cyanoacrylates are particularly well suited for rubber to metal
bonding applications, although they are slightly slower curing than the standard ethyl
cyanoacrylates.
Figure 10.6 The crack only gets as far as the rubber particle and the stress is
dissipated. The crack then has to reform, only to meet another crack arrester. The
resulting adhesive bond line is therefore considerably more resistant to peel and
cleavage loads than a conventional cyanoacrylate
265
10.4.3 Flexible Cyanoacrylates
Recent introductions in cyanoacrylate technology include a modified ethyl monomer

with considerably improved flexibility over the standard product. These cyanoacrylates
were developed for the loudspeaker industry where a degree of flexibility in the bonded
joint is desirable.
10.4.4 UV Curing Systems
Another recent introduction are UV curable cyanoacrylates. Light curing cyanoacrylate

adhesive technology combines the processing benefits of cyanoacrylate and light-curing
adhesives. Light-curing cyanoacrylate adhesives offer the ability to rapidly cure exposed
adhesive through exposure to light and the reassurance of the standard cyanoacrylate
cure mechanism to cure adhesive in areas shadowed from light.
10.5 Design Considerations
To obtain the best results, joints should be designed for adhesive bonding. Cyanoacrylates
can offer significant benefits over other methods of joining rubber. There are, of course some
additional factors to be assessed when contemplating the use of adhesives. The cyanoacrylate
must suit the substrates, be compatible with production methods, transmit anticipated service
loads and endure operational environments. Consideration must also be given to surface
preparation, application methods, curing time and the cost of this method of bonding.
The loads acting on a bonded joint will result in various types of stresses. Stresses are normally
expressed in N/mm2. In the case of pure tensile and pure compressive loads the stress
distribution over the bond line is very even, so that every part of the bond line carries the
same load, and to calculate the stresses, the acting forces are simply divided by the bond area.
In reality pure tensile and pure compressive loads are very rare and we are confronted more
with shear, cleavage and peel loads. The joint stress distribution, i.e., the location of the
stresses across the bond line, is less uniform and more complicated to calculate.
As a general rule, increase the joint width rather than the overlap area. Note from the stress
distribution curve (Figures 10.7 and 10.8), that the ends of the bond resist a greater amount
of stress than does the middle of the bond. If the width of the bond is increased, the bond
area at each end also increases; the overall result is a stronger joint. Rubbers and elastomers
are often flexible materials and although cyanoacrylates are by nature relatively rigid adhesives
(although see Section 10.4.3), good results can be obtained for a wide range of applications.
The designer should consider especially the effect of cleavage and peel stresses on the joint.
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Figure 10.7 Highest stresses are at the outside edge of the bonded area
Figure 10.8 Increasing the bond width is more beneficial than increasing the overlap length
10.5.1 Minimise Peel and Deavage Loads
Joints subjected to cleavage or peel loads are usually the weakest joints and have the lowest
strength. Cleavage loading will concentrate the stress at one end (or side) of the joint, and
this can result in uneven loading on the adhesive and possibly premature failure. Peel and
cleavage loads should therefore be eliminated as far as possible. See Figure 10.9 for some
proposals of how to convert peel or cleavage into more favourable loads.
267
Figure 10.9 Peel loads and their conversion by means of design measures
10.5.2 Bond Line Thickness
The gap between the parts, and therefore the thickness of the cyanoacrylate film, has an
important bearing on the characteristics of the joint. A thick bond line (>0.5 mm) will
generally be a weakening feature as the mechanical strength of the cured cyanoacrylate
film is likely to be less than that of the rubber or the other substrate. For rubber bonding
applications, thin films (<0.05 mm) often give the best results. For example, cyanoacrylates
bond exceptionally well to nitrile rubber, and substrate failure of the rubber is the typical
failure mode where the bond line is 0.05 mm or less. Adhesive bonds will always be
susceptible to environmental attack and a thick bond line offers a ready path for access
by moisture or other solvents. However, if dissimilar materials are being bonded and
there is a differential change in the dimensions of the two surfaces, due for example to
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differential expansion by heating, then the thicker film may be better able to accommodate
this without being stressed to failure.
10.5.3 Special Requirements for Bonding with Cyanoacrylates
Cyanoacrylates cure quickly and care should be taken during the selection process to
ensure that sufficient time is made available to position parts prior to the adhesive curing.
The fast cure of cyanoacrylates can in many applications offer benefits to the production
engineer, as process times will be fast and clamp times are usually short. The thinner the
bond line the faster the cure. Note however that the joint must not be disturbed during
the cure cycle as the cyanoacrylate will not properly re-configure itself if the molecular
chains are broken at the start of the polymerisation.
Cyanoacrylates are best suited to the smaller bond areas in rubber bonding applications,
as larger areas often require more time to position the parts, and the fast cure of
cyanoacrylates make this difficult. Typical applications are illustrated in Section 10.11.
10.5.4 Internal and External Mould Release Agents
Internal and external mould release agents are used to guarantee easy release of moulded
or pressed plastic or rubber parts. They often produce surfaces that can be difficult to
bond. Mould release agents are described as internal if they are already mixed into the
granules and take effect during the processing of the plastic or rubber. These mould
release agents may be distributed throughout the whole material, so that even mechanical
abrasion may not be effective.
External mould release agents, on the other hand, are sprayed into the open mould.
They are often based on paraffins, soaps and oils, e.g., silicone oil. Because of the manner
of treatment, these mould release agents may be found not only on the surface but also in
layers near the surface. Proprietary non-transfer mould release agents such as Frekote
are recommended to ensure optimum bonding surfaces.
If mould release agents are present, cyanoacrylates can sometimes be used successfully in
conjunction with a primer to give excellent bond strengths.
10.5.5 Successful Joint Design
Bond stresses, materials, type of cyanoacrylate, surface preparation, method of application

and production requirements should all be considered in relation to each other at the
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outset. Cyanoacrylates should not be selected for applications where the parts are subjected
to continuous immersion in water, or if one of the substrates is glass, as the durability
there is likely to be poor.
10.6 Bonding to Silicone Rubber [see also Chapter 12]
Silicone rubber is difficult to bond with cyanoacrylates. The adhesive does not wet the
surface properly without special surface treatment, due to the very low surface energy,
and therefore will not bond. Polypropylene (PP), polyethylene (PE), polytetrafluoro
ethylene (PTFE) and acetal plastics and Santoprene rubber also fall into this category
and cannot be bonded without prior surface preparation.
Surface primers are now available which can act as an adhesion promoter. Loctite 770
(Henkel Loctite Adhesives Ltd) is a heptane-based primer which can be brushed or sprayed
onto the surface of the rubber and then used with an ethyl-based cyanoacrylate.
This primer is recommended for PP, PE, Santoprene and other similar rubbers as well as
PTFE. It frequently enables cyanoacrylates to successfully bond polyacetals as well.
The primer should be applied once only to the surface; over-application will nullify the
effect of the primer. The on-part life of the primer is typically eight hours, but best results
are achieved if the surfaces are bonded immediately.
The Loctite 770 primer contains a fluorescent additive to reveal where the primer has
been applied. Treated parts can be inspected simply by passing them under a low intensity,
blue UV lamp.
Flame treatment, corona discharge, plasma etching or chromic acid are also acceptable
methods for pre-treating these types of rubbers and plastics. In some applications, surface
roughening can be a simple, low cost method of increasing the bondability of the rubber.
Surface roughening increases the bondability by dramatically increasing the number of
mechanical interlocking sites.
10.7 Environmental Resistance
There is such a wide range of substrates, joint configurations, bond areas, gaps, and
applications that cyanoacrylates can be used for, that it can be difficult for the supplier
to give accurate information about how a particular grade of cyanoacrylate will perform
for individual applications. Hot, wet environments should in general be avoided,
270
particularly constant immersion in water. Conversely, however, nitrile rubber bonded

with an ethyl cyanoacrylate shows excellent retention of strength after 1,000 hours at
40 C/95%RH. If the same cyanoacrylate were to be used for steel, the joint would
normally be expected to degrade after less than 100 hours at 40 C/95%RH. Excellent
retention of strength is also achieved for the bonding of nitrile rubber with
cyanoacrylates in oil or glycol. The substrate and the joint configuration will determine
the success of the joint. A useful test is to subject the parts to six weeks in an
environmental chamber where the conditions are 40 C/95%RH. It is often the case
that a bonded part will show signs of failure within the first 1,000 hours (six weeks) in
this environment. Figure 10.10 demonstrates the interpretation of the various outputs
of an environmental test.
In selecting a cyanoacrylate for a particular application, one of the most important

considerations is the environment or surroundings to which the adhesive will be
subjected.
Figure 10.10 The graph shows three possible results for an environmental test. Result
A is clearly ideal as there has been no degradation in strength. Result B shows an
initial fall in strength but no further degradation, and provided the strength remaining
still adequately meets the specification, this result may be acceptable. Result C is
clearly unacceptable as the strength has continued to fall during the test
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Thermal cycling and humidity are usually the most aggressive environmental factors for
a cyanoacrylate and the end user should conduct appropriate trials to ensure the adhesive
meets all requirements.
10.7.1 Glass Bonding
Cyanoacrylates are not recommended for permanent bonding of rubber to glass or glazed
ceramics as the cyanoacrylate will de-bond from the glass after a relatively short time
(typically 16 weeks).
10.7.2 Hot Strength
Cyanoacrylates cure to become thermoplastics and have a glass transition temperature

of 120 C. The products therefore have a typical operating temperature range of 50 C
to +80 C although many grades will survive higher temperatures. Figures 10.11, 10.12,
10.13 and 10.14 show the hot strength for an ethyl cyanoacrylate and a modified
cyanoacrylate with high temperature additives.
For the cyanoacrylate with the high temperature additives, the data are presented slightly
differently as the adhesive gains hot strength as it is aged at temperature. However, it can
be seen that there is still a 50% improvement in the performance.
Figure 10.11 Hot strength for a standard cyanoacrylate tested at temperature

indicated and given as a percentage of room temperature strength.
Test Procedure: Shear Strength ASTM D1002/DIN EN 1465 [1, 2]; Substrate: Grit
blasted mild steel lap shears; Cure procedure: 1 week at 22 C
272
Figure 10.12 Heat ageing for a standard cyanoacrylate aged at temperature

indicated and tested at 22 C and given as a percentage of the initial room
temperature strength
Test Procedure: Shear Strength ASTM D1002/DIN EN 1465 [1, 2]; Substrate: Grit
blasted mild steel lap shears; Cure procedure: 3 days at 22 C
Figure 10.13 Heat ageing for a cyanoacrylate with high temperature additives,
aged at temperature indicated and tested at 22 C and given as a percentage of
initial room temperature strength
273
Figure 10.14 Heat ageing/hot strength curve for a cyanoacrylate with high
temperature additives, aged under conditions indicated and tested at temperature
10.8 Activators
Activators are often required where the cyanoacrylate needs to be cured through a large
volume or where there is adhesive outside the joint line. Unlike primers, activators do
not improve the adhesion, but improve the cohesion of the cyanoacrylate by guaranteeing
proper curing.
A typical example of this is where a cyanoacrylate is used to tack wires onto a printed
circuit board (PCB). If an electrical modification is made to the PCB, a wire is taken
across the PCB and must be held securely down onto the PCB. A high viscosity
cyanoacrylate is applied to the PCB and the wire is placed into this drop of adhesive. The
activator is applied by spray over the area and the cyanoacrylate cures in seconds.
Activators may also be pre-applied to a surface. Note however that the active ingredient
in the activator is an amine which may oxidise fairly quickly, so the on-part life of some
of these activators may be less than a minute. Different concentrations of activators are
available for individual applications.
Cyanoacrylates are widely used for the manufacture of loudspeakers and one application
is the bonding of the rubber surround to the chassis where large gaps often exist and an
activator is used to ensure complete cure. The activator is sprayed over the bond line and
the cyanoacrylate is cured within a few seconds.
Some activators contain a fluorescent additive to allow easy inspection. The activators
are solvent-based and compatibility tests are recommended before use.
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UV curing cyanoacrylates are often an excellent alternative option if the use of activators
is undesirable (see also Section 10.4.4).
10.9 Application Methods for Cyanoacrylates

Cyanoacrylates can be dispensed precisely, cleanly and reliably using a range of dispensing
equipment, ranging from simple hand-held dispensers to fully automatic systems
incorporated into purpose-built special production equipment.
The most common principle of dispensing is to use the pressure/time system as described
in Section 10.9.1.
10.9.1 Pressure/Time Systems
The adhesive is put under pressure and the dispense valve is opened for a certain time to
provide the correct quantity of adhesive (see Figure 10.15). Since the cyanoacrylate
contacts the pressurised air, the dryness of the air is important and an air filter on the
mains air line is recommended. A pressure/time system is best suited for cyanoacrylates
up to a viscosity of 5,000 mPa-s, i.e., self levelling products.
Figure 10.15 A pressure/time dispenser
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A pressure/time system usually consists of a reservoir, a dispense valve and a controller.

The type of dispense valve depends on whether it needs to be hand-held, stationary or
advancing, and if there are standard or high precision requirements.
The type of application and workplace conditions, such as production rate, dispense
quantity and cure speed will determine whether manual, semi-automatic or fully automatic
dispensers will be required.
A number of dispense valves are available for dispensing cyanoacrylates including pinch
valves, diaphragm valves and seat valves. The wetted parts are typically manufactured
from PTFE or acetal to prevent premature curing and often incorporate some form of
stroke adjustment for fine-tuning of the dispense characteristic.
One of the major benefits of the pinch valve is that the fast curing cyanoacrylate is not in
contact with any moving parts. These valves have been used in a wide range of production
applications for many years.
10.9.2 Syringe Systems
Cyanoacrylates can be dispensed via a syringe system although care is required to

ensure that the follower bung does not bond itself to the side walls of the syringe as the
product is dispensed. Higher viscosity or gel products are generally more suited for
syringe systems.
10.10 Health and Safety and Handling Precautions
Cyanoacrylates have been used in industry for many years with an excellent safety record.
Vapour problems will not normally be of concern in a well ventilated working area, and
can be eliminated with the use of low odour/low bloom cyanoacrylates.
Cyanoacrylates will bond skin tissue very rapidly, but bonded skin can usually be relatively
easily prised apart by subjecting the adhesive to a peel action rather than direct tension.
Hot soapy water will help as well as proprietary hand cleansers. It should never normally
be necessary to have to resort to drastic measures such as surgery.
Dispensing equipment for production applications is available to ensure the correct

quantity of adhesive is accurately applied (see Section 10.9.1). For batch production
runs or development work the use of small containers fitted with fine bore needles is
recommended. This will minimise the quantity of adhesive applied, thus giving thinner
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bond lines and minimal excess adhesive. The thinner the bond line, the faster the cure
and the stronger the joint. This in turn means that there is less risk of fumes and less
chance of adhesive outside the joint line.
10.11 Typical Applications
This section shows some typical applications where cyanoacrylates have been used to
bond all types of rubber to an assortment of other substrates. It is important to note that
each application has its own unique features, and that an adhesive which works well in
one circumstance, may not necessarily be suitable in another.
10.11.1 Bonding Nitrile, Polychloroprene and Natural Rubbers
Cyanoacrylates bond well to nitrile, polychloroprene and natural rubbers and fast bonding
times can be achieved with ethyl cyanoacrylates (see also Section 10.1). Mould release
agents however, can sometimes affect the adhesion and further practical guidelines are
given in Section 10.12.
In the automotive industry, cyanoacrylates are used to bond a nitrile rubber sleeve to an
acrylonitrilebutadienestyrene (ABS) adjustment arm of an automotive mirror. The
adhesive supplements a push fit and tests showed that the cyanoacrylate fully exceeded
the strength requirements.
Sporting goods and toys are also important application areas. Items such as trophies,
rubber foam recoil pads for shot guns and assembling rubber strip inserts into wooden
cricket bat handles all benefit from cyanoacrylates unique bonding capabilities (see
Figures 10.16 and 10.17).
10.11.2 Bonding EPDM
Standard cyanoacrylates do not bond particularly well to EPDM but certain grades of
ethyl-based cyanoacrylates have been specially developed for bonding to EPDM. One
such grade is Loctite 406, an ethyl cyanoacrylate and this is used to attach an EPDM
rubber edge strip to an EPDM conveyor belt to prevent potash from falling off the
production line.
The same product is used for mitre bonding of EPDM rubber seals for automotive doors
and windows. The cyanoacrylate produces high strength invisible bonds in seconds.
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Figure 10.16 A toughened cyanoacrylate is used to bond a polychloroprene anti-slip

pad onto a cast iron machine foot
Figure 10.17 A fast curing ethyl cyanoacrylate is used to bond a nitrile rubber seal
onto an ABS cam belt cover
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For fixing an EPDM rubber seal to a polyvinyl chloride (PVC) beer pump mechanism the
cyanoacrylate must not only produce a reliable bond but also be approved for use with
potable water. The cyanoacrylate, once fully cured, is essentially an inert plastic and many
grades are approved for potable water as well as for medical applications (see Section 10.11.4).
10.11.3 Bonding Santoprene and Silicone Rubbers
These grades of rubber require priming prior to bonding (see also Section 10.6). Although
this makes it a two-stage operation cyanoacrylates are used for bonding Santoprene and
silicone rubbers.
Examples in industry include attaching a silicone rubber seal to an aluminium parachute

container. A primer is brushed on to the silicone rubber and the cyanoacrylate is applied to
the aluminium. Once fully cured the bonded seal assembly prevents dust or moisture entering
the safety critical box.
In another application a gel cyanoacrylate used with a primer eliminates unsightly mechanical
fixings and bonds a Santoprene finishing strip to melamine ceiling panels of railway carriages.
10.11.4 Bonding Medical Devices
Adhesives used in the medical industry are tested to the ISO 10993 [3] toxicological
classification requirements which essentially means that the physical properties of the cured
adhesive must be biologically inert, and corrosion and temperature resistant.
Medical grade cyanoacrylates are used by the medical industry for bonding sterile disposable
devices. Typical applications include: fluid and drug delivery sets, catheters, hypodermics,
hearing aid sub-assemblies and cardiopulmonary devices. Cyanoacrylates (which are solvent-
free) can replace solvent welding techniques particularly where two different plastics (or
rubbers) require to be bonded. Some solvents are highly flammable and some are considered
to be potential carcinogens. In addition, the cyanoacrylate has the ability to fill larger gaps
than a solvent and so offers the manufacturer wider scope for his manufacturing process.
Some sterile reusable devices may be used a number of times, e.g., endoscopes, surgical
instruments, and as such will require to be sterilised by autoclaving or exposure to one or
two or more cycles of ethylene oxide (EtO). Cyanoacrylates are not generally suitable for
applications where the device will be subjected to repeated autoclaving. Medical grades of
cyanoacrylates will generally survive single EtO or gamma radiation sterilisation processes.
However sterilisation resistance is always design and substrate dependent and must be
tested by the device manufacturer.
279
Silicone rubber is often used in medical devices as it offers good flexibility, a degree of
softness (for face masks, etc.) and good resistance to both EtO and gamma radiation
sterilisation processes. Silicone rubber can be bonded with the aid of a primer (see
Section 10.6).
10.12 Troubleshooting
Sometimes cyanoacrylates will form a white powder adjacent to the bond line. This is
known as blooming. This section explains the reason for blooming and suggests various
options to eliminate it from the production line. Also included are general guidelines for
troubleshooting an application.
10.12.1 Blooming of Cyanoacrylates
Blooming occurs when cyanoacrylate molecules escape from the main body of the adhesive
and react with water vapour in the surrounding air. The molecules of cyanoacrylate cure
and then fall to the adjacent surface as a white powder. Even with rubber toughened
cyanoacrylates, (which are often black in colour) it is the monomer which escapes and
the deposit will still be white (see Figure 10.18).
Figure 10.18 The monomer escapes from the bulk of the adhesive and falls onto the
adjacent surface as a white powder
280
There are three primary causes of blooming:
Excess adhesive
Slow cure
Low relative humidity
10.12.1.1 Excess Adhesive
When excess adhesive has been applied, the surface to volume-of-adhesive ratio is too
low and the moisture on the surface will be insufficient to neutralise the stabiliser in the
adhesive. The cyanoacrylate vapour will escape and fuming will occur. Reduce the quantity
of the adhesive by using fine bore application nozzles and/or dispensing equipment.
10.12.1.2 Slow Cure
In the same way as excess adhesive can cause blooming, a slow cure may give a similar
result. The cyanoacrylate at the periphery of the joint will search for available moisture
from the surrounding air and may then cure as a white powder on the adjacent surface. A
slow cure may be the result of excess adhesive, but is also likely to be caused by acidic
deposits on the substrate. These acidic deposits can cancel out the neutralising effect of the
initiators (moisture) and result in very slow polymerisation or in some cases inhibition of
cure completely (see also Section 10.4.1).
Slow cure can also be overcome by using an activator (or accelerator). There are a number
of different activators available to the production engineer and these increase the level of
initiators on the surface to negate the stabiliser and thus increase the speed of polymerisation.
Section 10.8 discusses the uses and application methods of activators in more detail.
Slow cure may also be due to a thick bond line (adhesive >0.2 mm). Cyanoacrylates are
most suited to applications where the bond line is less than 0.1 mm thick although a cure
through a volume up to several mm is possible using UV curing cyanoacrylates.
10.12.1.3 Low Relative Humidity
Low RH (less than 20%) will also encourage the formation of blooming and irritant fumes
because there is less moisture on the surface to initiate the cure.
The best results are obtained when the RH is between 40% and 60%. Higher humidities will
accelerate the cure process but could affect the final bond strength and in some cases increase
281
the risk of blooming. The use of activators can considerably assist the cure but placing a
container of water adjacent to the work station has been known to increase the local RH.
Blooming does not always occur during the first few seconds, indeed it is more likely that
parts will bloom some hours after assembly (up to 24 48 hours later). A bonding application
is often one of the last operations in a production cycle and care is required to ensure that
parts are not put straight into a sealed (or semi-sealed) container immediately after
cyanoacrylate bonding as there is a risk that the cyanoacrylate will bloom in the box resulting
in a poor aesthetic appearance to the end product. Trials should be conducted accordingly.
Blooming does not affect the strength of the bonded assembly and is usually only aesthetic.
However in some applications, e.g., the bonding of a rubber seal near an infra-red sensor
housing, blooming may occur on the surface of the sensor, thus rendering it inoperative.
In this case the use of a low bloom product will eliminate the possibility of blooming.
In summary, therefore, there are three methods of overcoming blooming:
Avoid excess adhesive
The use of dispensing equipment and ensuring that the minimum quantity of adhesive
required to fill the joint is applied will give best results.
Ensure fast cure
The longer the cyanoacrylate remains liquid the greater the risk of blooming. Designing
assemblies with close fitting parts and therefore achieving thin bond lines will increase
the speed of polymerisation and will decrease the risk of blooming. The use of activators
or a UV curing grade is recommended for the fast cure of exposed fillets of cyanoacrylates
after assembly.
Use a heavy molecular weight cyanoacrylate (low bloom product)
The heavy molecular weight cyanoacrylates are ideal for applications where bonds must
be cosmetically perfect, or for delicate electrical and electronic assemblies. The additional
low odour characteristic of these cyanoacrylates is ideal where operators are required to
work in confined unventilated spaces. The low bloom cyanoacrylates are also slower
curing than standard ethyl or methyl grades which means that more time is available to
assemble parts, where careful alignment is required.
See Table 10.1 for problems, causes and corrective actions when working with
cyanoacrylate adhesives.
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Table 10.1 Troubleshooting chart
Symptom Possible cause Corrective action
Poor adhesion. Low energy surface. Apply primer to surface and re-bond. Try writing on the
surface with a felt pen. If the ink globules, it is likely
that the adhesive will do the same and a poor bond will
result. In this case prepare the surface with a primer or
try flame etching.
Mould release agents. Can be difficult to remove. Good results can be achieved
by washing the parts in a warm water wash (40 C) with
5% sodium silicate. Isopropyl alcohol (IPA) can also help.
Cured adhesive has a This suggests that the cure was too fast. The Try a slower curing grade of cyanoacrylate, or wash the
glazed appearance. surface may be alkaline which causes the surfaces with water, or clean with a solvent to remove the
cyanoacrylate to cure too quickly and it alkalinity.
cures before it sticks.
Low strengths. Disturbance of partially cured adhesive. Check the production process. Cyanoacrylates should
not be moved just as they are polymerising from a liquid
to a solid.
Insufficient adhesive. Increase volume applied.
Blooming. Excessive quantity of adhesive. Reduce volume applied, e.g., use dispensing equipment.
Consider activators to speed up cure.
Slow cure speed. Use low bloom grade of cyanoacrylate (see 10.12.1).
No cure of the Acidic residues. The acidic residue may have originated from a surface
adhesive. treatment process.
Large gaps. Large gaps may exist between the two parts or there may
be insufficient surface moisture thus inhibiting cure.
Slow cure. Check the cure time - cyanoacrylates require between 4
24 hours to achieve full cure.
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References
1. ASTM D1002-01
Standard Test Method for Apparent Shear Strength of Single-Lap-Joint
Adhesively Bonded Metal Specimens by Tension Loading (Metal-to-Metal).
2. DIN EN 1465
Adhesives Determination of Tensile Lap-Shear Strength of Rigid to Rigid
Bonded Assemblies, 1995.
3. ISO 10993
Biological Evaluation of Medical Devices, 2003.
Bibliography
1. Manufacturing Engineers Reference Book, Ed., D. Koshal, Butterworth

Heinmann, 1993.
2. Industrial Adhesion Problems, Eds., D. M. Brewis and D. Briggs, Orbital Press,

Oxford, 1985.
3. H. W. Coover, D. W. Dreifus, and J. T. OConnor in Handbook of Adhesives, 3rd

Edition, Ed., I. Skeist, Van Nostrand Reinhold, New York, 1990, 463-477.
4. Loctite Worldwide Design Handbook, 2nd Edition, Loctite, Rocky Hill, USA, 1998.
5. Loctite Technical Data Sheet, Product 770, October1995.
6. Loctite Technical Data Sheet, Product 406, February 1996.
7. Loctite Technical Data Sheet, Product 480, February 1996.
8. Loctite Technical Data Sheet, Product 4204, August 1996.
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poor adhesion low strength blooming no cure glazed appearance

Commercial rubbers
11
Bonding Silicone Rubber to
Various Substrate
P. Jerschow, B. Stadelmann and W. Strassberger
11.1 Introduction
The bonding of silicone rubbers to other materials or to themselves is a very wide field.
Most commonly they are classified as:
High temperature vulcanising, solid silicone rubber (HTV),
Liquid rubber, liquid silicone rubber which is also curing at high temperatures (LR),
Room temperature vulcanising, one component (RTV1),
Room temperature vulcanising, two component (RTV2).
The intention of this chapter is to outline the advantages of using HTV and LR
silicone rubbers. These materials are most commonly used by the silicone rubber
industry. It would however be wrong to think that silicone rubbers and their bonding
were limited to just these two groups of materials and this chapter will also consider
other silicone specialities.
HTV and liquid silicone rubber LR, are used in moulding at elevated temperatures
(press, transfer or injection moulding).
Other silicone rubbers, RTV 1 and RTV 2 (also mouldable), are vulcanised at room
temperature. They can be used in a vast number of applications, many of which would
also contribute to the topic of rubber bonding. The applications range from baking
tray coatings to seals in electronics, encapsulation of electronic modules and devices
and cured in place gaskets to medium and high voltage insulators and pourable or
spreadable systems for mould making (prototyping). The intention of this chapter is to
concentrate on the processes used in both classical and modern rubber companies and
applications that are serviced by this fascinating industry.
The reader is encouraged to refer to publications on silicone rubbers used in the

applications mentioned above, and to trade literature from the industries and
applications [1, 2, 3, 4, 5, 6, 7, 8, 9].
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11.2 Why Bond Silicone Rubber?
In many applications, moulded parts, soft and hard, soft and soft or hard and hard are
put together in order to perform a specific task which a part made of one single material
could never perform. Very often it happens that at least one of the parts consists of
silicone rubber.
Before assembly both parts are produced separately, and then combined in a separate
production step, without any bond to each other. They are fixed mechanically.
Often, a soft elastic part is used, for example, as a gasket, valve, damper, etc. In order to
attach it somewhere, a hard component is required to act as a mechanical support.
The bonding is achieved by different methods. The hard component can contain undercuts
where the rubber is anchored during its vulcanisation, a primer on the hard component
or even using self-adhesive silicone rubber will give sufficient anchorage.
The formulation of the latter contains certain adhesion promoters which allow for
enhanced affinity between rubber and the other substrate. The chemical nature of self-
adhesive materials in most cases is proprietary information which cannot be disclosed.
But, several models for bonding are described in the literature [10].
The combination of two soft components such as silicone rubbers of different hardness,
colour, electrical conductivity, etc., is also commonly used in a wide range of applications.
Typical applications are electronic keypads (as for calculators, control panels, etc.), where
electrically conductive silicone rubber (so-called conductive pills required for establishing
an electrical contact when a key is pressed), is overmoulded with an insulating silicone
rubber pad, and cable accessories, containing an insulator body with a conductive silicone
core (so-called stress cone) which allows better control of the shape of the electric field.
In electronics transmission and distribution at medium and high voltage, automotive, medical
and many other applications silicone rubber is a preferred material for various reasons: its
outstanding chemical resistance, heat ageing, dielectric (insulating) properties, unlimited
pigmentability, flexibility in the cold and a wide spectrum of further advantageous properties
make it the ideal material. In many cases, there is no alternative to silicone rubber.
This chapter will focus on LR, because it is the most sophisticated material among silicone
rubbers used in moulded parts. It shows very productive processability (short cycle times,
no post-treatment like deflashing is needed), it allows use of complex geometry and,
moreover, waste free production of two component applications (soft and hard or soft
and soft) in only one machine without the need for a primer. In order to combine silicone
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Bonding Silicone Rubber to Various Substrates
with silicone, standard LRs or even any combination between LR, HTV and RTV may
be used. To make composites out of materials of a different chemical nature and silicone
rubbers a so-called self-adhesive LR would preferably be used. This is used in particular
for composites of thermoplastics with silicone rubber.
In most cases using a primer is undesirable. This requires the application of the primer
by spraying, dipping, painting, then drying and curing the primer at elevated temperatures.
If a primer has to be used it is not possible to produce a substrate, e.g., a thermoplastic
part, and a silicone rubber part, i.e., the whole composite, on one machine. Usually the
processor carries out a feasibility study to determine whether a production step using a
primer or twin shot technology is more favourable.
This chapter will also describe these numerous viable applications and technical solutions
using other silicone rubbers.
Textile coatings will not be mentioned here. Such materials also require the bonding of
the rubber onto the fabric which serves as a substrate. The bonding principles are
considered to be similar and thus will not be explained in detail in this chapter.
11.3 Material Combinations of Interest - Examples
11.3.1 Silicone to Silicone Bonding (Soft and Soft)
In a number of applications, silicone rubber bonded to silicone rubber is used. This can
be achieved either using a primer or without a primer. In most cases, the processor uses
a pair of materials with the same curing system. For example, addition curing silicone
rubber can be combined with another addition curing silicone, or a peroxide curing
rubber can only be used with other peroxide curing materials, e.g., an addition curing
silicone might not cure in the presence of peroxides.
Typically, one silicone part is cured to an intermediate degree of vulcanisation prior to

the introduction of the second silicone rubber portion. In the second step, when the
second rubber component is injection or press moulded onto the first component,
vulcanisation is completed. The incomplete degree of curing of the first material will
ensure proper bonding between the two materials as the two layers are fully cured while
in intimate contact with each other in the final step of vulcanisation or even as late as
during the post-curing step. The most recent development for bonding of silicone rubber
to metal is a one component, self-adhesive, solid silicone rubber which is addition curing.
It is described in Section 11.6, Table 11.2.
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11.3.2 Silicone to Plastic Bonding (Soft and Hard)
Typically, silicone rubber used in such cases bonds to a thermoplastic material which
exhibits a very high melting or glass transition temperature. This is necessary, as silicone
rubber will vulcanise at elevated temperatures such as 140 C upwards, whereas the
thermoplast should solidify in the first moulding step without cooling down too much,
providing some surplus heat for the curing of the silicone. In the case of insert parts
which are overmoulded with the silicone, the melting temperature is also of importance.
If too high a mould temperature is used for the silicone covering the thermoplastic
part, there is a possibility of warping, and loss of shape or mechanical properties of the
hard component.
Thermoplastic materials which could be used in conjunction with silicone rubbers include
nylons (polyamides), polybutylene terephthalate (PBT), polyphenylene sulphide (PPS)
and polyethylene terephthalate (PET).
Section 11.5. will explain the three alternatives for bonding, where mechanical anchorage
(undercuts) or self-adhesive silicone rubber allow for two colour injection moulding.
11.3.3 Silicone to Metal Bonding (Soft and Hard)
It is also possible to bond silicone rubbers to various substrates which are not injection
moulded. Such materials range from steel and aluminium to ceramics, glass or any
other solid.
In such cases the processor basically has the choice between undercuts, primers or
primerless self-adhesive silicone rubber.
The major difference is that the hard component cannot be produced in the same machine,
it is inserted into the mould in which it is finally overmoulded with the silicone rubber
part. Metals, ceramics, glass, etc., are not too sensitive to high temperatures, which allows
the process to run at a higher productivity than in the previous case, see Section 11.3.2,
where cycle times are longer due to lower moulding temperatures for the silicone part.
11.3.4 Why Use Silicone Rubber for Such Composites?
The entire group of rubbery silicones exhibits a vast spectrum of unique properties rarely
superceded by any other rubber. In most cases silicone rubber provides the best choice in
terms of processability, mechanical properties, high performance and material cost.
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Table 11.1 Qualitative comparison between a number of commonly

used rubbers
Fully Cold Heat
Waste free Chemical Pigmentable,
automatic flexibility Stable
production resistance any colour
production < 40 C > 200 C
TPE ++ ++ +/ +
EPDM + +/
Natural

Rubber
Silicone
++ ++ + ++ ++ ++
LR
TPE: thermoplastic elastomer ++ = very good + = good = negative
Self-adhesive LR is one of the only rubbers which can be processed fully automatically,
producing no waste and at a maximum productivity. Parts with a complex geometry
can be realised using quite reasonable injection moulding machines with a low clamping
force. Table 11.1 summarises the properties of silicone rubbers and the advantages
and disadvantages of some groups of other rubbers that potentially could be used in
rubber bonding applications. Please note that this table is intended as a rough guide
and is not intended to be a complete and a final statement on the rubbers mentioned
therein.
As for silicone rubbers other than LR, most of the above mentioned points apply, too.
Silicone HTV rubbers can be delivered in a wide variety of preforms which allows the
processor to optimise the production process. Such preforms range from blocks and
strips to coils and even pellets, use of the latter allowing a more or less continuous
operation.
Another, useful property of silicone rubbers is their unique electrical behaviour. Silicone
rubbers, if processed correctly exhibit extremely high volume resistivity, high dielectric
strength and excellent tracking and arcing resistance. This is also the reason why
substantial quantities of silicone rubbers are used by the cable, cable accessory and
insulator and electronics industries.
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11.4 Some Applications of Silicone Rubber Composites
Silicone rubbers, both, peroxide and addition curing, are used in the manufacture of
composite parts. Known applications focus on automotive, medical, sanitary, household,
transmission and distribution (T&D), electronics and food appliances.
Typical applications for silicone HTV and LR rubber composite parts are:
Automotive Connector seals

Crank shaft seals
Exhaust pipe hangers
Ignition cables
Membranes
Multi-functional switches
Radiator seals
Rain sensors
Spark plug boots
Medical Anaesthetic tubings (composite)

Body contact electrodes
Catheters
Respiration masks
Various pads
Various valves, e.g., dialysis apparatus
X-ray opaque shunts
Sanitary and household Gaskets for WCs

Gaskets in tap water equipment
O-rings (composite)
Various valves
Transmission and Medium and high voltage cable accessories

distribution (T&D) Medium and high voltage insulators
Electronics Anode caps and cables

Key pads (composite)
Various gaskets
Food appliances Baby care articles

Food dispensing valves
Various gaskets
This list of applications gives just a brief idea of items currently produced using two-
component injection moulding techniques or insert parts.
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primers self
bonding silicone
LR
Figure 11.1 Alternatives for bonding silicone rubber
11.5 Bonding Concepts
Figure 11.1 shows schematically the construction of the three most important concepts
of bonding.
11.5.1 Undercuts
This is the most traditional bonding concept. It allows the thermoplastic substrate to be
injection moulded in the same machine as the silicone rubber. Undercuts in the substrate can
be applied by special mould design, holes or other shapes, e.g., in steel sheet inserts. The
possibilities for using undercuts are numerous. However, the use of undercuts has the
disadvantage that the mould design for injection moulding of both the thermoplastic substrate
and silicone rubber becomes more complicated. In many cases this is due to the fact that the
design should allow proper venting during the filling stage of the silicone rubber part of the
mould. Undercuts always imply a high proportion of dead corners where air is entrapped,
leading to incomplete filling of the mould and finally to insufficient anchorage.
291
Another disadvantage of this concept is that the bonding contact between silicone rubber
and substrate is achieved only by mechanical ties. In other words, the interface between
substrate and silicone is a source for leakage, e.g., in a gasket application.
In some cases more silicone rubber is used to fill undercuts than would be required for
the rubbery function of the part.
11.5.2 Primers
The application of primers does not allow for the injection moulding of the substrate on
the same machine as the silicone rubber part.
A primer is usually applied onto degreased substrates by dipping or spraying. The primer
solution can be used as delivered or diluted in hydrocarbons. After application and drying
it is necessary to pre-cure the primer at an elevated temperature. In most cases 10 minutes
at 130 C is sufficient.
11.5.3 Self-adhesive Silicone Rubbers
Self-adhesive silicone rubbers do not require a primer and, therefore, the plastic substrate
can be injection moulded on the same machine as the silicone rubber.
Self-adhesive silicone rubbers for injection moulding are restricted to LR mainly. The
most peculiar property of these rubbers is the fact that the mould does not have to be
treated with a special release agent (which is expensive and complicated to use) when
working with these silicone rubbers.
However, at the same time it is possible to achieve sufficient bonding to steel without
having problems with the self-adhesive silicone sticking to the mould, as is the case with
conventional bonding agents for rubber to metal components.
Most recently self-adhesive HTVs have been developed. However, they require special
release agents or a specially structured mould suface. They are mainly intended for bonding
silicone rubber to steel.
11.5.4 The Build-up of Adhesion
In general, maximum adhesion is not achieved as soon as the part is moulded, rather it
increases after storage of the material for some time. At room temperature this time
292
could be as long as a few weeks. After that, adhesion can become stronger than the
mechanical properties of the rubber. In other words, when trying to separate the rubber
from the substrate, the rubber will break.
The storage period can be shortened significantly, if it is carried out at an elevated

temperature. Approximately 0.5 to 1 hour at 80 C to 130 C will provide sufficient
adhesion development. The storage or post cure temperature is determined by the
properties of the substrate, as, for example in thermoplastics, warping might be the
result of too high a temperature.
It is also essential, that demoulding should be stress free, so that a disruption of the
contact surface between silicone rubber and its substrate cannot take place. Once this
interface is broken, it is unlikely that proper adhesion will be possible later.
Adhesion depends strongly on the surface properties. It is built up faster on smooth

surfaces than on rough, sand blasted or electrically eroded substrates. Among other
reasons this can be explained by the fact that smooth surfaces are intimately covered to
100% before the cure of the rubber. Uneven surfaces can be interpreted as surfaces with
very tiny undercuts, and hence much less than 100% will be covered by uncured rubber,
as curing usually happens before these micro-undercuts are filled. As mentioned in Section
11.5.1, undercuts that are not entirely filled might lead to loss of anchorage.
When working with standard silicone rubbers stronger adhesion to smooth surfaces is
observed. However, cohesive failure is never found when separating the rubber from a
substrate which has not previously been primered.
11.6 Bonding of Liquid Rubber (LR)
The curing characteristics of LR will be described first as they differ from those for HTV.
LR consists of two parts, each of which contains reactive components. Once the components
are mixed, they start to cure. This curing speed is virtually zero at room temperature. It rises
dramatically when the mixture is heated in the mould. This allows the processor to produce
moulded parts by injection moulding. LR has viscosities between 300 and 8000 Pa-s and
exhibits extreme shear thinning properties. In other words, once sheared, its viscosity drops
and its consistency is very much like honey. HTV rubbers have viscosities far above those of
LR. The appearance of an HTV is more solid than liquid (see Figure 11.2).
The curable composition of LR (component A mixed with component B) consists of two

sorts of polydimethylsiloxane (PDMS) molecules. One contains vinyl groups on the ends
293
Figure 11.2 Chemical structures and mechanism for addition curing LR and HTV
of the chain and the other contains at least three hydrogen atoms across the chain. In
order to provide sufficient mechanical strength and rheological properties to allow proper
processing, this mixture contains a filler, usually fumed silica. A platinum catalyst and a
set of inhibitors control the curing characteristics.
This mixture is called addition curing, because silicon-vinyl groups and silicon-hydrogen
groups add to each other in the presence of platinum and heat. An advantage of this
curing mechanism is the absence of peroxides and their by-products and, moreover, the
fast speed of curing.
HTV rubber is available as peroxide or addition curing. In some applications LR is not

capable of out performing HTV rubber. LR is perfect for a vast number of applications,
but if very high mechanical properties are required, HTV will be the rubber of choice.
The recently developed self-adhesive HTV silicone rubbers are addition curing, one
component materials which remain processable for several weeks at room temperature.
Self-adhesive liquid silicone rubbers are always delivered as two components. This is due
to the fact that once components A and B are mixed the processing time is approximately
3 10 days at room temperature.
Table 11.2 shows a rough comparison between the curing behaviour of a peroxide curing
HTV, an addition curing HTV and an addition curing LR.
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Curing time Wacker Chemie GmbH
Table 11.2 Curing time for HT and self adhesive LR

Type of rubber/cure Curing time (s)
Addition Cure LR 25
Addition Cure HTV 50
Peroxide Cure HTV 120

Injection moulding of a test slab of 6 mm thickness
Moulding temperature 180 C
Cold runner mould
Materials used:
Addition Cure LR: ELASTOSIL LR 3070/40
Peroxide Cure HTV: ELASTOSIL R 401/60 (standard HTV)
Addition Cure HTV: ELASTOSIL R 4070/60, (self-adhesive HTV, one component)
all produced by Wacker Chemie GmbH
Table 11.2 shows clearly that LR is the material that by having the fastest cure rate, will
achieve the highest productivity among the group of silicone rubbers and most of all the
other rubbers. LR can be bought ready to use and then processed fully automatically
without any waste, providing parts with the highest precision and quality which do not
require any mechanical secondary treatment such as for example cryogenic deflashing.
Self-adhesive LR can be processed to form a composite part using:
Two machines and a robot, or

One machine and two-component (often called two-colour) equipment.
In the first case the substrate is produced in the first machine. It is either injection moulded,
punched from a metal sheet, etc. A robot then transfers and inserts it into the LR-mould
on the second machine. Self-adhesive LR is then injection moulded onto the part. After
the curing time the composite is carefully removed.
The second case, using only one machine, involves injection moulding the plastic part in
a thermoplastic cavity of the two-component mould. On solidification the moulding is
extracted by rotating the indexing platen or using a robot and then inserted into the
cavity for the LR which is then injection moulded onto it. Demoulding takes place as in
the first example.
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It is quite clear that it is essential to take into account the limits of the part to be coated
and the requirement of a perfect thermal household in the mould during the production
of composite moulded parts. The mould temperature of the LR cavity should be as high
as possible and the inserted part should be at the highest possible temperature when
placed into the silicone cavity, to allow for utmost productivity, which depends very
much on the speed of curing.
Some proposed conditions are shown in Table 11.3. It is again clear that in injection
moulding, LR will be the most viable option for such applications as it allows for a wide
processing window for adhesives with low curing temperatures.
Table 11.3 Curing times and minimum moulding temperatures for

LR and HTV
Minimum moulding Curing time
temperature (s)
Addition Cure LR 140 C 25
Peroxide Cure HTV 170 C 120
Addition Cure HTV 150 C 50
Low moulding temperatures also favour the formation of flash. This can be avoided by
using state-of-the-art mould technology.
The result of a composite moulding was checked with test specimens of a well known
dog bone shape, as shown in Figure 11.3.
These test pieces were produced by injection moulding. They break at a maximum load
of 4 kg or even above, if good adhesion has been built up. In many cases the silicone
breaks. In other words, its mechanical properties are weaker than the force of adhesion
between plastic and rubber.
Another similar test is the peel test [11]. A strip of self-adhesive material is peeled off the
substrate and the force needed for peeling is recorded. In order not to tear the rubber
during the peeling test it is reinforced with a glass fabric.
Duration of adhesion (in particular under service conditions) is possibly one of the trickiest
questions in connection with self-adhesive LR. In fact, it is unpredictable at present.
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PA
Self bonding LR
Figure 11.3 Test specimen for testing self-adhesive LR as a composite with polyamide (PA)
Surprisingly this is not only because of the lack of extended history but also because of
the infinite number of possible different service conditions. The number of factors that
could influence the duration of adhesion is vast. Some examples are:
Constant mechanical stress,

Dynamic mechanical stress,
High temperatures,
Low temperatures,
Varying temperatures,
Migration of additives in the substrate,
Surface of the substrate,
Ageing of the substrate,
Immersion in oil, solvents, chemicals in general.
11.6.1 Properties of Self-adhesive LR
Practically, all properties known for LR can be incorporated into a self-adhesive material.
Such modifications include LR with enhanced oil, tear and/or heat resistance.
In the case of the widely used self-lubricating LR, self-adhesive behaviour can be achieved
as well. Even conductive self-adhesive LR is theoretically possible.
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peel test
Table 11.4 Self-adhesive silicone rubber ELASTOSIL LR 3070/40

Test results of peeling test according to DIN 53531 [11]
Chemical Tear force
Thermoplast Manufacturer
composition [N/mm]
Miramid VE 30 CW PA 6 Leuna-Miramid GmbH 15,0 R
Ultramid B3EG6 PA 6.6 BASF 16.0 R
Ultramid A3EG6 PA 6.6 BASF 19.9 R
Miramid SE 30 CW PA 6.6 Leuna-Miramid GmbH 18.3 R
Grilamid TR 55 PA 12 EMS-Chemie 11.9 RM
Grilamid LV 3H PA 1 2 EMS-Chemie 17.3 R
Crastin SK 605 PBT Du Pont 15.5 RM
M = adhesion tear (adhesion failure)
R = rubber tear (cohesion failure)
RM = combines R&M
Table 11.4 gives a summary of results of peel strength achieved with different substrates.
The number of substrates is small in order to allow a very quick overview.
Slabs 60 x 25 x 2 mm were injection moulded and in a 2K injection moulding process

overmoulded by 6 mm of LR.
The peeling force was determined after storage for 48 hours at room temperature. No
post-cure or heat treatment was applied.
None of the substrates mentioned in the table was primered. The table shows various
types of plastics (including PA 6, PA 66 and others).
11.6.2 Limitations of Self-adhesive LR
The use of self-adhesive LR is limited. Firstly, such materials cannot necessarily be

used in applications with food contact, as post curing is required and the formulations
often do not comply with respective legislation such as recommendations by FDA /
177.2600 [12] and BgVV XV Silicones [13]. Post curing takes place over several
hours at 200 C. Most thermoplastics will not withstand this thermal treatment.
But, even much lower post curing temperatures are possible resulting in longer post
curing cycles.
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Secondly, if an application implying self-adhesive LR requires reliable bonding over the

whole service period, extensive testing will be necessary prior to its use.
At the moment self-adhesive LR cannot be used in medical device technology as no

testing according to protocols like ISO 10993-1 [14] or USP Class VI [15] has been
carried out. Medical devices should be using post-cured silicone rubbers only. One of the
latest developments is a self-adhesive liquid silicone rubber which is compliant to BgVV
and FDA, as post cured. It adheres to PBT and PA only.
11.7 Bonding of Solid Rubber (HTV)

The bonding of HTV to various substrates works analogously to the bonding of LR.
HTV has much lower curing speeds at any given temperature and this enables it to be
used in many different applications, which for the most part are described in Section11.4.
In addition, processing of HTV differs in most cases from that of LR. In moulding,
compression moulding techniques are used rather than fully automatic waste free injection
moulding. Consequently a deflashing procedure is required after the moulding step. In
many cases this is done by cooling the parts with liquid nitrogen. The rubber becomes
brittle and the flash can then be removed (this is also called cryogenic deflashing).
In the case of two-component composites such deflashing steps may become critical, if
the components have different coefficients of thermal expansion and because of a strong
increase of brittleness in case of thermoplastic substrates.
In most cases HTV rubbers are bonded to solid substrates using undercuts or primers.
Self-adhesive HTV rubbers work in the same way as their LR counterparts. However,
moulding is more critical because of substantially longer curing times which can lead to
demoulding problems, as mould stickiness increases dramatically with curing time. For
such purposes the processor might need to prime his moulds with a special PTFE primer.
It should be noted that self-adhesive HTV sticks to steel when moulded!
11.7.1 Self-adhesive HTV Silicone Rubber Applications
Self-adhesive HTV silicone rubber is formulated in a similar way to self-adhesive LR.

The ready-to-use formulation contains all adhesion promoters. However, other than LR,
which is two component and addition curing only, self-adhesive HTV can be purchased
both, as peroxide and addition curing. Because of fundamental differences in curing
speed between self-adhesive peroxide cured HTV and addition cured HTV the applications
differ quite substantially.
299
Furthermore, HTV silicone rubbers exhibit better mechanical properties than LR. As a
consequence applications might differ for the self-adhesive versions of these two family
of products, apart from much better adhesion to steel in case of self-adhesive HCR.
Properties
Table 11.5 gives a general overview of the properties of HTV silicones and LR. It is clear
that HTV will never be 100% replaced by LR. So far the mechanical properties and heat
resistance of HTV rubbers are more favourable than those of LR. However, this summary
should emphasise the characteristics of each family of materials and give an idea of how
to select the most suitable material for an application.
Table 11.5 Summary of properties of LR versus HTV silicone rubber

Liquid rubber HTV silicone rubber
+ self-adhesive LR available + self-adhesive HTV available
+ production highly automated + more reasonable moulds
+ very complex geometry of parts possible + lower cost for small scale production
+ lower cost for large scale production + heat stability higher than LR
+ no post treatment of parts + chemical resistance higher than LR
+ no yellowing such as with peroxide HTV + better mechanical properties than LR
+ weight reduction by lower density + available in pellets easy handling
+ lower curing temperature possible + calendering possible
relatively high investment costs + extrudable
+ addition curing lower transparency than LR, yellowing
+ low toxicity
+ no peroxides therefore often no post cure
+ much shorter cycle times
+ less flashes than HTV
+ available as addition curing
+ low toxicity
+ no peroxides therefore often no post cure
+ shorter cycle times than peroxide HTV
+ no yellowing for addition cured HTV
+ positive negative
300
Table 11.5 quite clearly shows why some applications are exclusively restricted to either
HTV or LR.
11.7.2 Applications for Self-adhesive HTV
11.7.2.1 Peroxide Curing Self-adhesive HTV
The application of self-adhesive peroxide curing HTV is restricted to rollers or similar

applications. They work much more effectively than primers. Table 11.6 shows a
comparison between a roller using a traditional primer and one using self-adhesive
peroxide cured HTV (see Figures 11.4 and 11.5).
Table 11.6 Comparison of rollers produced with primers and with

self-adhesive HTV ELASTOSIL R Adhesive Base 90, hardness 90 Shore A
Silicone roller with primer
Test results at roller function tester
Line pressure Diameter Structural Notice
rpm C Abrasion
N/mm mm break (test time, surface)
30 200 200 179 No No 240 min, OK
96 min, whole rubber
40 200 200 179 No Yes
layer was peeled off
Result 5% adhesion to the metal core
Figure 11.4 Silicone roller with primer rubber peeled off entirely
301
Table 11.7 Silicone roller with ELASTOSIL R Adhesive Base 90 (red colour)
Test results at roller function tester
Line pressure Diameter Structural Notice
rpm C Abrasion
N/mm mm break (test time, surface)
30 200 200 181 No No 240 min, OK
40 200 200 181 No No 240 min, OK
188 min, silicone layer
50 200 200 181 No Yes
broken
Result 100% adhesion to the metal core
Figure 11.5 Silicone roller with primer cohesive failure in adhesive base
In this case self-adhesive HTV is used as a substitute to the primer. As it is chemically

different from primers, which are not silicone rubbers, it is considered in this section.
11.7.2.2 Self-adhesive Addition Curing HTV

This material cures much faster than the peroxide curing offset, which results in much
shorter curing times. This makes it suitable for moulding applications. It needs not to be
processed in a PTFE treated mould, if the surface of the mould has the right electro-
eroded structure. The reader may understand that this development is very recent and
therefore no adhesion results can be provided in this review.
However, one can predict that it adheres stronger to any substrate than self-adhesive LR.
302
11.7.3 HTV Used in Other Bonding Applications
Using primers or undercuts the field of applications for HTV is increased dramatically. The
primers can be applied to normal solid substrates as well as to fabrics and single fibres.
Depending on the scale of production, HTV can be used for all applications as described in
Section 11.4. The only limitation is the speed of curing and the respective moulding
temperatures. In all cases HTV cures slower and at higher temperatures than LR. In most
cases this moulding temperature and curing time is responsible for the fact that it is hard to
combine plastics with HTV. Most typically, metals, steel, iron, etc., will be the substrates.
Other applications
A very popular technique using HTV is the combination of moulded silicone parts together
with extruded HTV profiles, tubing or mouldings. Examples of such composites are catheters
used as medical devices, electrical cables, long rod insulators and composite insulators.
11.8 Processing Techniques
This section will summarise the processing techniques applied in the manufacture of
composite parts from LR and HTV silicone rubber.
11.8.1 Liquid Rubbers in Inserted Parts Technology
The two alternative concepts for the production of composite products are the thermoplast
machine and the LR machine. The prerequisite for a successful product is the choice of
suitable materials. The advantages of using the LR machine are:
A higher mould temperature can be used for the LR cavity, resulting in shorter cycles,
A shorter cycle can be used,
Parts of complex geometry can be produced.
The main disadvantage is investment cost and that the machine occupies a large space.
As mentioned earlier, the insert parts can be produced by any apparatus. This can be extrusion
with subsequent cutting, injection moulding, two or multiple colour (also two or multiple
component) injection moulding, press moulding, punched and bent metal sheets, cast iron,
sintered metal, ceramics in any shape, cut glass, etc., or moulded or extruded silicone rubber
(as in catheters and insulators).
303
In order to achieve short production cycles it is advantageous to use pre-heated inserts.

In some cases, primers are applied to the degreased insert in addition to undercuts even
when using a self-adhesive LR. The application of such primers takes place by spraying,
dipping or printing with subsequent drying and (only after drying) curing for 10 minutes
at approximately 130 C (lower for more sensitive insert materials) or higher. Hence,
primered insert parts always are pre-heated. Using an unprimed LR, pre-heated inserts
are advisable. This allows substantial heat transfer from the insert into the silicone,
which allows faster curing.
Another very important property is the thermal stability of the insert. The processor
never faces problems using steel or other metals, as their thermal stability is determined
by their melting point. However, phase transitions in the plastic or metallic part, e.g.,
from one crystal structure to another might be dangerous for the subsequent performance
of the composite part.
For glass or ceramics, brittleness and eventual consequences of thermal shock treatment
have to be considered.
The trickiest inserts are thermoplastics. They exhibit a relatively low melting or softening
temperature that ranges from approximately 60 C up to 200 C or higher. In many
cases, injection moulded, extruded or press moulded plastic inserts have incorporated
residual stresses from their method of manufacture. Such structures, often caused by
process induced molecular and/or crystal orientation can relax at elevated temperatures
which often leads to warping of the inserts.
Table 11.8 shows some examples of melting temperatures of thermoplastic materials. These
temperatures can be taken as a guide only, as in most cases softening takes place approximately
30 C to 50 C below the actual melting point which is quoted in the literature. It is also clear
that a melt temperature will be reached only after sufficient contact time.
For plastic materials, an insert should enter the hot mould at the optimum temperature
that assures no or negligible change in quality when it leaves the mould after being
coated with a silicone moulding. One of the most important prerequisites for successful
production of composites is a very short heating time in the LR injection stage. Short
heating times will be insufficient to thermally harm the plastic but long enough to allow
curing of the silicone rubber.
For such purposes, so-called faster curing LR have proven to be advantageous. At a

given temperature and geometry, savings in cycle times (not heating time) have reached
between 25 to 70% in comparison to standard LR, as indicated in Table 11.9 which
shows a compilation of t90 values, the time needed to reach 90% vulcanisation in a
Goettfert rheometer.
304
Temperatures Curing times
Table 11.8 Melting transition temperatures of

various thermoplastic materials
Polymer Start of melting (C)
LDPE 105
HDPE 132
PB 124
PP 160
PA 170
PBT 230
Table 11.9 Curing times as average t90-values for standard and

fast curing LR
Liquid Rubber ELASTOSIL t90-values at t90-values at t90-values at
type LR 130 C, (s) 150 C, (s) 170 C, (s)
Standard, general
3003 50 38 26
purpose (GP)
Fast curing, GP 3004 38 27 24
Fast curing, NPC 3005 39 27 24
Standard, oil
3089 40 38 26
bleeding, NPC
Fast curing, oil
3080 39 31 28
bleeding, NPC
Fast curing, oil
3013 33 25 23
resistant, NPC
Fast curing, low
3001 30 25 22
inflammability
italic: fast curing
bold: corresponding figures between two temperatures
underlined: corresponding figures
bold and underlined: show the efficiency of fast curing grades
NPC = no post cure
The cycle time essentially consists of heating time and time for demoulding, closing,
opening of the mould and metering of fresh material. Therefore it strongly depends on
the shape of the individual product which is manufactured.
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Table 11.9 demonstrates quite well that new fast curing grades achieve the same or a
similar curing result at a certain time but at much lower temperature as the standard
curing LR. Such grades are highly suitable and their use advantageous for two-component
injection moulding applications. Bold and/or underlined figures in this table indicate the
time-temperature relationships.
It goes without saying that such fast curing technology also exhibits highly advantageous
curing characteristics in simple one-component injection moulding. In order to obtain
more reliable predictions of curing times for the injection moulding process itself, the
processor must conduct preliminary trials in a mould of related geometry or even a real
prototype mould.
Consequently, relatively short cycles at lower temperatures allow the use of polymer
substrates with lower melting temperatures and less sensitivity to heat treatment as the
contact times (curing times) decrease much more than the cycle times.
11.8.2 LR in Two-component Injection Moulding Technology

(Two Colour Mould)
This technology uses moulds with special indexing plates or handling robots that allow
the transfer of the thermoplastic substrate part from the plastic cavity into the cavity for
LR moulding. A specific problem in such mould design is the thermal separation cold
in the thermoplastic cavity and hot in the silicone rubber cavity. This is quite important
and thus needs to be optimised. A peculiar fact about this moulding technique is that the
plastic cavity requires a hot runner and that the LR mould requires a cold runner.
Needless to say, here we look at further two challenges for the mould designer with
respect to thermal household.
11.8.2.1 Injection Moulding of Plastic Substrates

In the two-component injection moulding processes the slower of the two steps is cycle
determining. The thermal properties of both silicone and plastic materials require
compromise with respect to temperature in both cavities which deviates from the ideal
conditions for simple injection moulding.
In ordinary thermoplastic moulding, to achieve optimum cycle times for the thermoplastic
part a temperature is needed that is as low as possible, or that is optimum for the injection
moulding of that specific material.
In two-component injection moulding for the production of thermoplastic/silicone composites,

the moulding temperature for the thermoplastic should be as high as possible for two reasons.
Firstly, when the thermoplastic solidifies, residual stresses are frozen in. This can lead to
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relaxation processes once the polymer is in contact with hot silicone rubber and consequently
warping of the plastic substrate later. If the moulding temperature is high enough, residual
stresses will generally be lower. Secondly, a higher moulding temperature for the plastic will
allow its residual heat to contribute to the curing of the silicone rubber.
For the injection moulding of the plastic parts, hot runners allow a waste free production.
The plastic is injection moulded as in a conventional process. When sufficient solidification
is reached, the mould opens, and an index plate (this is a rotating platen which takes the
plastic parts from the first cavity and puts them into the liquid rubber cavity by rotating
them through 180 degrees), robot, etc., extracts the plastic moulding and transfers it
into the silicone cavity.
11.8.2.2 Finishing of the Composite - The Moulding of LR onto the

Plastic Substrate
The plastic is inserted into the hot silicone cavity. The contact surface between plastic
and the walls of the cavity should be kept as small as possible, in order to minimise an
excess flow of heat into the plastic.
Liquid rubber is injected via a cold runner into the mould. The rubber is cured at as low
a temperature as possible and the composite is extracted.
The advantage of this set up is that less space needed but the disadvantage is that the
cycle maybe slightly longer.
It is of utmost importance to operate the liquid silicone cavities at the lowest possible
temperature that allows sufficient curing times for the rubber but which will not harm
the plastic substrate. A qualitative description is shown in Figure 11.6.
Figure 11.6 shows the strong dependence of solidification time for the thermoplast and/
or curing time for the liquid silicone rubber from moulding temperature. It is not intended
to be symmetric as it may differ for various pairs of materials.
The term optimum indicates that at a given temperature the time for solidification
equals the time needed for curing the silicone.
Shorter curing times in the silicone cavity lead to shorter contact times for the
thermoplastic. The shorter the contact time, the higher the temperature of the silicone
cavity that can be used without it being critical for the plastic substrate. In other words,
the temperature of the silicone rubber mould strongly depends on the speed of curing of
the liquid rubber used in the processing.
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Figure 11.6 Simplified choice of processing conditions
State-of-the-art technology allows the manufacture of such composites in 32 cavity moulds

with modern cold runner technology using needle shut off valves.
Materials suitable for two-component injection moulding are both normal and
self-adhesive LR.
At the time of the release of the component from the mould, adhesion is at its weakest
level. Therefore, in the case of self-adhesive or primer technology, it is essential to demould
cautiously as, once silicone and substrate are separated, no adhesion will form again. In
the case of self-adhesive LR, upon cooling and after sufficient storage and/or further
heat treatment, adhesion will develop to its utmost extent. This will be explained further
in Section 11.11.1. It is essential that the plastic material used for the moulding of the
hard substrate solidifies quickly at a high mould temperature.
11.9 Silicone to Silicone Bonding (Soft and Soft)
Such applications are widely used across all fields which use silicone rubbers. The technique
is quite simple. In the first step a tubing or a moulding is cured to an incomplete degree
of curing. This is achieved by curing at a lower temperature or too short a curing time
for complete vulcanisation. These parts are then inserted into another silicone cavity
(HTV or LR) and coated with the silicone rubber. It is advisable to make silicone-silicone
composites from silicone rubbers with only one curing system. In other words, a peroxide
308
curing HTV silicone rubber should be combined with other peroxide curing HTV silicone
rubbers. Addition curing HTV can be combined with addition curing HTV or with LR,
the latter invariably being addition curing. This technique is used to produce medical
catheters, components which require various combinations of two hardnesses, and
technical parts, e.g., electronic keypads.
As an example consider silicone keypads. The first silicone components are conductive
pills. They can be incorporated using inserted part technology as well as in two-component
injection moulding, the latter preferably using LR.
In inserted part technology, these pills can be produced after moulding or extrusion
by punching.
The second component, a LR or HTV, is injection moulded onto the conductive pellets.
Again, it is highly advisable to use the same curing system for both components -
conductive pills and electrically insulating keypad.
It is quite clear that this moulding technique can be utilised to produce simple two or
multiple coloured parts.
11.10 Cable Industry
In some cable applications a bond between insulating silicone and conductive wire or
conductive silicone is necessary for various reasons. For cables used in measuring devices
and applications used under similar circumstances, adhesion of the insulator to the wire
is necessary when the cable is pulled out of a plug. If there is no adhesion the insulating
silicone will just come off the wire, if it is pulled strongly.
A typical application is ignition cables where some automobile manufacturers specify an

adhesion force of 70 N per 5 cm of ignition cable. This type of specification has been set-
up to assure proper adhesion when the ignition cable is disconnected from the spark plug.
If a conductive silicone rubber is used instead of a copper wire, adhesion is built up

during the curing process, when the outer insulating layer cures onto the inner conductive
silicone lead.
11.11 Duration of Bonding Properties
It is technically possible to produce very strong bonding between silicone rubber and another
material. However, the silicone-plastic, silicone-metal or silicone composite obtained usually
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undergoes ageing in a severe environment typical for the proposed application. Examples
are oil or coolant resistant gaskets, spark plug boots, electronic housings, anode caps, etc.
After receiving a set of different stresses a chemical and moreover a physical bond can
weaken or even be disrupted. Earlier in Section 11.6 a number of examples of influencing
factors are given to indicate what could affect the bonding process.
Under normal conditions, chemical bonding will not change over time provided the article
is not deformed, in particular not deformed dynamically, and provided thermal,
mechanical and chemical stresses cannot influence it negatively. In such a case this bonding
will persist for years, maybe decades.
For mechanical bonding using undercuts or even clamping (clamping in fact is related to
undercuts but it is a result of a secondary operation), the situation changes, as the material
faces a stress relaxation process (also called set of a certain mechanical parameter).
This means that each composite has an initial stress distribution as moulded. This stress
decays over time. As this stress is also responsible for the strength of the mechanical
bond or anchorage the decay should be as slow as possible. A closely related and prominent
example for that is the compression set which is analogous to the tension set and related
to stress relaxation. If an article is compressed over a certain period of time, the elastic
force acting against the compression usually decays. In other words, once a material
cures at a high temperature around undercuts it will be under tension upon cooling
down to room temperature - either slight compression or elongation. The resultant set
starts to grow from this very first moment. If a moulded part is under a certain load
(stress) during its use and moreover it has some residual stresses built in during the
production, such a set can become critical for the performance of the composite.
In order to achieve low mechanical setting properties, the silicone rubber has to be post
cured. A post cure of composites is not possible in many cases as hardly any thermoplastics
will withstand a heat treatment of several hours or more at 200 C.
As an example Table 11.10 shows the compression set of various rubbers as post cured
and NPC. It is quite remarkable that special NPC materials exhibit a low compression
set (and hence a lower tendency to the decay of internal stresses) without the need for
post-curing.
This group of materials contains certain additives which result in a low compression set
as moulded and after post cure. However, as NPC grades they are suitable for technical
applications only.
Table 11.10 contains some ranges for the compression set. Such variations originate with
batch to batch fluctuation and the accuracy of determination of the compression set.
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Table 11.10 Comparison between compression sets (CS)

(Compression set; 25% deformation for 22 h at 175 C) post cure and NPC. Duration of
post cure is 6 h at 200 C
ELASTOSIL type CS NPC [%] CS post cure [%]
LR standard LR 3003/60 60 70 10 20; max. 35
LR fast curing LR 3004/60 60 70 10 20; max. 35
LR self-adhesive LR 3070/40 60 70 10 20; max. 35
LR fast curing NPC LR 3005/60 15 25; max. 30 10 20; max. 35
LR oil resistant NPC LR 3013/60 20 30; max. 30 10 20; max. 35
HTV standard R 401/60 15 25; max. 30 10 20; max. 35
HTV oil resistant NPC R 701/60 20 30; max. 30 10 20; max. 35
All materials from Wacker Chemie GmbH
The compression set is an interesting parameter and not only relevant for mechanical
bonding but also for the overall performance of a gasket or any other related application
irrespective of whether it is a simple moulding or a composite structure.
11.11.1 Duration of Bonding - Chemically Bonded Composites
From investigations carried out by Wacker-Chemie GmbH it was found that bonding
quality increases over time. Nonetheless, a bond cannot be guaranteed to last over a
certain time under all possible circumstances.
It is imperative for processors to apply sufficient testing to the bonding. Once a composite
part is used under certain conditions where the function of the part essentially depends
on the bonding force, sufficient testing of a prototype or a trial series is inevitable prior
to use in the field. In many cases an enhanced ageing test under laboratory conditions
will provide the solution.
A viable solution could be the combination of primer and self-adhesive material, or even
a combination between self-adhesive and mechanical anchorage. Mechanical anchorage
will ensure a residual stability of the composite, and the self-adhesive material will
guarantee hermetic sealing.
311
In many other cases adhesion is only required until the assembly of a part. In this
case a growth or loss of adhesion over time becomes irrelevant.
Having mentioned the factors influencing the bond between the silicone rubber and
the substrate and bearing in mind the vast number of possible material combinations
the necessity of preliminary extensive tests for adhesion is obvious.
Figure 11.7 shows the development of adhesion of self-adhesive LR over time.
During injection moulding, i.e., on a very short time scale, adhesion is quite weak.
Once the part is carefully extracted from the mould and stored for a certain period
of time (weeks or months) the adhesive force increases significantly - sometimes to
an extent where silicone and substrate cannot be separated and the silicone rubber
will break before the hard and soft components can separate. This quite long storage
time leading to the desired adhesion can be shortened substantially by using a heat
treatment.
Figure 11.7 shows that adhesion increases with the course of time. This property is
used as evidence to assume that composites made of self-adhesive materials or
materials and primers will not fall apart after any time under normal circumstances.
Figure 11.7 Formation of bonding of self-adhesive ELASTOSIL LR 3070/40 as a

function of time
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11.12 Alternatives to Injection Moulding
Alternatives to multi-component injection moulding are worth considering too. These

techniques have not yet been referred to in the present chapter.
If the available mould technology is outdated (there are only a few good mould makers
capable of providing the appropriate mould design for LR and/or HTV), it is also possible
to choose adhesives or even welding (the latter may be considered a special form of two-
component press curing) for bonding. A further alternative is to use clamping technology
which is related to undercuts. Some brief remarks on applications and their required
properties will follow.
11.12.1 Adhesives
RTV1 (room temperature vulcanising) adhesives are available for joining silicone parts
to one another, or to join silicone rubber mouldings or extrusions to a number of different
substrates. Adhesive joining also achieves a chemical and/or physical bond between
materials which cannot be combined in one of the processes mentioned previously. As
RTV1 systems cure at room temperature, the processor faces less temperature restrictions.
However, curing takes much longer at room temperature than at high temperatures. It
can last as long as 24 hours, depending on the geometry of the adhesive layer. In some
cases, it is advantageous to change to an HTV adhesive. This will be the case if the
contact surface between the joined parts is too large to provide an unhindered path for
the moisture in the air - a reactant in the crosslinking process of RTV1 materials.
HTV adhesives require heated parts and will only work with materials suitable in terms
of thermal stability and bonding properties. PTFE and polyvinylidene fluoride (PVDF)
cause problems because no suitable bonding agents exist.
A number of RTV1, RTV2 and HTV self-adhesive materials are available which will not
only work as an adhesive at first sight but also in cured in place gasket, a technology of
growing importance in the automotive industry and many other areas.
A silicone adhesive can also be used for many types of general purpose bonding of materials
other than silicone rubbers.
11.12.2 Welding
Welding is widely used for bonding silicone rubbers, and is closely related to injection or
press moulding. However, usually one does not apply a complicated mould technology
313
or a process similar to HTV and LR processing. It is also related to the adhesive bonding
technique previously described.
The method is quite simple. Extrusions and/or mouldings are mated in a heated cavity
and an HTV material is pressed into the gap between the parts. The HTV material cures
and a chemical bond remains, as the HTV crosslinks internally to the same extent as
with the surfaces of the parts to be joined.
Welding is a technique widely used in plastics processing, however, welding of silicone

rubbers is different. In this case a cold liquid is heated to solidify by crosslinking. In
other words, no melting process with subsequent solidification upon cooling is involved
at all, which is a contradiction to common experiences with thermoplastics.
11.12.3 Mechanical Bonding Techniques After Moulding
A silicone rubber can be bonded to a solid substrate if it is clamped into or onto it. A
very good example is the baby soother. The silicone nipple is injection moulded by a
common LR process and then post cured. After that the nipples are clamped into a
plastic construction or even overmoulded by thermoplastic.
In clamping it is essential to protect the silicone part from any mechanical damage such
as cuts or scratches. These ruptures of the silicone moulding will lead to potential sources
for defects during its use. Mechanical damage after clamping can also be a risk.
Another example is insulators for cable connectors which have been previously injection
moulded from LR or HTV. Then, they are expanded and held in that state by a plastic
spiral which is removed when it is applied onto the cable (thus retaining the original
shape of the insulator). A large number of similar applications can be found in the
automotive, medical fields, etc.
To minimise risks of mechanical rupture a range of silicone rubbers, both LR and HTV
grades are available in different levels of mechanical strength and Shore hardness. Table
11.11 gives a brief survey and comparison with standard properties. This table is
simplified as it refers to tear resistance only.
11.13 Summary
For additional information on general aspects of silicone rubber bonding and latest
developments in silicone rubber technology, the reader is encouraged to refer to literature
such as [17, 18].
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Tear resistance
Table 11.11 Comparison of tear resistance between standard silicone

rubbers and high tear grades
Tear resistance
ELASTOSIL
Material Hardness (Shore A) ASTM D624-00 Remark
Grade
[16] [N/mm]
Addition cure
LR standard LR 3003/40 40 25
standard grade
Addition cure high
LR high tear LR 3043/40 40 40
tear grade
Addition cure
LR standard LR 3003/50 50 28
standard grade
Addition cure high
LR high tear LR 3043/50 50 47
tear grade
40; Elongation at Peroxide cure
HTV standard R 401/40 20
break ca. 600% standard grade
Peroxide cure high
HTV high tear R 420/40 40 50
tear grade
40; Elongation at Addition cure high tear
HTV high tear R 4105/40 50
break up to 1000% grade low modulus
70; Elongation at Peroxide cure
HTV standard R 401/70 20
break ca. 600% standard grade
Peroxide cure high
HTV high tear R 420/70 70 50
tear grade
70; Elongation at Addition cure high tear
HTV high tear R 4105/70 50
break up to 1000% grade low modulus
There is much more that could be written on the subject of bonding silicone rubber. The
main intention has been to provide a brief overview of what it is currently possible to
achieve using silicone rubbers in the rubber industry. Fabric reinforced tubing and related
applications have been left out, as there are too many processing techniques to be covered
in a chapter of this size.
This latter field is closely related to coextrusion. The remarks in Section 11.10 on cables,
give some idea of what can be done with general purpose coextrusions. This processing
technique opens up a much wider set of possible material combinations. This is due to
the large differences in the process of extrusion compared to injection or press moulding.
315
A further topic not mentioned here is the bonding of silicone on plastic inserts or moulded
preforms, the surface of which has been plasma treated. Another less important technology
is the necessity of priming the mould with a release coating, e.g., Teflon. These two
techniques imply additional production steps and are therefore less relevant for the future
of silicone bonding to plastics.
As mentioned, existing technology allows the use of primerless moulds (not to mix up:
primering mould = improvement of mould release properties and primer to achieve
bonding).
Summing up, composite technology is capable of providing simple but very elegant
technical solutions. Composites have been known for decades or maybe even centuries.
Composites comprising soft and hard materials are quite new and the extraordinary
speed of development of their scope of applications is not only incredible but also
unforeseeable. We would like to predict that such technology and in particular technology
focussing on silicone composites is going to be underestimated at any time - too many
substrates, an indefinite number of ideas and the creativity of material scientists account
for that.
References
1. K. Pohmer, Kunststoffe, 2000, 90, 2, 94.
2. K. Pohmer, Kunststoffe Plast Europe, 2000, 90, 2, 34.
3. P. Jerschow, Presented at the Processing of Liquid Silicone Rubber, Seminar, IKV

Aachen, Germany, December 1998.
4. P. Jerschow, Presented at the Injection Moulding of Composites of Hard and Soft

Materials Seminar, SKZ Stuttgart, Germany, December 1998.
5. K. Pohmer, Presented at the Injection Moulding of Composites of Hard and Soft

Materials Seminar, SKZ Stuttgart, Germany, June 1999.
6. P. Jerschow, Kautschuk Gummi Kunststoffe, 1998, 51, 6, 410.
7. P. Jerschow, Presented at the IRE conference, Manchester, UK, June 1999.
8. VCI, Umwelt und Chemie von A - Z, Herder Verlag, Freiburg, 1990, Germany,
8th Ed., p.136.
9. A. Tomanek, Silicone und Technik, Hanser Publishing, Munich, 1990, p.42.
316
10. J. Comyn, Presented at the Rapra, Rubber Bonding Conference, Frankfurt,

Germany, 1998, Paper No.1.
11. DIN 53531-1

Determination of the Adhesives of Rubber to Rigid Materials by the One-plate
Method, 1990.
12. FDA, Code of Federal Regulations, 177.2600
13. BgVV, German Health and Veterinary Authorities, Ed., Franck Kunststoffe, 1995,
Chapter 15.
14. ISO 10993-1

Biological Evaluation of Medical Devices - Part 1: Evaluation and Testing, 2002.
15. United States Pharmacopeia, current XXIII USP Class VI protocol, Washington DC.
16. ASTM D624-00e1

Standard Test Method for Tear Strength of Conventional Vulcanized Rubber and
Thermoplastic Elastomers, 2000.
17. P. Jerschow, Presented at the Rapra, Rubber Bonding Conference, Amsterdam,

The Netherlands, 2000, Paper No.14.
18. K. Wieczorek, Presented at the Rapra, High Performance Rubbers Conference,

Berlin, Germany, 2000, Paper No.10.
317
318
12
Failures in Rubber Bonding to Substrates
B. Crowther (Sections 12.1 and 12.3) and

K. Dalgarno (Section 12.2)
Bonds between rubber and substrates can fail for a number of reasons. Section 12.1 deals
with some of the causes of rubber to metal bond failures. Section 12.2 examines the type of
failures which are adhesion related, in fabric or cord reinforced power transmission belts.
Section 12.3 discusses a phenomenon which causes service failures of rubber components,
mainly in sealing applications. This phenomenon arises through a bond which is formed
between the rubber (nitrile) and the metal mating surface of a valve or similar, which is of
sufficient strength to rupture the rubber surface when the valve is opened.
12.1.1 Introduction
Bond failures in rubber to metal products are fortunately of relatively rare occurrence.
When failures do occur they can stem from a number of fundamental areas and the
faults are generally very characteristic of those problem areas. The main areas of bond
inconsistencies and failures are:
faulty product design,

faulty metal preparation,
incorrect moulding procedures,
incorrect production quality testing procedures,
corrosion in service,
product abuse,
other failure modes.
12.1.1.1 Rubber to Metal Bonded Components
Rubber to metal bonded components have been designed and manufactured since the
early days of the rubber industry and their technology and manufacture has been discussed
elsewhere [1]. However, the design of the rubber to metal component in the modern car
engine mount has provided other problems for the rubber manufacturer not related to
319
Commercial rubbers
its engineering properties. Simple sandwich mountings cause no problem to the rubber
to metal bonder, neither do the multi-plate products such as bridge bearings, but modern
engine mounts of complex fail-safe nature can often be totally impossible to mould in
one operation. This is due to the simple fact that complete bonding of rubber to the
complex interlocking metals would create a product which, after bonding, would be
totally locked into place in the mould, with no means of removal. This type of product
can of course be made by a different bonding procedure known as partial post
vulcanisation bonding. The technique is to partially bond within the mould and then to
add the final metal plate externally to the mould. These bondings are more expensive
because of the additional operations to complete the metal application necessary for the
satisfactory operation of the unit.
12.1.2.1 Product Design and its Effects on Bond Failure
All rubber to metal product designers must consider the effects of stresses exerted between
the metal and rubber at the interface. This is particularly important at the edges of a
component. Correct shaping of this part of the moulding will remove the stresses away
from vulnerable conjunction points of metal and rubber.
It is very important that rubber section corners should be radiused at the point of contact
with metal components which exceed the area of the bonded rubber portion. This small
modification of the rubber portion design can increase fatigue life by a factor of 7. In
components which have the metal and rubber of the same dimension, then it is vital that
the metal component be chamfered back to allow rubber to be moulded over a larger
area than the end of the metal presents. The ideal shape for this removal of metal should
be a wedge shaped chamfer which will give maximum bonding area and stress relief.
This type of chamfer, which is simple to machine and does not detract from the component
design or function can increase fatigue life by a factor of 6.
It is particularly important in the finishing of rubber components that feather edges of

rubber are not mutilated by brushes, grinding wheels or other excess rubber removing
devices. Too enthusiastic an application of a buffing or grinding wheel against a metal to
remove excess rubber will very quickly generate sufficient heat to successfully debond
most rubber products. Excessive heating from any external source to the metal to which
the rubber is adhered will result in debonding taking place. Likewise nicking of the
rubber surface can result in the tearing of the rubber back into the mass during flexing in
service. If the body of the flange of rubber becomes pierced then this will allow atmospheric
pollutants and corrosion creating materials to penetrate to the region of the bond and to
commence the process of corrosion, usually electrochemical in nature, which will gradually
undermine the bonding agent primer and destroy the bond.
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12.1.2.2 Faulty Metal Preparation

Many bonding failures can be traced back to faulty metal preparation, poor application
of bonding agents or careless handling techniques on the factory floor.
Metal Cleaning
Poor metal cleaning, or the use of contaminated cleaning medium, can be spasmodic in
appearance unless good housekeeping is practised. Metals must be thoroughly cleaned
of any grease or oil protective coating applied to prevent corrosion, before grit blasting
to prevent oil/grease contamination of metal cleaning grits or chemical solutions used
for the removal of corrosion and foundry products. Abrasives used for the cleaning of
the metals, after the removal of greases, must be monitored to ensure that the correct
type and grade is being used for the application (see Section 3.2.2, Tables 3.2 and 3.3).
Incorrect metals used as abrasives can leave metal particles on the cleaned surface, which
will set up galvanic cells under the applied primer. Grease contaminated abrasive will
apply grease to already cleaned surfaces. Round shot must not be used as a cleaning
media only grits with the correct properties (see Sections 1.1.4.1 and 3.2.2), otherwise
unwanted detritus can be caught into cavities formed by the shot and then the lips of the
craters peaned over and the contaminant trapped. Finally, worn abrasive will not
efficiently clean the surface of the metal and will also create considerable dust which
may be left on the surface of the metal.
Improperly or insufficiently treated metal being prepared for bonding, may mean that
scale and corrosion are not completely removed. Most of this type of surface lying material
is only loosely attached to the metal surface and can, under load in service detach itself.
The result, of course, is a partial delamination of the contact area for the rubber with the
metal. Once this detachment has taken place there will a gradual widening of the detached
area usually accompanied by some corrosion.
Application of the primer coat to freshly prepared metal must be as quick as possible to
prevent atmospheric agents causing corrosion. Oxide films (corrosion) are not usually
securely adhered to the surface of the parent metal and thus can be easily pulled away. If
the bonding primer has adhered to the corrosion layer it too will be pulled away from
the desired contact between the primer and metal. This corrosion may not be visible to
the naked eye, but can result in underbond corrosion continuing after vulcanisation.
Obviously ambient conditions in the metal preparation area dictate the timing and speed
of primer application.
Dust from the metal cleaning operation must be removed from the surface of the metal
before the application of the primer. Observation of the application of the primer should
also show that there has been a complete wetting out of the metal surface by the primer.
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This is particularly necessary with water-based primers and bonding agents. Solvent
borne bonding agents wet out a clean metal surface with far greater ease than do the
water-based products.
The water-based bonding systems are much more sensitive to the presence of greases on
the metal surface, and even though the metal degreasing has been carried out efficiently
it will be necessary to ensure that no finger marks are found on the areas to be bonded.
Solvent-based systems are capable of absorbing and dispersing small amounts of fats
without causing problem to the bond. Water-based systems cannot absorb and disperse
fats and therefore greater care has to be taken in the handling of metals.
Metal cleaning using non-solvent systems
The trend for metal cleaning is to move away from using solvents in general and
chlorinated systems in particular. A number of alternative cleaning systems exist, but
those which use water must be used in such a way that the metals are totally dry and
corrosion free when being presented for bonding agent application.
N.B. Beware of cross contamination of abrasive and metal treatment plant by personnel
other than correct operatives. It has been known for engineering departments and
individuals to not clean extremely greasy components and car engine decarbonisation
parts prior to using an abrasive plant and thus to completely foul the abrasive supply.
The result has been observed to cause extensive bonding problems until the contaminated
abrasive was discarded and the plant cleaned of traces of grease and flakes of carbon.
Preparation of metal surface by chemical modification

(anodising, plating, sheradising)
The alternative metal pre-treatment process to grit blasting uses 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 prepared surfaces
of variable quality. 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.
Treatments for stainless steels
There are various suggested 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
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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 and hydrofluoric acid, sulphuric or chromic acid are suggested as
most suitable for this. However, the nature of the substrate alloy and the steels heat
treatment all have a bearing on the bondability of the metal.
Phosphate coating (see also Section 1.4)
Steel is often phosphate coated for use within the engineering and decorative laminate
industries to reduce corrosion. Iron or zinc phosphate can also be used. However, although
for some years used as a corrosion protection technique for rubber to steel bonding, it
can be difficult to control the process, resulting in a variable thickness of phosphate
deposit of varying crystalline structures. If too thick a phosphate layer is obtained it
becomes too friable and lacking in cohesive integrity to produce the adhesive strength
required to sustain 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, with chromium oxide to prevent
corrosion of the areas of minimal phosphate cover. Chromium oxide, does not readily
react with a bonding agent. Chromic acid is an hazardous chemical and alternative
materials can be recommended by bonding agent suppliers for the passivation or sealing
of the phosphate coating.
The nature of the phosphate deposited on the surface of the steel depends to a large
extent upon the nature of the steels microstructure 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, whereas cold-rolled steel, having acquired a different surface
orientation structure, can acquire a lumpy large flake phosphate structure, which is easily
broken apart under stress.
Any waste water draining 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 about 1 2 parts per million.
Zinc coating or galvanising
Metals treated in this way are supplied to the rubber bonder already in a treated form.
To be effective the zinc coating must be hot dipped to the cleaned metal, to give a
galvanised finish. Bonding to this finish is not easy. The crystalline structure of the
galvanised zinc and its dipped coating thickness, can result in the flaking off, under
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stress, of some of the coating, resulting in bond failure. The recommended treatment [2]
for cleaning a galvanised finish is:
i) degrease metal part,
ii) abrade the galvanised surface with grit,
iii) degrease then apply adhesive as soon as possible.
or
i) immerse in a solution of 20 pbw concentrated HCl with 80 pbw deionised water,

for 2 4 minutes at 25 C,
ii) rinse thoroughly in cold, running deionised water,
iii) dry for 20 30 minutes in a 70 C oven,
iv) apply adhesive as soon as possible.
The second method is more widely used.
Zinc sheradising
A method can be specified which has to be carried out by specialist processors to give
what is in effect a fused zinc surface to a steel component, which gives very good
environmental protection for the steel component. 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 does cause problems with zinc build-up in screw threaded components (the
latter would have to be protected by a sleeve or would 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.
Aluminium - anodising
Aluminium is usually anodised electrolytically, in the presence of an acid, either

sulphuric, chromic or phosphoric, to give a tough resistant oxide film, which generally
forms good bonds with the usual bonding systems. The anodising must be carried
out with care and the type of crystalline structure being formed on the aluminium
surface must be considered. A uniform reticulated structure is desired, not a
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microscopically fragmented rippled surface, sometimes called ice flows [3], which
is unstable, easily fractured, and therefore unable to maintain good adhesive quality.
If anodising is carried out by a custom plater he will need to be informed of the type
of anodised structure desired.
N.B. The final stage 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 metal storage areas must be held at least 5 10
C above the dewpoint and ideally be as near to the ambient temperature in the bonding
agent application shop, which itself should be in the region of 18 22 C minimum.
12.1.2.3 Application of bonding agent to metals
Metals must be completely grease and dust free when the primer is applied. The primer
must be properly prepared, especially if new supplies are being prepared from bulk
containers, to ensure that all the constituents of the bonding primer system is in suspension
when being applied to the metal surface. The application of the primer is the most critical
part of the metal pre-treatment process, for if not correct, bonding will either be patchy
or non-existent. If spray application is being used, especially hand spraying, then care
must be taken to ensure that the primer spray hitting the metal surface is capable of
wetting out the complete surface and not dry (loss of all solvent) at the time and point
of contact with the metal. If dry then cobwebbing (the condition of the bonding agent
resulting from drying out before reaching the substrate surface and is in the form of fine
filaments) will occur and although the metal may appear to be covered, poor and patchy
bonding will result.
Application of the primer to the metals must be carried out in such a way that there is no
possibility of entrapping air between the primer and the metal. Any such trapping will act
as a buffer between the primer and the metal and no bond will be achieved. The bond
between the primer and the metal is essentially a mechanical one taking place around the
asperities of the cleaned metal surface; although some degree of chemisorption also takes
place. Intimate contact with the metal is therefore essential for good bonding to take place.
Addition of primer and rubber bond coat
Bonding agents, especially the primer systems, are very prone to settlement during
storage. The result of the settlement of the suspended materials to the bottom of the
drum is the formation of a layer of quite hard material which is very reluctant to
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return to the suspended state. It is therefore important that as soon as possible after
delivery, and certainly some 24 hours prior to use, the drums contents are agitated
continuously to achieve re-suspension of the deposited materials. Drum rolling on ball
mill rollers for 24 hours prior to 24 hours stirring with a motor with suitable paddles
to lift the suspended material is the only way to ensure that satisfactory reproducible
bondings are continuously achieved. At the end of the stirring period the critical visual
quality control must be carried out together with a cone bonding test to ensure quality
of the bonding agent. Viscosity and flow cup checks do not fully indicate the state of
the dispersion of the vital ingredients of the bonding system and cannot readily be
used in any case with the water-based systems. Hydrometer measurements are suggested
by bonding manufacturers for measurement of the degree of dispersed materials with
these emulsions.
If multiphase waterborne systems are being used then special considerations concerned
with storage conditions and stirring must be observed. Having a surfactant system
incorporated to facilitate the preparation and stability of the product, it is necessary to
strictly observe the manufacturers instructions, as otherwise flocculation will occur.
Once an adequate suspension has been achieved it is then essential to keep that suspension
operational whilst treating the metal components. The ideal method is to use a
continuously agitated system which does not allow settlement but is not so agitated as to
cause bubbling, especially with water-based materials.
Before the application of the rubber bonding adhesive layer to the primer it is necessary
to ensure that contamination has not occurred to the primer surface in the drying and
storage period. Dust should be removed and any parts with embedded contamination in
the primer layer must be recycled, otherwise failure will result. Good housekeeping is
essential to achieve a well run bonding shop.
The rubber bonding coat, which is usually the second layer of bonding agent to be applied
to the metal, must only be applied when the solvent from the application of the primer
has all evaporated. Failure to allow adequate drying time for the primer coat will result
in either bubbling of the surface of the primer or a separation of the two bonding layers
at the interface. This is usually seen as polished bonding agent surfaces being evident on
both rubber and metal.
Application of tie cements to the surface of the rubber bonding coat to assist with the
bonding of difficult compounds also need care, to ensure that the solvent is totally
removed from the various bonding agent layers before passing the prepared metals to
the moulding presses.
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The addition of the primer and bonding coat to the metal should be strictly within the
specified thickness parameters laid down by the supplier of the bonding agent system.
Too little bonding agent or over-diluted systems being used for spraying application
will often be insufficient to give an even coating of the bonding agent to cover the hills
and valleys of the asperities created during the cleaning process. It is vital that all
peaks are covered adequately and evenly by the bonding agent otherwise bond failure
by tearing can be initiated from such peaks.
Conversely the addition of too much bonding agent is unwise not only economically
but also from a bonding integrity point of view. The primer is a rigid coat when
vulcanised and the bonding coat only semi-flexible and thus too much of either system
coating will tend towards a weakness line being formed at the juncture of the bonding
agent systems. This fault is usually characterised by bonding agent attached to the
surface of the rubber in the failure area being visible.
Incomplete drying of the layers of bonding agent prior to the application of the next
coat is visible in a similar manner to that described for too much bonding agent being
used. Often the detached bond will show that there have been bubbles formed in the
bonding agent layer with the result that the outer bubble layers adhered to the rubber
are brittle and easily fracture, with resultant bond failure. This problem is much more
prevalent with the water-based systems, although heated metals help.
N.B. Use of waterborne bonding systems has some major requirements which differ
from the way solvent-based systems are handled. Failure to follow the following rules
may well result in significant bond failure problems:
Initial storage requires precautions against low temperatures which will result in
possible freezing or flocculation. Similarly too high a storage temperature will have
similar effects on flocculation.
Too violent agitation of adhesive will result in flocculation.
Dried waterborne bonding agent solidified on the edges of a drum, and on

equipment, cannot be redissolved back into solution (differs from solvent-based
system). Consequently dried agent MUST NOT BE ADDED BACK INTO A
SOLUTION, as otherwise failures will result from bits being deposited with the
bonding agent onto the metal. These bits will not bond and will inevitably result
in localised bond failures.
Cleaned metals need to be heated to help water to evaporate. It may also be necessary
to provide some degree of forced drying to ensure economic drying times.
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Dilution of the waterborne systems requires deionised or distilled water, and definitely
not tap water.
Cleanliness of metals is more critical when using waterborne systems. Solvent-based

systems can absorb very small quantities of oily contamination without affecting
bonding quality. Waterborne systems cannot absorb oils but are repelled by them,
and if small traces of oils are present they will prevent the bonding agent wetting out
the surface and will result in patchy cover of the metal by the bonding system.
12.1.2 Incorrect Moulding Procedures
It is unlikely that incorrect vulcanisation time will result in poor bond strength, because
of normal factory control systems. An exception can occur when an incorrect batch of
compound has reached the presses. If correct control limit gates for compound viscosity
and Mooney scorch are applied for the compound then the cure-rate should have been
designed to allow for adequate compound flow, and consolidation in the mould cavity
prior to onset of any cure, to ensure that totally unvulcanised compound comes into
contact with the bonding agent surface. If this condition is met then the ability to
generate the maximum bond between the bonding agent and the rubber will be
maximised. Any compound condition other than this will result in variable bonding
values and could lead to field failures in service. Quality control procedures should be
such that this cannot happen.
Incorrect metal handling techniques or improper storage of prepared metals can be a

serious problem at the moulding press and can be the cause of subsequent failures. This
type of fault is the responsibility of the manufacturing and quality control departments
and should be quickly corrected. If control is lax, dust layers on prepared metals, or
contamination by sweaty and greasy moulders gloves, can give bond failures. Greasy
thumbprints on metals or rubber blanks can have similar effects.
Some organisations prefer to heat treat (bake) metals which have been treated with
bonding agents, to ensure that the degree of plasticity still present in the bonding agent
does not enable it to be swept off the surface of the metal whilst the rubber compound is
being injected or transferred into the mould cavity. Careful mould design can usually
eliminate most bonding agent sweeping problems by careful direction of the flow of the
injected rubber compound. If it is necessary to prebake the bonding agent to the metal
surface, care must be taken to ensure that the prebake does not fully crosslink the bonding
agent and thus leave no crosslinking possibilities between the bonding agent and the
rubber. Overbaked bonding agent systems usually give bond failures which leave the
rubber/bonding agent system faces quite shiny and polished (see also Section 4.3.2).
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It is far more likely that incorrect component removal techniques from the mould cavities,
causing overstressing of a very vulnerable bond, will affect the integrity of the component.
One problem is the over-enthusiastic application of bonding agent causing overspill onto
metal edges which come into contact with flat areas of the mould. Bonding agent will bond
to mould surfaces just as well as to component metals and can cause severe product removal
problems which will result in stressing of the components. Levering out of mouldings with
metal tools, instead of hydraulic ejectors, will also give uneven stresses to the bond.
The other very significant danger in moulding of rubber to metal components is the
prescribed or accidental application of release agent to the mould cavities to ease release of
the finished product. Release agents can be trapped between the rubber and the bonding
agent faces and prevent an adequate bond being achieved. Ideally no release agent should
be used in a mould producing bonded components, neither should it be used in the vicinity
of such presses. Moulding shop air contamination by minute droplets of release agents is
very easily achieved and these will condense on any exposed metal surface. Ideally the
press shop producing bonded components should be at a positive pressure to neighbouring
shops to prevent cross contamination taking place.
12.1.3 Incorrect Production Quality Testing Procedures
The forming of the required shape and the vulcanisation of the rubber in a rubber to metal
bonding process or the production of any rubber component, does not complete the
crosslinking and full attainment of the ultimate network structure. Cure times for products
are calculated using curemeter information to usually 90 or 95% cure. The 5 to 10%
additional cure comes from retained heat in the product after demoulding has taken place.
Rubber to metal bonded components are required to mature after vulcanisation, to enable
the full crosslinking, structural networking and chemisorption linkage processes to take
place between the various layers of the metal/primer/bonding agent/rubber complex.
Some structural strength within the bond is achieved immediately after full vulcanisation
time has been reached, sufficient to allow removal from the mould. However, it is
important to ensure that full stressing and testing of the bond be carried out only after a
period of 24 hours has elapsed.
Rubber has a poor thermal conductivity and thus rubber to metal bondings which often
have a low surface to volume ratio, i.e., large rubber volume, take a considerable time to
cool to ambient temperature. This heat retention is often compounded by the close location
to the vulcanising press of the skip into which the product is placed at the end of the cure
cycle, the moulding shop ambient temperature, and the piling up of hot product as the
work shift continues.
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Vulcanisation of the rubber does not cease completely at the end of the press/cure
cycle. As the temperature of the moulded product reduces, the rate of vulcanisation
decreases, but it does still continue, even into service life. Many maturation reactions
take place as the product returns to ambient temperatures and even in service some
crosslinking reactions will still take place over an extended period of time. The filler,
usually carbon black for most components, will form its own reinforcement structure
over a period of time, thus contributing to the required product properties. Testing of
the product too early can result in overstressing of the rubber in critical stress zones
and this in itself can lead to premature failure of the product in service.
Particularly prone areas of bond stress in the early part of the components existence
are concentrated by protrusions of metal components, such as bolt heads, into the
rubber mass. An extensive load created in the area of such protrusions concentrates in
their vicinity and localised bond failure can occur. This may not be evident to the
observer but cavitation may have been created which can expand under stressing of
the product in service, with resultant complete failure through rubber tear.
Proof testing of product after manufacture using a calculated limited stress can, if
incorrectly carried out, be a source of subsequent product failure. It is necessary to
calculate a suitable set of stress parameters to use for testing the product, i.e., a load
and extension, such that the product does not become overstressed and does not retain
permanent evidence of damage as a result of proof testing. This can appear as distortion
or incorrect dimensions.
12.1.4 Corrosion in Service
Corrosion in service can occur from a number of different sources:
electrochemical attack - salt or similar,

galvanic sources - underbond,
overheating,
chemical attack.
12.1.4.1 Electrochemical
Electrochemical corrosion of a metal beneath a rubber coating necessitates the presence

of an aqueous phase. There will also need to be anions and cations to provide
conductivity in the aqueous phase and the presence of oxygen to support the cathodic
330
reaction. To be present at the site of potential corrosion the materials have to find
passage through the rubber layer, usually by migration. If an electrical potential is
present the migration of water through the rubber is facilitated [3]. A similar effect
occurs influencing the migration rate for cations by chemical type, i.e., Ca+ migrates
faster than Na+. Thus the rate of cationic delamination occurs at a faster rate in calcium
chloride solution than in sodium chloride.
Anodic
Residual stress in the metal component gives rise to an anodic condition which is
largely eliminated when the metal is fully annealed. Cold working of a metal by plastic
deformation will result in the electrical potential of the metal being moved in the
direction of the areas of greatest activity and will be anodic in character. Incompletely
cleaned metal surfaces can also be the source of potential differences. Presence of
dissolved gases and the formation of protective layers during the corrosion processes
are all factors affecting the generation and degree of the corrosion and its spread over
the metal surface.
Anodic undermining can occur beneath a rubber coating or between the components of
a rubber to metal bond. Anodic undermining and delamination occur very slowly in
comparison with cathodic delamination.
Cathodic
Alkali can be generated by the cathodic half of a corrosion reaction or the cathodic
reaction may be driven by means of an electrical potential. When the cathodic reaction
occurs between the rubber and metal surface the pH of the solution under the rubber
may be as high as 14. Many factors (summarised by Leidheiser [3]) concerned with
cathodic delamination are detailed. No definitive mechanism for this type of delamination
has been determined although a number of suggestions have been put forward [3]. These
include alkaline attack on the polymer, surface energy considerations and attack of the
oxide at the interface.
Moisture absorption into textile and fibre reinforcements in specialised seal compounds
is often possible where exposed fibre ends are exposed to the surface of the rubber
compound, either during moulding or subsequently during trimming operations. As the
amount of moisture absorbed alters with atmospheric conditions of humidity and
temperature there will be a variation in the activity of the electrolyte formed in the
textile/rubber and thus the corrosivity of the compound to contacted metals.
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12.1.4.2 Galvanic Attack
Galvanic attack usually occurs as the result of an incorrect choice of abrasive metal
cleaning media. Incompatible metals used in assembly of components in service can also
result in galvanic cells being generated and the resulting corrosion will, with time, cause
bond decay.
12.1.4.3 Overheating
The bond between rubber and the metal surface is essentially a mechanical one achieved
by the use of various resins and chlorinated rubbers, which when heated and crosslinked
within their mass form a rigid network. Subsequent application of a high temperature
directly to the area of the bond will result in the loosening of the grip of the primer
material, and under the application of a load the bond will fail. This method is sometimes
used to reprocess metals from components which have been rejected by quality tests.
12.1.4.4 Corrosion by Chemicals - Not Electrochemical
This type of attack can be from a variety of sources, some of which can be deliberately
applied to the component. Application of unsuitable metal finishing paints or metal
preservatives to the moulded component can soften the primer and/or bonding agent
layer with the subsequent loss of product integrity and failure of the component.
This type of corrosion can also occur, fortunately infrequently, in rubber to metal bonded
components which have been designed to meet specific, often onerous service conditions.
High levels of plasticisers necessary to meet very low temperature operating conditions
have been known, after long periods of service, to migrate through the layers of bonding
agent and effectively debond the component. The mechanism of this type of debonding
is not fully understood. However a possible explanation which can be given is as follows.
Primer to metal adhesion is fundamentally a combination of a mechanical keying, with a

degree of chemisorption taking place. Bonding primers can be based on a complex system
of materials with high resin, high chlorinated rubber combinations which probably give
an interpenetrating type of structure. Obviously the penetration into and through such a
primer layer by a plasticiser from the rubber layer will have the effect of softening and
loosening the grip of the primers contact with the metal surface irregularities. If the bond
adhesion failure occurs at the primer/bonding agent interface, a very similar explanation
can be put forward. At this interface the reactions taking place are a combination of
interdiffusion, adsorption and chemical crossbridging and migration of the plasticiser
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can cause problems of debonding by either softening of the crossbridging or by chemical

interference. In addition of course there may be a chemical attack at the metal surface of
the bonded component by the migrating plasticiser which will cause pitting and erosion.
12.1.5 Product Abuse
It is difficult to be precise about details of product abuse, as the form this takes can be
wide-ranging. Some of the abuse to which rubber to metal bonded products are submitted
is totally preventable whilst others are purely accidental. The most frequent cause of
failure are:
exposure to high temperatures,

exposure to oils and solvents,
painting to match machinery to which bonding is fitted,
serious misalignment of flexible couplings,
service loading too high compared to original specification,
corrosive ambient service conditions not originally specified,
mechanical interference, e.g., grinding of outer metal surface generating high heat.
These are a selection of the problems that can occur to cause either failure or unsatisfactory
operation, through ignorance of the properties and susceptibilities of rubber to metal
bonded components.
12.1.6 Other Failure Modes
Evidence of metallic particles clinging to the rubber surface can be an indication of a

number of factors:
poor cleaning and removal of foundry materials from the surface of the metals prior
to the coating with bonding agent,
failure to remove all dust from metal cleaning from metal surface prior to addition
of first bonding agent coat,
poor adhesion of plating applied to metals as decorative or anticorrosion finishes,
inadequate removal of zinc dust if zinc sheradising has been used to give metal
corrosion resistance in service without painting,
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incorrect coating being laid down during phosphating process of metal treatment,
resulting in flaky, porous layer being deposited on the metal. The strength of this
flaky coating is insufficient to resist workload stressing of rubber to metal bond,
incorrect anodised coating on aluminium metals which resists bonding to the primer.
Some decorative anodised finishes have this problem.
12.1.7 Factors Affecting Adhesion of Rubbers
The adhesion of rubbers is further complicated by the rheology of rubber and its added
compounding constituents. Blending two or more rubbers will give more complexity to
the flow and adhesion behaviour of the system. The ability of the rubber compound to
flow and establish intimate contact with the substrate is of paramount importance, to
enable the forces discussed previously to establish the conditions required for optimal
adhesion. Any material which interferes with the establishment of the interface must be
avoided. The establishment of a stable, strong interface between the two materials is the
foremost requirement for successful adhesion.
The processes which are likely to determine the interface formation are:
the ability of the adhesive/rubber mass to flow uniformly,

complete wetting of the adherend by the flowing adhesive/rubber mass,
the stabilisation of the rubber/adhesive interface.
12.1.7.1 Rubber Flow
The ability of the rubber to flow must be a priority in the compound design. Without the
ability to flow readily the rubber compound will not be capable of wetting out the surface
of the adhesive film and thus the necessary interfacial contact will not be completely
achieved. Reduction of the molecular weight of the rubber is beneficial, but other means
of promoting flow may be problematical, i.e., addition of oils and plasticisers. Oils,
plasticisers and waxy materials will almost certainly exude to the rubber surface either
immediately after compound preparation or during the establishment of the interface.
Similarly some plasticisers are known to travel to and into the interface layers with time,
breaking down the adhesion and resulting in complete failure of the bond.
12.1.7.2 Complete Wetting of the Adherend
Complete wetting of the adherend surface is essential if the best interfacial bond strength is
to be achieved. However, because of incomplete wetting not all of the surface transforms
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into an interface. The surface energies of the adhesive mass and the adherend rarely coincide
and thus ready and complete wetting is rarely achieved. The areas of incomplete interfacial
bonding impairs bond strength which in turn leads to bonding defects or failure.
12.1.7.3 Stabilisation of the Rubber/Adhesive Interface
It is necessary to establish the greatest area of interface between the adherend and adhesive
mass. A high contact pressure between the adherend and adhesive mass will ensure the
formation of an interface despite the adherend being resistant to wetting purely on grounds
of interfacial chemistry. The yield of the interface is proportional to the contact pressure,
though naturally the interfacial area will decrease and the surface area increase when the
contact pressure is removed. For a stable interface to be retained an area of interface must
exist in a stable condition after removal of the contact pressure. Stabilisation of the interface
requires that the excess energy in interface formation is minimised by binding between the
dissimilar surfaces (for example rubber and metal). Thus the bond in rubber adhesion results
from the formation and stabilisation of the interface via the three processes outlined previously.
12.1.8 Topography of Substrate
The topography of a substrate is considered to be a direct influence on the occurrence and

degree of adhesion. The adhesion is created by the adhesive being locked around protrusions
and into cavities of the adherend surface. The rougher the surface, the greater the adhesion
strength. The cleanliness of the surface, the ability of the adhesive to wet out the total surface
area in contact and the viscosity of the adhesive being critical factors in the achievement of
good bond strength. The viscosity of the adhesive must be sufficiently low to enable it to flow
into the valleys and to ensure that a minimum of air, or solvent vapour, is trapped in the
depths of a cavity, but be sufficiently high to ensure that asperities in the surface to be bonded
are adequately covered. Failure to achieve the correct adhesive viscosity and a maximum
adhesive/substrate coverage will diminish the overall bond strength.
12.1.9 Surface Conditions of Adherend
The effecting of intimate contact of the surface of the adherend to be bonded and the
adhesive depends on two major factors:
the surface roughness of the adherend,

the flow characteristics of the adhesive.
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12.1.9.1 Surface Roughness of the Adherend
Rowe [4] argued that many substances are polycrystalline in nature, as, for example, the
oxide layers on metals and in roughening metal surfaces the crystalline form of structure is
likely to persist, but with a different size of crystal. Wake [5] points out that the empirical
fact remains that for metals, the apparently rougher surface given, as the particle size of
grit used in grit blasting is increased, the poorer the adhesion obtained. This is probably
because although visually the surface of the adherend appears rougher, in fact the
irregularities themselves have smoother walls when viewed under an electron microscope.
Even polished, lapped, metal surfaces have irregularities of about 10-7 m and such pits
can trap air. If no air is trapped in the pits of the metal then one can see that the surface
wetting and adhesive coverage would be complete. Any entrapment of air will lead to
incomplete adhesive/metal coverage and much will depend upon the contact angle of the
adhesive and capillary attraction. The critical angle for perfect contact between adhesive
and substrate approaches zero.
12.1.9.2 Flow Characteristics of the Adhesive
The viscosity of the adhesive is obviously a significant factor in the correct application of
the correct and complete contact layer on the adherend. A number of adhesive factors
will need to be addressed:
The optimum viscosity of the adhesive will need to be determined by experimentation

to achieve optimum bond strength.
The application temperature of the adhesive should be consistent and not vary widely
due to ambient fluctuations.
Similar controls are desirable for the substrate to ensure consistent adhesive flow.
Too low a temperature for the substrate would reduce adhesive flow rate, while too
high a temperature would result in too much flow, causing adhesive to drain away
from asperities (peaks). A further complication would be encountered when using
solvent-based adhesives in possible solvent evaporation causing increased viscosity.
Solvent loss can occur during application through temperature fluctuations, or simply
by evaporation from open adhesive containers in the case of the more volatile solvents.
12.1.10 Classification of Rubber According to their Wettabilities
Lee [6] classifies rubbers by wettability, ranking them according to Zismans critical
surface tension c (mJ/m2), see Table 12.1.
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Table 12.1 Classification of rubbers by wettability

Rubber Critical surface tension
Isobutylene - isoprene 27
cis-Polyisoprene 31
cis-Polybutadiene 32
Styrene butadiene 33
Epichlorohydrin 35
Chlorosulphonated polyethylene 37
Acrylonitrile butadiene 37
Polychloroprene 38
12.1.11 Bonding Interphase or Interface Considerations
The interphase is a thin region which exists between the bulk adherend and the bulk
adhesive [7]. A surface oxide, either native or one produced by pre-treatment, is present
on most metal adherends. These oxide layers will frequently be contaminated, even after
cleaning. The net effect of absorbed layers is:
that the adsorbed layer dominates over the bulk material for separation less than the
thickness of the adsorbed layer,
that the bulk dominates where the separation is large compared with the adsorbed
thickness,
that the adsorbed layer not only acts as a spacer but causes additional screening of
the bonding reaction [8].
A primer is often applied in a production process after pre-treatment and before the
application of the adhesive. Typical thickness for the oxide are 0.003 0.4 m, for the
primer 5 10 m and for the adhesive 10 15 m. The interphase region is expected to
have mechanical properties different from either the adherend or the adhesive. Filbey
and Wightman [9] comment that measurement of these properties is important in
understanding adhesion, for example, poorly durable bonds are often a consequence of
337
poor interphase properties. Thus, one of the frontier areas in adhesion science today is
determining interphase properties.
Interfacial imperfections, such as trapped air bubbles [7, 10] can be the site for high
localised stresses. The air responsible for the bubbles may have been trapped into the
adhesive during mixing or occur when bridging of high viscosity adhesive occurs over
cavities in the substrate surface. Some degree of interfacial imperfection may arise from
even normal curing conditions, because volume changes can occur within adhesives en
route to full cure. Gaseous by-products and solvent residues can also be the source of
problems. Plueddemann [11] has detailed the stresses which can occur due to adhesive
shrinkage and coefficient of shrinkage difference between adherend and rubber in the
interfacial area.
Minford [12] discusses at some length cohesive versus adhesive failure. On the topic of
failure due to water desorption of the adhesive Laird [13] has shown that water can
progress by diffusion along the interface as much as 450 times faster than by permeation.
Adhesive systems can also be sensitive to certain of the strong polar solvents as they
contain polar elements themselves. Dilution of an adhesive can be achieved by the use of
this principle but after the adhesive has been cured in the bondline the same solvent can
attack the adhesive and destroy the adhesion at the interface.
A further interfacial factor can be the presence of non adsorbable or non desorbable
contaminating films (as previously mentioned above) at the interface. Such materials can
be oils, fatty acids, plasticisers from the rubber and metal processing oils from inadequately
cleaned metal components. Some of these lubricants can be absorbed by the adhesive if
it is solvent-based but in the case of the new waterborne rubber to metal systems this
absorption cannot take place, for the systems are neither miscible or compatible with
oils. These new waterborne systems have a critical tolerance level for surface contamination
of the metal and if this is exceeded then wetting out of the metal by the adhesive will not,
at the worst be possible, or at the best complete.
When examining the surface of a failed bonding it is extremely difficult to determine

whether the failure has taken place at the original interface or whether a new interface
has been opened, either in the adhesive or in the rubber, for the distance from the old to
the new interface can be extremely small. Thus it may not be possible to determine
whether contamination of the interface was the cause of the failure or not. Examination
of the surface of the failed bond using very specialised equipment such as Secondary Ion
Mass Spectroscopy (SIMS), Ion Scattering Spectroscopy (ISS) and Auger Electron
Spectroscopy (AES) can greatly assist with determination of some of the causes of this
type of failure.
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12.1.12 Problems in Adhesion
Most polymeric adhesive systems undergo some degree of shrinkage during the process
of crosslinking and this will create stresses within the adhesive/substrate interface.
Adhesives with filler content have a lower shrinkage and thus lower stresses.
The presence of water at the interface will cause interference with the establishment of a
good bond. Some materials occurring as the substrate are hydrophilic in nature and will
always attempt to achieve a monomolecular water film on their surfaces. This can occur,
after the substrate has been cleaned and before the adhesive has been applied, from the
atmosphere direct to the substrate surface, or later after the bond has been established,
by diffusion. The presence of a water film at the interface can result in leaching of materials
from the substrate which then can cause corrosion of the substrate, with resultant
progressive loss of adhesion as corrosion spreads under the adhesive.
Removal of solvent from the adhesive layer can present problems especially if evaporation
from the adhesive surface is prevented in some way. If the bond is made before most of
the solvent has been removed it will result in significant internal stresses in the adhesive
and also lower adhesion strength. If the layer of adhesive is thick and solvent loss from
the outer surfaces is rapid, viscosity changes in the outer adhesive layers will also hinder
solvent loss. If the adhesive also is of the crosslinking type there can be some solvent left
indefinitely internally. Crosslinking of the adhesive restricts molecular chain movement
and thus prevents the movements necessary to allow the solvent molecules to travel
through the mass. Solvent remaining trapped in the adhesive, usually close to the interface,
results in a softer than expected adhesive/substrate interface and thus allows easier
breakdown of the adhesion by stripping, etc. Choice of the solvent for the adhesive and
its molecular configuration and thus size plays a considerable part in the establishment
of a satisfactory bond.
12.2 Rubber Bonding in Power Transmission Belting
12.2.1 Introduction
Power transmission belts are largely rubber composites which transmit mechanical power
between shafts through either friction or a combination of friction and the engagement
of formed teeth in pulley grooves. All power transmission belts have fibre reinforcement
of some description, and so they all rely to a great extent on the quality of the bonding
between fibres and rubber compounds in order to function correctly. However, there is
relatively little literature concerning the role of the adhesion system in ensuring that belts
retain structural integrity throughout their working life. This chapter reviews the role of
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the adhesion system in belting applications, considering synchronous belts, V and V-

ribbed belts and conveyor belts. Whilst conveyor belts are not strictly power transmission
belts some consideration of the failure of these belts has been taken into account in
characterising power transmission belt failure modes. The section begins with an
assessment of which belt failure modes are adhesion related, before examining the adhesion
systems used in belting applications, and the tests which can be used to examine adhesion
strength in belts. As the chemistry of rubber bonding is covered elsewhere in this volume
the emphasis within this chapter is on mechanical and applications-based issues rather
than on the chemistry of the adhesion systems.
12.2.2 Power Transmission Belt Failure Modes
Four different types of belt are considered: synchronous belts, V-belts, V-ribbed belts
and conveyor belts. Each type of belt has a distinct set of failure modes and so each is
considered in turn below. Only failures which can be considered to be belt failures have
been considered, rather than belt/pulley system failures, so that failures as a result of
pulley misalignment, for instance, have not been included. For adhesion related failure
modes, methods of predicting belt failure where they have been developed, are outlined.
12.2.2.1 Synchronous Belts
Most of the literature pertaining to synchronous belts considers the automotive application
of these belts and so this section inevitably has an automotive bias. Figure 12.1 shows
the structure of a synchronous belt. As Figure 12.1 shows the belt is made up from an
rubber compound with two reinforcements, the first being a tension bearing cord which
runs through the middle of the belt, and the second a facing fabric which covers the belt
Figure 12.1 Synchronous belt construction
340
teeth, strengthening them and protecting them from wear. The tension bearing cord is
normally glassfibre or aramid, with the facing fabric normally polyamide. The belts
transmit power through the engagement of the moulded teeth in pulley grooves.
The belts are manufactured by first putting a fabric sleeve around a mandrel which has
the belt teeth formed in it. The cord is then helically wound along the mandrel (this
means that in a finished belt the cords do not lie along the axis of the belt but at a slight
angle to it). The rubber compound (mixed but uncured) is then placed around the cord
before an outer casing applies pressure to force the rubber compound into position and
heat is applied to cure the rubber compound once it is in position. Once the curing
process is complete individual belts are cut to width from the stock. Similar methods are
used to manufacture most types of power transmission belt.
Test results from experimental studies on belt life suggest the following as the major belt
failure modes: tooth root cracking, wear, cord failure and fabric separation [14, 15, 16,
17, 18], and this classification has support from field data [19, 20]. Figure 12.2 shows
examples of tooth root cracking, cord delamination and fabric separation failures.
Tooth root cracking is the prevalent failure mode for belts and the literature suggests
two mechanisms for its generation. The most commonly reported mechanism is fatigue
and eventual failure of the facing fabric in the tooth root, followed by rapid crack
propagation through the tooth rubber compound, usually across the rubber compound/
Figure 12.2 Synchronous belt failure modes. a) tooth root cracking,

b) cord delamination, c) fabric separation
341
cord interface leaving the tooth (if it remains on the belt) unable to support load and the
belt unable to transmit power. Kido [21] point out that this mechanism is often accelerated
by wear of the fabric, leaving less material to support the loads. Iizuka [18] reports on
both the mechanism outlined above and on a second mechanism to explain tooth root
cracking, in which the failure initiation site is at yarn interfaces in the cord; cracks
originating in this region propagate first into the tooth rubber compound and then out
to the facing fabric in the tooth root. Iizuka observed this second mechanism in belt life
tests at torques of around 5 Nm, with facing fabric fatigue observed in tests carried out
at a higher torque, and relates the initiation of cracks at the yarn interfaces to local
maxima in the belt curvature whilst engaged on the pulley [22].
There are also a number of reported mechanisms for cord failure in the belts. The most
obvious of these is the belt tension being so high that the cords simply cannot support
the load, as identified by Koyama [14], while Murakami and Watanabe [23] suggest that
localised bending in the cord causes debonding within the cord, resulting in interfilament
abrasion and a reduction in the tensile strength of the cords leading to cord failure.
Dalgarno [17] observed belt failure through debonding of the cord at the sides of the
belt, leading to failure when the cord at the side of the belt becomes trapped between belt
and pulley. One further source of belt tensile failure is back cracking [21, 24]. In this case
failure is initiated through cracking in the back cover of the belt, generally associated
with significant ageing of the rubber compound. The cracks have been observed to run
across the back of the belt, and once the cracks have propagated to such an extent that
the belt cords are exposed, belt tensile failure follows.
Fabric separation failure occurs when the belt teeth and fabric land become detached
from the belt cords [17] and is essentially seen as purely an adhesion failure, although
there may be links between this failure mode and the tooth root cracking failures
observed by Iizuka [18], originating from cracks developed in the cord itself through
internal delamination. Wear causes belt failure through changing the tooth profile to
such an extent that the belt teeth can no longer support the required load [25].
Overall it is interesting that adhesion within the belt can be the root cause of most
types of failure, with fabric fatigue (often accelerated by wear), wear itself, and rubber
compound cracking, the root causes of those failures not related to adhesion. The
observations made by various researchers suggest that both the cord/rubber interface
and the fabric/rubber interface are potential failure initiation sites, with interyarn and
interfilament adhesion within the cord providing further possible failure initiation sites.
In attempting to identify parameters which allow the belt life to be predicted within the
adhesion related failure modes identified above, the most common approach has been to
use measures of belt distortion. Dalgarno [17] examined belt life data from belt failures
within the tooth root cracking, fabric delamination and cord separation failure modes,
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and showed that the belt tooth deflection correlated well with belt life regardless of the
failure mode. Childs [26] developed a failure analysis based on a combined tooth deflection
and bending distortion measure, and Iizuka [27], in examining the same data as Childs
[26], used the curvature of the belt as the parameter to which belt life was related. Both
Childs and Iizuka show that there is good correlation between belt life and their distortion
measures, and Iizuka concludes that the two measures may in themselves be related.
12.2.2.2 V and V-ribbed Belts
V-belts
Recent literature on the failure of V-belts has concentrated on raw edge V-belts of the
type shown in cross section in Figure 12.3, this type of V-belt being the most commonly
implemented belt in automotive applications.
As Figure 12.3 shows, the V-belt consists of three distinct zones, a rubber compound
which forms the bulk of the V, the tension cord (normally polyester) embedded in a
softer cushion rubber, and a rubber impregnated fabric. In addition the rubber compound
may be axially reinforced by chopped fibre to give the rib a greater resistance to
deformation in the axial direction. To improve the flexibility of the belts the belt may be
cogged as shown in Figure 12.4.
Figure 12.3 Typical raw edge V-belt cross section
Figure 12.4 Side view of cogged V-belt
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The failure of these belts has been studied in detail by Gerbert and Fritzson [28, 29]. With
support from field data and laboratory tests they identified four common failure modes for
the belts: tensile failure, cord separation, radial cracking, and wear. Belt tensile failures
were associated with short belt lives and may be assumed to occur where the belt has been
underspecified, or the drive is ill-conditioned. Cord separation was defined as crack
propagation along or across the belt, close to the cord layer. Debonding between cord and
cushion rubber, and between cushion layer and the V rubber compound were both observed,
together with crack propagation in the V rubber compound and in the cushion rubber.
Edge cord separation was also observed, and this is thought to be a similar failure mode to
cord delamination in synchronous belts. Radial cracking involves the growth of cracks
from the bottom of the V towards the belt cord, with the cracks eventually leading to the
disintegration of the belt. Belt wear is obviously an ongoing process for the belts, and
becomes a failure mode when the shape of the belt has changed so much as a result of wear
that the belt is no longer able to transmit power at the required level.
The cord separation failure mode is obviously adhesion related, and Gerbert and Fritzson
[30] present a systematic method for recording the development of delamination failures.
A 100% cord separation failure is defined as when the delamination occurs either across
the entire belt width or along the belt for a distance equal to the belt width. Delamination
which has not reached this level is then classified through a percentage value of the
length of the crack to the width of the belt, with 50%, 10% and 1% the classifications
used in this case. The 1% damage level represents the first recorded observation of damage
through the failure mechanism of interest. One attribute of this classification system is
that it allows the development of damage through more than one failure mechanism to
be recorded through the life of the belt, so that failure modes which are developing
simultaneously can be monitored, and situations where one failure mode is initiated by
another clearly understood.
Gerbert and Fritzson also developed a procedure for predicting belt life within the cord
separation failure mode, based on the shear stress in the cushion region. The overall
shear stress arises from four individual components of shear stress:
i) the shear stress due to friction between belt and pulley,
ii) a shear stress arising from the fact that the outer cords in the belt carry a higher
tension than central belt cords (as a result of the belt section bending axially),
iii) the cord layer and the rubber compound having a different resistance to
longitudinal bending,
iv) shear stresses around the cords as a result of radial pressure on the cord layer.
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Of these shear stress components i), ii) and iii) all act along the length of the belt, with iv)
acting across the belt width. The combined effect of these four shear stresses is shown to
have a good correlation with belt life where cord separation is the failure mode, and is
used as part of a belt life prediction procedure (based on finite element analysis) which
encompasses all the failure modes identified by Gerbert and Fritzson.
V-ribbed belts
Figure 12.5 shows a schematic of the structure of a V-ribbed belt. The most commonly
reported mechanical failure mode for this type of belt is wear, with delamination not
generally perceived as a problem. This is of interest as most flexible composite elements
will have a delamination failure mode of some description, and so the most obvious
question to ask is why the V-ribbed belt does not. The probable answer is that the belt
cord in a V-ribbed belt is isolated from the major distortions of the belt through its
position above the belt/pulley interface. The large majority of the distortion of the belt
takes place in the belt ribs, away from the cord. If the four shear stresses identified
previously by Gerbert and Fritzson for a V-belt are considered, it can be seen that of the
four i) and ii) do not apply to the cord layer in a V-ribbed belt. The cord layer in a V-
ribbed belt therefore does not incur shear stress to the same extent as that in a V-belt.
Thus the V-ribbed belt may be considered a better design in composite terms, with the
individual elements of the composite more effectively employed and protected.
Figure 12.5 V-ribbed belt construction
12.2.2.3 Conveyor Belts
Kozhushko and Kopnov [30] identify a number of possible failure modes for fabric
conveyor belts. Abrasive wear, fabric breakage or joint failure are all possible failure
modes but the failure mode of most interest here is that of fatigue delamination, and it is
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this mode that Kozhushko and Kopnov investigate. Their approach is to consider the
delamination as a shear fatigue mechanism with delamination occurring when the shear
strain magnitude reaches the permanent shear fracture strain, and with the permanent
shear fracture strain seen as a variable which reduces with the number and size of loading
cycles a belt has undergone. Kozhushko and Kopnov test this theory through fatigue
testing and show reasonable correlation between theory and experiment, and conclude
that the approach has value in belting applications but that further work is required to
fully validate the approach.
12.2.2.4 Prediction of Belt Life in Delamination Failure Modes
If we take an overview of how the belt delamination failure modes have been analysed
by researchers to develop belt life prediction routines it is clear that the different
methodologies have a lot in common, and it may be of value to highlight how these belt
life prediction routines have been developed.
The first step is to identify the belt life determining parameter, and for both V-belts and
conveyor belts this has been identified as the shear deformation, as would be expected
for delamination failures. For synchronous belts the belt life determining parameter has
generally been identified as a measure of belt distortion, the success of these belt distortion
measures in correlating with belt life would suggest that the belt distortion measures and
the shear deformation are related. With this key parameter identified the precise nature
of the relationship between the parameter and belt life must be identified. The approaches
for synchronous belts and conveyor belts outlined above both sought this relationship
through correlation with experimental data, whilst the approach outlined for V-belts
was rather more fundamental, using crack growth analysis to follow the progression of
the failure (but still using experimental data to validate the approach). All that then
remains is for a model of belt behaviour to be developed which can relate the belt
operational parameters to the belt life determining parameter, and then an analytical
structure exists which allows the belt life to be predicted for a given set of operating
parameters.
12.2.3 Adhesion Systems in Power Transmission Belts
As with most rubber composites the adhesion system used in power transmission belts is
based on an resorcinol/formaldehyde/latex (RFL) type system. General overviews of RFL
adhesion systems from a tyre cord perspective have been previously published by
Takeyama and Matsui [31], and more recently by Solomon [32]. Bonding with RFL
systems is achieved through applying an RFL coating to the fibre structure prior to the
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belt being manufactured. The cords and rubber compound are then positioned and cured,
with the RFL also curing at the same time. RFL systems work through using the resin
part of the RFL to adhere to the fibre, with the latex part used to provide adhesion to the
rubber compound through crosslinking. For some fibrous materials a two-stage RFL
system is required. This involves precoating the fibre structure with an adhesion promoter
of some description prior to the RFL coating being added. Polyester, glass and aramid
fibres normally require a two-stage adhesion system. Broadly the strength of an RFL
adhesion system will depend on the relative reactivity of all of the components of the
composite, on how completely the cord is treated (wetting and penetration), and on the
effectiveness of any diffusion mechanism.
As the basic RFL system and its application is well documented elsewhere, the RFL
system will be considered here from a power transmission belting perspective (see also
Chapter 9). The introduction of new materials to belting applications is the most common
reason for re-examining the RFL system, and Kubo [33] states that a re-examination of
the adhesion system is essential if the perceived benefits of switching to a new material
are to be obtained in practice. Kubo specifically examined adaptations to the RFL system
required to ensure good adhesion to hydrogenated nitrile rubber (HNBR) for belting
applications. Several authors have examined which specific RFL system is of most value
where aramid fibres are being utilised in rubber composite applications [34, 35, 36].
Aramid fibres have excellent mechanical properties but are difficult to adhere to other
materials, and as such much effort has been expended to develop adhesion systems which
allow their excellent mechanical properties to be exploited in belting applications. Often
linked to new materials introduction is the development of belts for high temperature
applications, and the implications of this on conveyor belt adhesion systems has been
examined by Sarkar [37].
12.2.4 Adhesion Testing in Power Transmission Belts
Tests to assess the level of adhesion of fibre structures to rubber compounds can be
divided into three classifications:
pull out tests to test the adhesion of individual cords to rubber compounds,
peel tests to test the adhesion of fabrics or a row of cord to rubber compounds,
belt tests.
Cord pull out tests are commonly used to assess the adhesion between a single cord and
a block of rubber compound. As the name suggests the tests concentrate on measuring
the load required to pull a cord from a block of rubber compound. There are various
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configurations which the pull out tests can take [31] with the T configuration [38], and
in particular the H configuration [38, 39, 40, 41] most common where belting applications
are considered. For the H configuration ASTM D4776 [42] is the most commonly quoted
standard. However, Brodsky [43], in presenting a three cord adhesion test, questions the
value of the H pull out test as it does not allow the stress state at the point of failure to
be known. The three cord adhesion test presented by Brodsky deliberately generates a
known stress state in order to overcome this limitation. Both Kubo [33] and Klingender
and Bradford [40] observe that temperature and ageing are important parameters in
defining the pull out strength in cord/rubber adhesion systems, with the pull out strength
generally declining with an increase in either temperature or amount of ageing. Kubo
also presents a methodology for assessing whether or not a cord material has been affected
chemically by the adhesion system or the rubber compound. Cords are bonded into
rubber compound blocks using the adhesion system of interest, before being dissolved
out of the rubber compound blocks using toluene. The strength of cords treated in this
way can then be compared to the strength of cords as new.
Peel tests are generally used to assess the adhesion between rubber compounds and rows
of reinforcing cords or fabrics. The most common format for these tests is a T-peel,
where separation between one-half of the rubber compound and the reinforcing layer
will be induced or manufactured in. The separated halves of the specimen are then attached
to the jaws of a tensile tester and the force required to continue to separate rubber
compound from reinforcement layer recorded. Such tests have been used by a number of
authors with respect to belting applications [33, 34, 36, 37, 38], with the most commonly
quoted standard being ASTM D4393 [44]. The importance of temperature and ageing
are again both highlighted in the literature to ensure that the tests are as representative
of application as possible.
Both the pull out tests and the peel tests are rather idealised methods of assessing adhesion
strength and may be considered as most appropriate for comparative testing of different
adhesion systems rather than an indicator of potential belt performance. The relationship
between the results of the standard pull out and peel tests and more representative tests
resulting in belt failures through delamination has not been investigated in the literature.
It is possible however to carry out a peel test on a synchronous belt which has been
shown to be an indicator of the potential for a belt to fail through fabric separation [45].
The test procedure was to initially cut and peel back the facing fabric and belt teeth from
the belt until three belt teeth were separated from the belt. The cut was then carefully
extended under the fourth tooth into the tooth root area, taking care not to damage the
fabric in any way. The cut section of belt was then T-peel tested as described above, with
the fabric being peeled from the rest of the belt as the test progressed. The results of this
test together with the results from belt life tests showed that adhesion systems with low
peel strength values were more likely to fail through fabric separation.
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12.3 Undesirable Adhesion Occuring Under Service Conditions (Fixing)
This topic does not strictly comply with the title of the chapter, but represents a problem that
can be very serious in nature and cause total failure of a seal system under service conditions.
When nitrile rubber vulcanisates and metals are kept in contact, under pressure, for long
periods of time an adhesion force develops between their surfaces; this force has become
known as fixing. The strength of the bond between the two materials can be termed the
fixing strength.
Fixing when it occurs in a component in the field can be very dangerous as it often
occurs within the sensor mechanisms for such applications as gas control units and motor
fuel systems for vehicles. Less critical occurrences can be seen when attempting to remove
a hose from a metal coupling after a period of service; apart from requiring a cleanup of
the metal surface before reassembly with a new hose this case causes little problem.
Mori [46] examined a number of factors concerned with the phenomenon and developed
tests to determine the problem and suggested four indicators of preventative measures to
eliminate or control fixing (see Section 12.3.2).
Their compounds were moulded using a mould surface with an average surface roughness
of 0.41 m. Samples were compressed, in a similar manner to a conventional compression
set test between sheets of the desired test metal. The adhesion between the metal and
rubber were tested after periods of time and the load required to separate the metal and
rubber sheets were plotted. The strength of the fixing was found to increase with the
time of compression contact between the two materials. Initially the increase was rapid
and then followed by a slow steady increase with time. The two rates were considered to
be quite different and were attributed to two different mechanisms, i.e., physical and
chemical (see Section 12.3.1). The initial physical bond is defined as FSo and the final
fixing strength including the chemical bond is defined as FS.
12.3.1 Factors Affecting Fixing
Environmental factors
It is known that the effects of fixing are more prevalent under conditions of high
humidity and high ambient temperatures. The rate of the chemical force generation is
strongly influenced by the increase in ambient temperature which causes generation of
chemical bonds from the nitrile surface of the rubber to the metal surface. The effects
of humidity and the presence of bloomed materials on the vulcanisate surface were
also investigated [46]. These blooms were created artificially and wiped from solution
349
onto the surface of the rubber before the fixing test was carried out. Dependent upon
the type of metal being tested there is also a corrosion factor to be considered. This
usually proceeds from the surface of the metal plate, travelling towards the centre as
corrosion proceeds. The corrosion forms an amorphous oxide layer on the metal surface
which acts as a weak bonding layer. This type of corrosion occurs rather easily and is
widely known as crevice corrosion [47, 48]. Crevice corrosion results from a galvanic
cell forming in areas of stagnant water formed in small recesses in the metal surface.
The interface of both the materials in contact must have a significant effect on the fixing
strength. Their topography caused by moulding of the vulcanisate and the metal finishing
and/or plating has a significant influence on the fixing strength. The rougher the surfaces
of both materials, the less will be the points of surface contact and this will reduce the
strength of a bond developing.
The hardness of the compound will also become a significant factor; the harder the
compound the lower will be its ability to deform and follow the contours of the metal
surface; this will affect the level of FS0. If however the increase in hardness of the rubber
compound is produced by the addition of sulphur then there will be an increase in the
chemically active units on the nitrile rubber surface and thus bond strength because of
copper/sulphur bonds being formed gives an increase in FS.
Material factors
The softer the metal the higher will be the fixing force, FS0. This relationship is also
reflected in the properties and thickness of the oxide films which are generated on the
surface of the metals. Metal surface tensions and their ability to attract and hold water
affect the level of FS. The surface of metals with low adsorbed moisture will generally give
a high FS. The lower FS found in nickel and iron could well be attributable to their lower
surface tension. Crystal size within the metal surface in contact with the rubber could well
also be a significant factor in determining areas of contact. Metals which develop only a
thin oxide film and having a chemically active surface will obviously generate a higher
bond strength. However, copper will have a thick oxide film but this and the metal itself
are very chemically active to sulphur and polysulphide chains. Aluminium and zinc plates
give a low FS, since their oxide films are generally thick and chemically inactive to sulphur
and polysulphide chains. The surface treatment of copper therefore has a significant effect
on the fixing properties. Organic metal treatments [47] give low FS when used in contact
with NBR because the plates have a low surface tension below 0.3 mN/cm.
The polarity of the NBR has an influence on the level of FS0 which increases with the
acrylonitrile (ACN) level. FS also increases with the polarity of the NBR, but to a far less
extent than does FS0.
350
Carbon black fillers generally do not have much effect on fixing except in the differences
associated with general hardness increase or decrease. However the high fixing strength
of NBR may have an association with the included carbon black as it is widely known
that carbon black provides active radicals in NBR during mixing and blending. These
radicals can easily change to peroxides and give carboxyl groups at the surface of the
NBR. The groups will be physically absorbed into the metal surface or react chemically
with them. Silica however is generally inert and in fact with increasing dosage the value
of FS decreases as the hardness increases.
The generation of strong adhesive forces can be considered to result from chemical
interaction between the metal and NBR. This generally results from the reaction of the
metal with sulphur compounds and carboxyl compounds to give their metal salts, which
have a high bond energy. Polysulphide reactivity is high for copper and brass plates.
12.3.2 Prevention of Fixing
Mori [46] summarises the fixing phenomenon by suggesting that first the segmented
molecules of the vulcanisate diffuse into the metal surface and then polar groups such as
a nitrile groups are adsorbed onto the surface. At this time, secondary order bond forces
such as van der Waals forces and hydrogen bond forces are generated between both
materials. Following this chemical reactions occur at the contact points between the two
materials, and then both materials are combined by the first order bonds formed. As a
result, strong adhesional forces are generated between the two materials. They suggest
that that four preventative measure may be used:
control of contact area,

suppression of molecular motion of the NBR segments,
inhibition of interfacial reactions,
introduction of inactive crosslinks and side chains.
12.3.3 Other Methods of Preventing Fixing - Examined Experimentally
Surface irradiation with UV light [46]
Vulcanisates pre-treated by exposure to UV irradiation are influenced by the

atmosphere in which the treatment is carried out. NBR treated in this way in an
oxygen atmosphere did not significantly reduce in FS0, but there was remarkable
increase in the FS value. This was deemed to show that the active groups such as -
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OH, -CO, and -COOH are present near the surface of the metal and are also formed
on the surface of the NBR vulcanisates during the UV treatment in air. If the UV
treatment is carried out in an argon atmosphere then the NBR vulcanisates had a
greatly decreased value of FS. This however would not be considered an industrial
feasibility.
Prevention of Fixing by Bloom Generation
Wax films, especially paraffin wax were not found to be effective as a preventative for
fixing, but in fact accelerated it. If the wax is close to melting or melted then a sucking
effect will be encountered between the two materials. Mori found that amide type materials
in blooms with long alkyl or alkenyl groups, provided excellent bloom films with low
surface tension and high melting points on the surface of the NBR vulcanisates. Provided
that the temperatures did not exceed 60 C the amide bloom inhibited the chemical
reactions occurring during fixing. The use of blooming agents is very effective for
preventing the fixing between metals and NBR vulcanisates. The materials used were
stearamide and methylene bis-erucamide.
References
1. B. G. Crowther, Rubber to Metal Bonding, Rapra Review Report, 1996, Vol. 8,

No 3, Rapra Technology Ltd., Shrewsbury 1996.
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355
356
Abbreviations and Acronyms
ABS Acrylonitrile-butadiene-styrene
ACM Ethyl acrylate copolymer
ACN Acrylonitrile
AEM Analytical electron microscopy
AES Auger electron spectroscopy
ASTM American Society for Testing and Materials
ATR Attenuated total reflectance
BATNEEC Best available technology not entailing excessive cost

BDTPTS Bis (di-ethyl thiophosphoryl) trisulphide
BGDMA 1,3-Butyleneglycol dimethacrylate
BIIR Bromo butyl rubber
BR Polybutadiene rubber
BTSE Bis-[triethoxysilyl]ethane
CBS N-cyclohexyl-2-benzothiazole sulphenamide

CIIR Chloro butyl rubber
CM Cement/metal failure
COR Coefficient of restitution
CPD Controlled product design
CP Cement/primer failure
CPE Chlorinated polyethylene
CR Polychloroprene
CS Compression set
CSM Chlorosulphonated polyethylene
DCBS N,N-dicyclohexyl benzothiazole sulphenamide

DCPD Dicyclopentadiene
DIOP Diisooctyl phthalate
DOA Dioctyl adipate
357
Commercial rubbers
DOS Dioctyl sebacate

DPG N, N-diphenyl guanidine
DPTT Dipentamethylene thiuram tetrasulphide
ECO Epichlorohydrin
EDX Energy-dispersive X-ray (analysis)
EELS Electron energy loss spectroscopy
ENR Epoxidised NR
EP Ethylene-propylene rubber
EPC Easy processing channel black
EPDM Ethylene propylene diene monomer
EPR Ethylene propylene rubber
EPTPE EPDM/PP-based thermoplastic rubbers
ESCA Electron spectroscopy for chemical analysis
ETO Ethylene oxide
EV Efficient vulcanisation
EVA Ethylene vinyl acetate copolymer
EVM Ethylene-vinyl-acetate rubber
FDA Food and Drug Administration (USA)

FEP Fluorinated ethylene propylene copolymer
FKM Fluorocarbon rubbers
FMEA Failure mode and effect analysis
FMQ Silicone rubbers
FPM Fluoropolymer
FRP Fibre-reinforced plastic
FTIR Fourier transform infrared analysis
GP General purpose
GPF General purpose furnace black
GRP Glass-reinforced plastic
HAF High abrasion furnace black

HB Brinell hardness
HDPE High density PE
358
HMMM Hexamethoxymethylmelamine
HMT Hexamethylene tetramine
HNBR Hydrogenated acrylonitrile butadiene rubber
HR Hexamethylenemelamine-resorcinol
HRC Rockwell hardness C
HRH Hexamethylenemelamine-resorcinol-hydrated silica
HRL Heat resistant litharge
HTV High temperature vulcanising
HV Vickers hardness
HVLP High velocity low pressure
IAD Isopropyl azodicarboxylate

IASF Intermediate superior abrasion furnace black
IIR Butyl rubber
IPA Isopropyl alcohol
IR Isoprene rubber
IRHD International rubber hardness degree
ISO International Organisation for Standardisation
ISS Ion scattering spectroscopy
LDPE Low density polyethylene

LR Liquid rubber
MBT Mercaptobenzothiazole
MBTS Mercaptobenzothiazole disulphide
MEK Methyl ether ketone
MF Melamine-formaldehyde
MHF Maximum torque
MIBK Methyl isobutyl ketone
MOR 2-(4-Morpholinyl mercapto)-benzthiazole
MW Molecular weight
NBR Acrylonitrile butadiene rubber

NOBS N-oxy di-ethylene benzthiazyl sulphenamide
359
NPC No post cure

NR Natural rubber
NRTPE NR-based thermoplastic rubbers
OBTS N-oxydiethylene benzothiazole sulphenamide

ODC Ozone depleting chemicals
ODR Oscillating disk rheometer
PA Polyamide
PB Polybutadiene
PBT Polybutylene terephthalate
PC Polycarbonate
PCB Printed circuit board
PDMS Polydimethylsiloxane
PE Polyethylene
PEEK Polyetherether ketone
PES Polyethersulphone
PET Polyethylene terephthalate
PG Propylene glycol
PHR Parts per hundred rubber
PIXIE Particle-induced X-ray emission
PNR Polynorbornene
POM Acetal (polyoxymethylene)
PP Polypropylene
PPO Polyphenylene oxide
PPS Polyphenylene sulphide
Pt Platinum
PTFE Polytetrafluoroethylene
PU Polyurethane
PV Post vulcanisation
PVC Polyvinyl chloride
PVDC Polyvinylidine chloride
PVDF Polyvinylidene fluoride
PVF Polyvinyl fluoride
360
R&D Research and Development

RC Rubber/cement failure
RF Rubber failure
RFL Resorcinol/formaldehyde/latex
RFR Resorcinol/formaldehyde/resin
RH Relative humidity
RIM Reaction injection moulding
RPN Risk priority number
RT Room temperature
RTV1 Room temperature vulcanising, one component
RTV2 Room temperature vulcanising, two component
SBR Styrene butadiene rubber

SBS Styrene-butadiene-styrene
SDS Safety data sheet
SEBS Hydrogenated SBS
SEM Scanning electron microscopy
SEV Semi-efficient vulcanisation
SG Specific gravity
SIMS Secondary ion mass spectroscopy
SMR Standard Malaysian rubber
SNMS Secondary neutral mass spectrometry
TAC Triallyl cyanurate

T&D Transmission and distribution
TCAT Tyre cord adhesion test
TCBQ Tetrachlorobenzoquinone
TCE Trichloroethane
TCICA Trichloroisocyanuric acid
TEM Transmission electron microscopy
TETD Tetraethyl thiuram disulphide
Tg Glass transition temperature
THF Tetrahydrofuran
361
TIC Trichloroisocyanuric acid

TLV Threshold limit value
TMTD Tetramethyl thiuram disulphide
TMTM Tetramethyl thiuram monosulphide
TOFSIMS Time-of-flight secondary ion mass spectrometry
TOTM Trioctyl trimellitate
TPE Thermoplastic elastomer
TPO Thermoplastic olefinic elastomer
TPU Thermoplastic PU
TR Thin rubber
TRIM Trimethylolpropane trimethacrylate
TSA Toluene sulphonic acid
UF Urea-formaldehyde
USP United States Pharmacopoeia
UV Ultra violet
VAMAC Ethylene acrylic terpolymer

VMQ Silicone rubber with methyl and vinyl substituents
VOC Volatile organic compounds
VP Vinyl pyridine
VS Vinyl silane
WC Water closet
WDS Wavelength dispersive X-ray (analysis)
XPS X-ray photoelectron spectroscopy

XNBR Carboxylated NBR
ZDA Zinc diacrylate

ZDMA Zinc dimethacrylate
362
Author Index
A Bobrov A. P. 182, 193, 194

Bomal Y. 193, 210, 211
Ahmad S. 211
Bond K. M. 51, 136
Ahn J. H. 179, 191, 193, 209 Boros A. 354
Alarcon-Lorca F. 212 Borroff E. M. 161, 256
Aldred D. H. 256 Bourrain M. P. 210
Allen K. W. 54 Bowden P. J. 212
Alliger G. 78 Bradford W. G. 348, 355
Alstadt D. M. 78 Bragole R. A. 19, 52
Andries J. C. 160 Brandon D. G. 55
Ayres R. L. 51 Brass I. 52
Brecht H. 51
B Brewis D. M. 29, 51, 52, 53, 54, 283
Briggs D. 14, 51, 52, 54, 209, 283
Ball J. J. 168, 192, 211
Brindoepke G. 211
Bantjes A. 194
Brodsky G. I. 348, 355
Barker L. R. 211
Brunat W. 54
Barr T. L. 210
Buchan S. 78, 191
Basaran M. 209 Burkhart T. 211
Bascom D. 353 Burrows F. H. 212
Beamson G. 16, 52 Busscher H. J. 54
Beatty J. R. 160 Butcher D. 193, 211
Beecher J. F. 192 Butler D. P. 239
Beers R. N. 212
Benarey H. A. 51, 78
C
Benderly A. A. 52
Benko D. A. 212 Carlson G. L. 54
Bhowmick A. K. 51, 78, 160, 192, 193, Carne R. J. P. 53
209, 210, 354 Carter A. R. 20, 53, 161
Biemond M. E. F. 167, 192, 193, 201, 209 Cartier J. F. 51
Binder H. 51 Cayless R. A. 52
Biswas A. 192, 210 Chakraborty S. 354
Blow C. M. 78 Chakravarty S. N. 160
Blythe A. R. 51 Chaler N. A. 170, 193
363
Chandra A. K. 169, 181, 192, 193, 202, Del Vecchio R. J. 79

209, 210 De Lollis N. J. 54
Chen J. K. 54 Denq Y. L. 54
Chew A. 28, 52, 54 Deryaguin B. V. 150, 161
Child T. F. 194, 212 Deuri A. S. 193, 210
Childs T. H. C. 343, 353, 354 Dietrick M. I. 211
Clearfield H. M. 51 Dillard J. G. 23, 53, 54
Cochet P. 193, 206, 211 Dogadkin B. A. 160
Coleman Jr., E. W. 78 Downes J. 212
Collins G. C. S. 14, 52 Drake R. E. 160
Colson J. C. 210 Dreifus D. W. 283
Combette C. 26, 54 Duc T. M. 54
Combette P. 212 Duffour T. 193, 210
Comyn J. 53, 317 Dwight D. W. 14, 52
Coover H. W. 283
Cope B. C. 53
E
Corish P. J. 160
Cornell J. A. 239 Edington R. A. 256
Costin R. 79, 239, 240 Eirich R. 239
Coutsoucos A. 353 Ekwall R. 239
Craft J. 88 Eley D. D. 256
Crawford D. 239 Elliot D. J. 78
Creasey J. R. 211 Ellul M. D. 52, 143, 160
Crowther B. G. 160, 352 Elman J. F. 15, 52
Elschner A. 192, 211
D Engelhardt M. L. 212
Erickson D. E. 212
Daan H. A. 354 Ershov E. A. 193
Daft L. 59, 78 Evans L. R. 193, 206, 211, 212
Dahm R. H. 52, 54 Everaert E. P. 54
Dalgarno K. W. 342, 353, 354, 355 Extrand C. W. 21, 53
Darwish N. A. 354
Davis G. D. 51
F
Day A. J. 353, 354
De Bruyne A. 352 Fahrig M. 257
De Gryse R. 210 Feast W. J. 209
De P. P. 161 Feng Y. 240
De S. K. 161 Fernndez-Garca J. C. 53, 161
De Volder P. 210 Feuer H. O. 239
De Vries J. 54 Filbey A. 337, 353
Debruyne E. 210 Flanagan P. 239
364
Author Index
Flemming R. A. 210 Han M. H. 194, 212

Friedel C. 88 Hannell W. J. 210
Fritz J. L. 54 Hansen R. H. 52
Fritz T. L. 52 Harris S. J. 195, 212
Fritzson D. 344, 345, 354 Hartz R. E. 257
Fujii T. 353 Hashimoto K. 354
Fujikura Y. 53 Hawkins I. M. 193, 210
Fujino A. 239 Hazelton D. R. 52, 143, 160
Fuller K. N. G. 160 Hennemann O. D. 52
Hess R. H. 211
G Hewitt N. L. 193, 211
Hill J. M. 18, 51
Garbassi F. 55
Hirahara H. 195
Gatza P. E. 239
Hiratsuka S. 195
Gent A. N. 21, 53, 160, 161, 352
Hisaki H. 354
Gerbert G. 344, 345, 354
Hivert D. 54
Gerenser L. J. 15, 52
Hoekje H. H. 211
Gesang T. 52
Hofer F. 192, 209
Ghosh S. K. 354
Hoff C. M. 182 193, 211, 212
Ghosh T. B. 209
Hofmann W. 79
Gibbs H. W. 192, 193, 210, 211
Hojjati M. H. 354
Giridhar J. 169, 189191, 193, 195, 209
Hollahan J. R. 54
Goerl U. 257
Holtkamp D. 192, 211
Goralski E. G. 193, 212
Hope J. C. 193, 211
Goryaev V. 184, 194
Horie H. 195
Grabov I. F. 195
Hrnstrm S-E. 194
Gregory H. J. 54
Grigorev M. F. 194 Hoshiro T. 353
Grogger W. 192 Howath T. 239
Grubbauer G. 192, 209 Huang J. 193, 208, 212
Gupta B. R. 354 Hudis M. 54
Hummel K. 192, 209
Hupje W. H. 256
H
Haemers G. 191, 210 I
Hall J. R. 52
Hall M. M. 51, 78 Ichikawa M. 160
Halladay J. R. 58, 79 Iizuka H. 342, 343, 353, 354
Hamed G. R. 159, 161, 168, 182, 192, Ikeda A. 239
193, 203, 208, 210, 212 Ikeda K. 195
Hammer G. E. 209, 210 Ikeda Y. 195
365
Ishikawa Y. 209, 210 Kranz G. 52

Iwabuchi H. 53 Kretzschmar T. 192, 209
Iyengar Y. 257, 354 Krone R. 184, 194
Krger R. 51
J Kubo Y. 347, 348, 354
Kurian J. 161
Janssen H. 354 Kurosaki T. 160
Jayaseelan S. K. 192, 194, 212 Kusano T. 353
Jazenski P. J. 78 Kusano Y. 22, 24, 53
Jeon G. S. 194, 212
Jerschow P. 316
L
Job L. 161
Joseph R. 161 Labarre D. 181, 193, 210
Labriola J. M. 160
K Lai J. Y. 54
Lai S. M. 160
Kagatoni M. 353 Laird A. 338, 353
Kang K-K. 212 Lake G. J. 160
Kaplan W. D. 55 Landrock A. H. 55
Karbashewski E. 18, 51 Lawson D. F. 19, 20, 23, 24, 25, 52, 53
Kato N. 53 Le Prince P. 54
Kawakami S. 210 Lee K. S. 78
Keller C. 240 Lee L. H. 352
Kendall C. R. 51 Legeay G. 54
Khavina E. Y. 192 Lehrle R. S. 210
Kido R. 342, 353 Leidheiser H. 331, 352
Kilduff T. J. 52 Levi D. W. 52
Kim H. J. 160 Lin A. 51
Kim K. J. 52 Lin Y. Y. 54
Kimu S. 195 Lingjun C. 193
Klingender R. C. 239, 348, 355 Loha P. 160
Klyachtin Y. 53 Lowe A. C. 52
Konar J. 209 Luginsland H-D. 194
Kondo A. 355 Lschen R. 52
Kondyurin A. 19, 53 Lyons C. S. 51
Konieczko M. B. 51, 52
Kopnov V. A. 345, 354
M
Koshal D. 283
Koyama T. 342, 353 Macintosh C. 256
Kozhushko G. G. 345, 354 Maeseele A. 210
366
Author Index
Mahoney C. L. 51, 352 N

Manino L. G. 78
Nagel W. 79, 239, 240
Manoj N. R. 161
Naito K. 53
Martin S. 239
Nakamura M. 195
Martn-Martnez J. M. 23, 53, 54, 161 Nakamura Y. 355
Mashimo S. 353 Nando G. B. 161
Mason M. G. 15, 16, 52 Nangreave K. R. 53
Mathieson I. 52, 54 Nawafuna H. 195
Matsui J. 346, 354 Nelson E. R. 52
Matyukhin S.A. 190, 195 Nicholas D. 52
Maucourt J. 54 Niderost K. J. 210
Mayer F. 51 Noguchi T. 53
McNamarra D. K. 51
Meier K. 257 O
Melley R. E. 160
Occhiello E. 55
Melvin T. 239
OConnor J. T. 283
Michel G. 54
Ohsako N. 353
Middletown O. H. 209 Ohura K. 354
Minagawa M. 19, 26, 53 Oishi Y. 195
Minford J. D. 51, 338, 353 Okel T. A. 193, 211
Mitchell B. 256 Okumoto T. 160
Mittal K. 18 Oldfield D. 20, 21, 22, 25, 26, 29, 51, 53
Mizumoto S. 195 Olson L. R. 239
Molitor P. 239 Oplochenko N. A. 195
Montgomery R. E. 51 Opperman G. W. 54
Montoya O. 54 Orgils-Barcel A. C. 53, 161
Moore M. J. 136 Orjela G. 195, 212
Moore R. B. 354 Othman A. B. 160
Morawski J. C. 210 Owen M. J. 54
Oyama M. 239, 354
Morel-Fourrier C. 211
Mori K. 190, 195, 349, 351, 355
Mori O. 354 P
Morra M. 55 Panchuk F. O. 190, 195
Mowrey D. H. 51, 136 Parker I. K. 353
Mukhopadhyay R. 192, 193, 209, 210 Pastor-Blas M. M. 23, 24, 53, 54
Munro H. S. 209 Pastor-Sempere N. 24, 53
Murakami Y. 353 Patrick R. L. 55
Murray P. F. 191, 209, 210 Paul R. 192, 203, 210
367
Pawlowski L. B. J. 256 Salych G. G. 192, 193

Pelletier J. B. 210 Samay G. 354
Persoone P. 210 Snchez-Adsuar M. S. 53
Peterson A. 211 Sanderson C. 59, 120
Petrich R. P. 352 Sarkar P. P. 354
Pettit D. 20, 22, 53, 161 Sartre A. 193, 210
Pieroni J. K. 239 Sasaki T. 53
Pieroth M. 168, 192, 211 Sato T. 353
Plasczynski T. 136 Schaefer R. J. 211
Pleuddemann E. P. 194, 338, 353 Schlett V. 52
Pochan J. M. 15, 52 Schoenherr D. 51
Pohmer K. 316 Schonhorn H. 52
Possart W. 161 Schoon Th. G. F. 257
Potapov E. E. 169, 192, 193 Schramm E. C. 52
Potente H. 51 Schrmann K. 121
Prescott L. E. 54 Seibert R. F. 209, 212
Prokofev Y. A. 168, 183, 192, 193 Semak B. D. 195
Sen A. 354
R Seo G. 194, 212
Setiawan L. 51
Rance D. G. 52, 54 Sexsmith F. H. 51, 78
Rangarajan V. 191
Sharma S. C. 186, 194
Rauline R. 209, 211
Shekhter V. E. 193
Reed T. F. 212
Shibata T. 353
Rhee C. K. 160
Shieh C. H. 160, 161
Ridha R. A. 212
Shields J. 54, 55
Riggs W. M. 52
Shijian L. 212
Rijpkema B. 243, 256
Shoaf C. J. 256
Roach J. F. 212
Shofner D. L. 51
Roberts A. D. 146, 160
Shvarts A. G. 193
Rodriquez G. 239
Shyu S. S. 54
Roland C. M. 161, 239
Siverling C. E. 78
Roseboom F. 194
Sjothun I. J. 78
Rowe D. 352
Skeist I. 51, 55, 283, 352
Skewis J. D. 161
S Smilga V. P. 161
Saito M. 355 Snodgrass L. J. 193, 212
Saito T. 53 Snogren R. C. 55
Saito Y. 239 Soldatos A. C. 160
Sakharova E. V. 192, 193 Solomon T. S. 346, 354
368
Author Index
Sommer F. 192 van der Mei H. C. 54

Song J. 194 van Ooij W. J. 165, 166, 167, 169,
Souchet J. C. 211 177, 180, 181, 185, 186, 191, 192,
Sowell R. R. 54 193, 194, 195, 199, 200, 201, 204,
Starinshak T. W. 212 205, 209, 210, 212
Stohrer W. D. 52 Verbanc J. J. 160
Strain F. 211 Vincent M. 195, 212
Strobel M. 18, 51 Voyutskii S. S. 148, 161
Stubbs J. A. 353
Stuck B. 211
Subramanian V. 194 W
Sugimoto M. 160
Sutherland I. 52 Waddell W. H. 183, 193, 211, 212
Swanson M. J. 26, 54 Wagner M. P. 206, 211
Symes T. E. F. 20, 21, 22, 25, 27, 51, 53 Wake W. C. 159, 161, 256, 352
Wallerswein S. 211
Walz G. 211
T
Walzak M. J. 18, 51
Takeyama T. 346, 354 Watanabe 342
Tarney R. E. 160 Watanabe A. 355
Tate P. E. R. 192, 206, 210, 211 Watanabe K. 353
Teets A. R. 239 Watanabe M. 353
Terashima K. 160 Watanabe N. 354
Tessier L. 193, 210 Watanabe T. 53
Thomas J. 51 Watts J. F. 52
Thornton J. S. 51 Weening W. E. 191, 209, 210, 243,
Todani Y. 354 256, 354
Toesca S. 210 Wegman R. F. 54
Tomanek A. 316 Weih M. A. 78
Tommasini F. 195, 212 Weihe J. 51
Torregrosa-Maci R. 53, 54 Wenghoeffer H. M. 257
Torr-Palau A. 53 Westerdahl C. A. L. 52
Touchet P. 239
Wheeler E. L. 212
True W. R. 212
Whelan A. 78
Tsutsumi S. 353
Wieczorek K. 317
Tutt M. J. 354
Wightman J. P. 337, 353
Wiktorowicz R. 52
V Wilson J. C. 193, 210
Vakula V. L. 161 Wolff S. 211, 257
van der Aar C. P. J. 194 Wootton A. B. 51
369
X
Xie H. 240
Y
Yamaguchi K. 195
Yan H. 212
Yoshi F. 53
Yoshikawa M. 53
Yu D. Q. 354
Z
Zaporozhchenko V. I. 194
Zhang J. Q. 194
Zierler L. 257
370
Company Index
A Lord Corporation 12, 57, 58, 61, 63,

77, 81
Abrasive Developments 42
Advanced Elastomer Systems 259
M
B Metallgesellscahft 61
Metalok 61
Bayer 60
Michelin & Cie 209
Morton International 128
C
Chemical Inovations Limited (CIL) 61
N
D Nagase Co. 246
Degussa AG 60, 257

P
E Par Chemie 61
Pirelli 189
E. I. du Pont de Nemours and
Company 160, 256, 259 Proquitec 61
Electro-Chemical Rubber & Manufactur-
ing Company 78 U
EMS American Grilon 246
Union Carbide Corporation 160
Uniroyal Chemical Company Inc. 212
G
Goodyear Tire and Rubbers (US) 212 V
Vulnax International Ltd. 246
H
Henkel KGaA 61, 81, 88
W
Honda Motor Company 42
Hughson Chemicals 81 Wacker-Chemie GmbH 295, 311
L Y
Loctite 283 Yamashita Rubber Company 42
371
372
Main Index
A retention 189
rubber-to-metal 224
Abrasive wear 345
surface irradiation 351
Accelerator 175, 176, 177
T-pull 237
Accelerators
temperature 349
2-mercaptobenzothiazole 65
test methods 76
mercaptobenzothiazole disulphide 65
theories 148
sulphenamide 183
tyre cord 197
tetramethyl thiuram disulphide 65
Adhesion of rubbers 334
Acrylic acid 215
rubber flow 334
butyleneglycol dimethacrylate 214
metallic salts 215 stabilisation 335
Addition curing 294 wetting 334
Additive 164 Adhesion peel tests 224
Adherend Adhesion promoter 226, 230
surface conditions 335 internal 226, 230, 231
surface roughness 336 Adhesion test
Adhesion 76, 148, 312 T-pull 236
braided wire 235 three cord 348
build-up 292 Adhesive 25, 62
corrosion 350 characteristics 62
curing system 251 cyanoacrylate 37
duration of 296 dispersions 234
environmental factors 349 epoxide 25
fabric 235, 236 flow characteristics 336
factors affecting 253, 352, 349 heat reactive contact cements 37
hardness 350 hot melt reactive urethane
humidity 349 prepolymers 37
in service 254 polyurethane 156
interfacial 205 primers 71
mechanisms 250, 252 rubber to metal 62, 63
monofilament 235 selection 66
prevention 351 silane treatments 37
problems 339 tie layer 232
373
two-part epoxies 37 B
two-part urethanes 37
Bearing pads 102
wetting 128
Belt failure 341
Adhesive application 69
abrasive wear 345
brushing 69, 71
back cracking 342
dipping 69, 70
cord failure 341
spraying 69
cord separation 344
tumbling 69
fabric breakage 345
Adhesive bond
fabric separation 341, 342
strength 231
joint failure 345
Adhesive systems 241
radial cracking 344
solvent-based 248
tensile failure 344
urethane 158
tooth root cracking 341
Alloys
wear 341, 344
metal 59
Belt life
ternary 189
prediction 344
Aluminium 326
shear stress 344
anodising 12
Blooming 145, 146, 147, 151, 280, 282,
Analysis 19, 20, 24 283, 349
Fourier transform infrared 19, 23 Boiling water tests 107
infrared 20, 24 Bond failure 74, 319
X-ray fluorescence 20, 25 corrosion 319
Antidegradants metal preparation 319
antioxidants 66 moulding procedures 319
antiozonants 66 product abuse 319
prevulcanisation inhibitors 66 product design 319
waxes 66 Bond formation 71, 144
Application methods 98, 101, 117 Bond integrity 73
brush 98 Bond strength 190
dip 98 Bondability 64
electrostatic 98 index 64
flowcoat 98 Bonded parts 72
reverse roller coat 98 knit lines 72
roller 98 splits 72
sponge 98 Bonding 29, 73, 152, 337
spray 98 concepts 291
Aramid 247 duration 311
ASTM test methods 122 interface 337
Autohesion 137, 139, 141, 144, 148, 150 interphase 337
374
Main Index
mechanical ties 292 organic solvent-based 127

post vulcanisation 36, 73, 100, 101 primer/cover-coat 63
properties 309 waterborne 98, 103, 127, 128, 129,
rubber to brass 163 130, 131
rubber to fabric 241 disadvantages 134
rubber to metal 319 factory usage 128
polymer 134
rubber to plastic 29
pre-bake resistance 133
silicone to metal 288
primers 134
silicone to plastic 288 product range 134
silicone to silicone 287, 308 thickness effects 131
solid rubber 299 Bonding techniques
strip 152 mechanical 314
test procedures 76, 77 Braid
test specimen geometry 76 Nylon 236
vulcanisation 37 Brass 59, 163
Bonding agent 93, 98, 99 composition 164
application methods 98 electrodeposited 59
application to metals 325 Brass adhesion 181
applications 93 additives 181
moisture-sensitive 114 boroacylate 181
photosensitive 115 cobalt-naphthenate 181
prebake 118 compounding 180
preparation 97 neodecanoate 181
re-certification 113, 114 silica 180
solvent 103 stearate 181
testing 110 Brass plating 163
thickness 99 Bridge bearing pads 100
waterborne 103 Bush components 102
Bonding concepts 291
primers 291, 292
C
self bonding silicone LR 291
self-bonding silicone rubbers 292 Cable connectors 314
undercuts 291 Cable industry 309
Bonding mechanism Calcium hydroxide 142
rubber to metal 62 Car emissions 197
Bonding systems 63, 97, 98 reduction 197
application 129 Carbon black 141, 351
in situ 249 easy processing channel 140
metal preparation 129 high abrasion furnace black 147
one coat 63 Chain scission 141
375
Chemical treatments 37, 68 Corona discharge 26

phosphatising 68 Corona treatment 17, 19
Chemisorption 63 after derivatisation 17
Chloropyrimidines 208 Corrosion 5, 6, 62, 68, 164, 177, 186,
Chlorotriazines 208 321, 330
Cleaning anodic 331
abrasives 321 by overheating 332
metal 321, 322 cathodic 331
Coagents chemical 332
metallic 60 electrochemical 330
methacrylate ester 214 galvanic 5, 74, 332
triallyl cyanurate 215 inhibitors 62, 205
trimethylolpropane trimethacrylate resistance 68
214, 215 underbond 69
Coated components Cotton 244
assembly 102 Coumarone-indene 141
Coatings Coupling agents 186, 206, 213
primer 325, 326
titanate 213
rubber bond 325, 326
zirconate 213
Cobalt salts 60, 174, 187, 189, 202, 207
Cover coat 38
boroacylate 202
Covulcanisation 140
metal organic 197, 201
Crosslinking 62, 141, 329
naphthenate 164, 168, 202, 203
agents 61
stearate 202
peroxide 213, 216
Coefficient of restitution 215
polysulphide 216
Cohesive failure 232
Cryogenic techniques 178
Compounding 59, 60, 223
Cryoblasting 27
characteristics 64
isopropyl azodicarboxylate 138 deflashing 118, 299
self-bonding 60 Curative 234
soft rubber 59 peroxide 234
Compression moulding 299 sulphur 234
Compression set 224, 310 Cure characteristics 224
Contact pressure 144 Cure rate 224
Contact temperature 144 Curing 223
Contact time 144 peroxide 235
Contamination 118 Curing times 295, 305
Copper sulphide 178 Cyanoacrylate 37, 260
Cords acidic substrates 264
brass 202 activators 274
heavy cabled 249 adhesives 263
376
Main Index
application methods 275, 277 cure speed 263

applications relative humidity 262
blooming 280, 282, 284 temperature 263
bond line thickness 268 volume 262
bonding EPDM 277 Cyclohexyl benzothiazole sulphenamide
bonding medical devices 279 170
bonding natural rubbers 277
bonding nitrile 277 D
bonding polychloroprene 277
Debonding 200
bonding Santoprene 279
Deflashing 73, 118
bonding silicone rubbers 279
cryogenic 118, 299
bonding to silicone rubber 270
non-cryogenic 73
cleavage loads 267
Degreasing 35, 37
design considerations 266
aqueous 35
environmental resistance 270
Delamination 344
excess adhesive 281
Demoulding 119
external release agents 269
Dezincification 164, 167, 184, 201, 204
glass bonding 272
Drying 102, 128, 129
glazed appearance 284
health and safety 276
heavy molecular weight 282 E
hot strength 272 Ebonite 58, 59
internal release agents 269 Electrochemical corrosion 200
joint design 269 Electroplating 73
liquid 259 Engine mounts 57, 100, 102
low strength 284 car 319
no cure 284 fluid 57
peel loads 267 Environmental aspects 254
poor adhesion 284 of processing 255
porous substrates 264 pollution limits 127
pressure systems 275 storage and handling 254
relative humidity 262, 281 wastes and disposal 255
slow cure 281 Ethylene propylene diene rubber 64
special requirements 269
syringe systems 276
F
time systems 275
toughened 265 Fabric breakage 345
Cyanoacrylate, curing 260, 261 Fabric separation 348
acidic deposits 263 Fabric treatments 241
adhesive 262 aqueous 241
377
Fabrics Hexamethoxymethylmelamine 206, 207

cotton-based 250 Hexamethylene tetramine 205, 207
Failure 61, 74, 145, 319 High abrasion furnace black 140
bond 235 HTV silicones 300
cement/metal 74 properties 300
cement/primer 75 Humidity 147
cohesive 61, 158, 236 Hydrogenated nitrile rubber 214
cord separation 344
interfacial 145, 158 I
rubber 74
rubber/cement 74 Ignition cables 309
Fatigue life 320 Infra red analysis
Fibre reinforcement 339 attenuated total reflection 182
Fillers 65, 140 Injection moulding 313
carbon black 65 hot runners 307
channel blacks 65 plastic substrates 306
silica 65 two colour mould 306
Film Instruments
interfacial 178, 179, 182 surface tension pens 128
Film thickness 101, 106 Instruments, measuring 71
Fixing. See Adhesion beta backscatter 71
Flocculation 127, 128, 327 dry film 71
Formaldehyde 346 magnetic induction current 71
Formulation preparation 222 Interdiffusion 148, 149
Interface 62, 205
dip/rubber 250
G
dip/textile 252
Galvanic cell 350 primer to adhesive 63
galvanising. See also Zinc coating 11 primer to metal 62
Gibbs free energy 149 rubbermetal 205
Green strength 137, 138, 148 Internal mixer 223
Green tyres 197, 206 Banbury 223
Grit blasting 9 34, 37, 321 Ionic bonds 216
Ionomers 216
H Isobutylene-isoprene (butyl) rubber 64
Isocyanate 248, 252
Hardness 224
Shore A 224
J
Health and safety 109
inorganic lead salts 110 Joint 147
solvents 110 butt 147
378
Main Index
peeling 147 heat treatment 328

Joint failure 345 mechanical pre-treatment 6, 7
oxide layers 4
K pre-treatments 6
preparation 3
Keypads removal of grease 8
silicone 309 removal of oil 8
silica 351
L smutting 4
substrates 3
Latex 346
surface tension 350
Layover 106, 119
Metal preparation 117
Leaking moulds 118
anodising 322
Liquid rubber 227
chemical modification 322
bonding 293
faulty 321
silicones 300
plating 322
Liquid squalene 168
sheradising 324
Metallic coagents 213, 215, 216
M Saret 216
Maintenance Metallography 3
spray equipment 70 Methacrylic acid 215
Martensite 11 metallic salts 215
surface 323 Microscopy 19, 198
Mass spectrometry 165 analytical electron 198
secondary ion 168 electron 33
secondary neutral 168 scanning electron 19, 168, 202, 208
time-of-flight secondary ion 165 transmission electron 168, 169
Mechanical bonding Mill 223
clamping 310 two-roll 223
undercuts 310 Modulus 224
Metal 4, 6, 8, 10, 67, 129 Montreal Protocol 126
activation 67 Mould design 328
adhesion 229 Mould release agents 269
alloys 3 external 269
carbon black 351 internal 269
chemical pre-treatment 6, 10 Moulding 30, 33, 35, 72
cleaning 129 compression 30
complexes 208 extrusion blow 30
crystal size 350 high pressure 35
degreasing 7 high temperature 33
379
incorrect procedures 328 Physical tests 224

injection 30 Plasticisers 141
operation 118 reactive super 213
reaction injection 30 Plastics 12, 13, 31, 40, 41
transfer 30 pre-treatment 12, 13
Moulding operation 118 primers 37
Moulds 72 substrate preparation 31
bonding process 72 Platen temperatures 119
designing 72 Polyamide 244
Polybutadiene rubber 138
maleated liquid 141
N
Polybutylene terephthalate 288
Natural rubber 64, 138 Polycarbonates 32
Natural rubber or polyisoprene Polychloroprene 64
Nitrile rubber 64 Polydimethylsiloxane 293
Novolak resin 242, 243 Polyester 245, 246, 248
Nylons 288 textiles 248
Polyethylene 33
O Polyethylene terephthalate 245, 288
Polyisocyanate 60, 154
Organic resins 62 Polyisocyanates
Oscillating-disk rheometer 224 Polymer micelles 104
Oxide films 7 Polymers 62
Oxides halogenated 62
surface 9 polyphenylene oxide 32
Ozone exposure 142 solvation 214
Polyphenylene sulphide 32, 288
P Polypropylene 33
Polysulphides
Paints oligomeric 168
high solvent 73 Polyureas 32
Peaning 9 Polyurethanes 27, 32
Peel energy 145 Post vulcanisation bonding 102
Peel strengths 21, 23, 24, 26, 28, 157, cure cycle 102
237 partial 320
Peel test 110, 148, 237, 296, 298, 300, Power transmission belts 339
348 adhesion systems 346
T-peel 348 adhesion testing 347
Phenol-formaldehyde 141 belt life 341, 346
Phosphate treatment 68, 94, 95 bonding 339
coating 10, 323 conveyor belts 345
380
Main Index
failure 340 Q
synchronous 340
Quality testing 329
V-belts 343, 345
Pre-treatments
abrasion 13 R
chemical 68 Rayon 244
chlorination 73 Re-certification period 114
corona 13, 28 Reactive dispersion 230, 235
etching 28 Recycling 190
flame treatment 13, 28 Reinforcing material 197
metal 69 Relative tack 141
phosphatising 68 Release agent 329
plasma 28 accidental application 329
sodium complexes 13 Resins 205
solvent wipe 13 one component 207
trichloroisocyanuric acid 13 Resorcinol 205, 346
Prebake resistance 99, 106 RFL adhesive system See also Resorcinol
Preparation methods 60, 241, 244, 246
substrate 3 dip 248
Primers 62, 321 formulation 242
application 116 novolak resin 243
rubber to metal 62 preparation 242
Processing oils 66, 141 Rubber 6, 12, 20, 21, 25, 26, 27, 28,
aromatic-based 66 29, 138
ester-based 66 butyl 20
naphthenic 66 conventional 41
Processing techniques 303 ethylene-propylene 19, 28, 138
inserted parts 303 ethylene propylene diene 138
Product abuse 333 fully cured 159
high temperatures 333 halogenated 25
mechanical interference 333 hydrocarbon 19
oils and solvents 333 liquid 225
service loading 333 natural 20
Product design nitrile 26
effects on bond failure 320 peroxide cured 65
Profile pre-treatments 12
carbon depth 180 shrinkage 6
Properties silicone 26
interphase 338 solid 221
Pull out tests 347, 348 strain crystallising 138
381
sulphur cured 65 S
thermoplastic 156
Safety data sheet 109
unsaturated hydrocarbon 20, 28
Scorch safety 217, 219
unvulcanised 150
Scorch time 224
vulcanized 150, 152
Sealants 225
Rubber classification
EPDM 227
wettability 336 formulation 225, 226
Rubber retention 106, 107, 109 natural rubber 225
Rubber to brass bonding 198 polybutadiene rubber 225
ageing 177, 200 polybutadiene glass 229
degradation 200 pumpable 225, 226, 228
mechanisms 198 Self-bonding HTV
organofunctional silanes 185 applications 301
Rubber to fabric bonding 247 peroxide curing 301
conveyor belting 247 Self-bonding LR 289
hose 247 limitations 298
V-belt cord 247 properties 297
Rubber to metal bonding 205 Shear adhesion 227
interface 205 Shelf life 112, 113
Rubber-to-rubber bonding Sheradising
zinc 324
ageing 146
Shoaf system 245
blooming 145
Shrinkage 339
contact time 144, 159
Silanes 186, 188, 208
effects of surface modification 142
polysulphur 187
filler 140
Silica 141, 206, 207, 351
ozone exposure 142
Silica/resin systems 205
plasticisers 141
Silicone HTV
polymeric additives 156 applications 290
polymers 156 Silicone LR
pressure 144 applications 290
process oils 141 Silicone roller 301
strip thickness 155 Silicone rubber composites 290
surface bloom 159 applications 290
surface roughness 144, 156 Silicone rubbers 285
surface treatments 158 bonding 286
tackifiers 141 high temperature vulcanising 285
temperature 144, 156 liquid rubber 285
vulcanisation 139 primer 287
Rust preventation 73 processing conditions 308
382
Main Index
undercuts 286 rigid plastics 69

Solvent 126 topography 335
cleaning 35 Sulphidation 175, 199
dip 8 Sulphide
elimination 126 copper 165
Spectroscopy 14, 19, 183, 198 interfacial 165
auger electron 198, 200, 207, 208, interfacial film 177
338 zinc 165, 174
electron energy loss 169 Sulphurating species 171
electron for chemical analysis 14 Surface analysis 19
ion scattering 338 Surface primers 270
proton induced X-ray emission 208 Suspension bushes 100
reflection infrared 14 Sweep tests 111
Secondary Ion 338
secondary ion mass 198
x-ray photoelectron 14, 19, 23, 183, T
198, 208
Spraying equipment 70, 105 T-peel test 23
Sputter etching 19 Tack 137, 141, 144, 145, 147, 148, 150
Squalane 171, 175 relative 137
Squalene 170, 171, 175, 184 Tackifiers 141
Stabilizers 62 Tear resistance 220, 221, 315
viscosity 62 Temperatures
Stainless steel 10 melting transition 305
pre-treatment 10 Tensile
treatments 322 elongation 224
Stearic acid 176 modulus 224
Steel cords 182, 184, 197 properties 219
brass plated 201 strength 108, 219, 220, 224
brass-coated 197 testing 148, 224
Storage stability 130 Testing 69, 147
Strength autohesion levels 147
adhesive 165 dog bone shape 296
interfacial 165, 167 tack 147
Stress cracking 35 Test specimens 296
Stresses water break 69
at interface 320 Textiles 248
Styrene butadiene rubber 64, 139 treated 253
Substrate 3, 69 Thermal ageing 177, 200
preparation 101 Threshold limit values 110
383
Tie coat layer 230, 233 Vulcanisation 30, 139, 213, 329, 330
cements 326 autoclave 30
Top coat 38 bonding 30
preparation 117 efficient 65
Torque values 224 peroxide 213
Treatment 34 semi-efficient 65
abrasive belts 34 sulphur 219
acid etching 34 system 65
alkali etching 34
chlorination 35 W
corona discharge 35
high pressure water 34 Waterborne bonding 12
hydrosonic/ultrasonic cleaning 34 metal preparation 12
mechanical 68 Welding 313, 314
oxidation 34 Wet blast process 42, 43, 47
phenol 34 degreasing agent 43
plasma treatments 35 phosphate treatment 45
satinisation 34 phosphating plant 42
UV treatments 35 VAQUA pump 43, 44
Tyre cords 163, 178, 179, 187, 189, 198 Wood rosin 141
coating 191
Tyres 150 X
precured retreading 150
X-ray analysis
radial 163
energy dispersive 19, 168, 169, 183
reinforcement 197
wavelength dispersive 169
retreading 152, 154
X-ray emission
particle induced 183
U
Unvulcanised rubbers Z
bonding 137
ZDA
scorch retarded 218
V ZDMA
V-belts 249 scorch retarded 218
cut-edge 249 Zinc coating 11, 323
Viscosity 97, 115, 130 Zinc diacrylate 60
reduction 213 Zinc dimethacrylate 60, 214
sensitivity 114 Zinc sheradising 11
viscometry 114 Zirconates 214
Volatile organic compounds 62 neoalkoxy 214
384

Handbook of Rubber Bonding

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Handbook

Bryan Crowther (Editor)

Editor: Bryan Crowther

Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Rapra Technology Limited

2001, Rapra Technology Limited

All rights reserved. Except as permitted under current legislation no part

Typeset by Rapra Technology Limited

1 Substrate Preparation Methods ....................................................................... 3

1.4.3 Comparison Between Conventional and Wet Blast Phosphating .. 45

2 Rubber to Metal Bonding ............................................................................. 57

3 Rubber to Metal and Other Substrate Bonding ............................................. 81

3.2.2 The Abrasion Process ............................................................... 90

3.9 Shelf Life Considerations ................................................................... 112

4 Bonding Rubber to Metals with Waterborne Adhesive Systems .................. 125

5 Rubber to Rubber Bonding ......................................................................... 137

5.1.1 Tack/Autohesion .................................................................... 137

6 Rubber-Brass Bonding ................................................................................. 163

6.2.3 Updated Rubber-Brass Adhesion Model ................................ 170

7 Review of Tyre Cord Adhesion ................................................................... 197

8 Rubber to Metal Bonding Using Metallic Coagents .................................... 213

9 Rubber to Fabric Bonding ........................................................................... 241

10 Bonding Rubber with Cyanoacrylates ......................................................... 259

10.5.1 Minimise Peel and Deavage Loads .................................... 267

11 Bonding Silicone Rubber to Various Substrate ............................................ 285

11.4 Some Applications of Silicone Rubber Composites ......................... 290

12 Failures in Rubber Bonding to Substrates ................................................... 319

12.1.3 Incorrect Production Quality Testing Procedures .............. 329

Abbreviations and Acronyms............................................................................. 357

Author Index ..................................................................................................... 363

Company Index ................................................................................................. 371

Main Index ........................................................................................................ 373

The Handbook of Rubber Bonding

Wim van Ooij

B. Crowther (Section 1.1)

1.1 Metal Preparation General Techniques

1.1.1 Structure of Metal Substrates Metallography

The Handbook of Rubber Bonding

1.1.3 Rubber Component with Metal Support

1.1.4 Metal Pre-treatments

1.1.4.1 Mechanical Methods

Alkaline removal of oils and greases

Solvent dip methods for large scale removal of greases

Removal of surface oxides

Metals, after degreasing, have to be blasted with a sufficiently abrasive material to

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

a) degrease metal part

a) immerse in a solution of 20 parts by weight concentrated hydrochloric acid with

The second method of zinc coating is more widely used.

Aluminium is usually electrolytically anodised, in the presence of an acid, either sulphuric,

Metal preparation - for waterborne bonding systems

1.2 Pre-treatments of Plastics and Rubbers

1.2.2 Studies of Pre-treatments for Plastics

A given pre-treatment may result in the introduction of several different chemical

Figure 1.1 Derivatisation reactions to identify functional groups introduced by pre-

Table 1.2 Quantification of surface functionalities after corona treatment

C OOH 1.2 0.9

NO3 0.8 0.4

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

Quantification of the chemical changes caused by pre-treatments,