FRP+Technology Book PDF
FRP+Technology Book PDF
FRP+Technology Book PDF
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FRP TECHNOLOGY
Fibre Reinforced Resin Systems
R. G. WEATHERHEAD, B. Sc.
Consultant and Resin Specialist, Epsom, Surrey, UK
(Formerly Senior Scientist with Shell Research Ltd,
Egham Research Laboratories, Surrey, UK)
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APPLIED SCIENCE PUBLISHERS LTD
RIPPLE ROAD, BARKING, ESSEX, ENGLAND
Weatherhead , R, G .
FRP techno logy.
I . Fiber reinforced plastics
I. Title
668.4'94 TPll77
All rights reserved. No part of thi s puhlication may be reprod uced, stored in
a retrieval system, o r transmitted in any form or by any mea ns, electronic,
mechanical, photocopying, recording. or otherwise. without the prior
written permission of the publisher.;, Applied Sciena: Publishers Ltd.
Ripple Road, Barking. Essex, England
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PREFACE
Synthetic resins have become increasingly important over the years, finding
wide application in a variety of fields. Not least have been the tremendous
strides made in the use of fibre reinforced resin systems. Although by far the
bulk of all fibre reinforced products are made from unsaturated polyester
r~sins reinforced with glass fibres, other resins and other fibres are playing
an increasingly important role. It is with this in mind that the present book
has been written. An attempt has been made to combine within one book
information on the various resin systems and reinforcing fibres in use
today, together with some properties and processing details.
Since most of the resins available are formulated products rather than
pure chemical compounds, some information has been included on
commercially available materials. For convenience, where commercial
data have been included, these have been located at the end of the
appropriate chapter or, where only limited data are presented, at the end of
the appropriate section. Such data have been included for the benefit of
designers and fabricators, to indicate the wide choice of materials available
and to enable them to select materials without having to approach a vast
number of suppliers and then to sift through an even greater number of
data sheets. It is not claimed that these lists are complete, nor that these are
the only suppliers of such materials, nor that the products mentioned are in
any way superior to any which may have been omitted, although every
attempt has been made to make the lists as comprehensive as possible. Also
included is a list of some of the test methods likely to be encountered in the
use and evaluation of fibre reinforced resin systems.
Thus this book is intended to serve not only as a text book but also as a
reference book for all those interested in commercial materials, trade
names, etc., used in the reinforced plastics industry.
As with all commercial materials, product specifications may be changed
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vi PREFACE
from time to time and whilst the data included can be used as a guide to
material selection, up-to-date information should always be sought from
the appropriate supplier.
Where trade names are mentioned, it should be borne in mind that these
are the property of various companies and before use, enquiries should be
made of those companies. Likewise, some of the processes mentioned are
covered by patents and licencing agreements and should not be used
without prior consultation with the appropriate company.
I should like to thank all those suppliers who have provided technical
data on their products for inclusion in this book and who are mentioned in
the text. In particular I should like to thank the following companies for
providing photographs and figures or for assisting in obtaining such
illustrations: Binks-Bullows Ltd; British Industrial Plastics Ltd;
Fibreglass Ltd; Hoechst AG; Huls (UK) Ltd; Johnston Pipes Ltd; A/S
Jotungruppen; K & C Mouldings (England) Ltd; Scott Bader Co. Ltd;
Shell Chemicals UK Ltd; Symes International BV; and Vetrotcx (UK)
Ltd.
I should also like to thank my brother-in-law C. A. White for reading
through the draft and offering valuable suggestions as to where improve-
ments would be beneficial.
R. G. WEATHERHEAD
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CONTENTS
Preface v
Chapter I
GENERAL INTRODUCTION 1
1.1 Introduction . 1
1.2 Why Use FRP? 2
1.3 Which Resin? 3
1.4 Reinforcements 4
1.5 Process Development 5
References 6
Chapter 2
DESIGNING IN FRP 7
2.1 Introduction . 7
2.2 Design 7
2.2.1 Material selection 9
2.2.2 Process selection . 10
2.2.3 Section thickness. II
2.2.4 Flanges and corners 12
2.2.5 Inserts. 12
2.3 Flat Sheets 12
2.4 Building and Cladding Panels 13
2.5 Hollow Structures . 13
References 14
Chapter 3
MOULDS 15
3.1 Introduction 15
VII
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VllI CONTENTS
Chapter 4
MOULDING PROCESSES 33
4.1 Introduction . 33
4.2 Contact Moulding-Wet Lay-up 38
4.2.1 Hand lay-up 41
4.2.2 Spray lay-up 45
4.3 Vacuum Bag Moulding. 49
4.3.1 Wet lay-up. 49
4.3.2 Prepreg systems . 50
4.4 Pressure Bag Moulding . 51
4.5 Resin Injection or Resin Transfer Moulding. 52
4.6 Pressure Injection . 55
4.7 Vacuum Impregnation and Injection 55
4.7.1 Vacuum impregnation. 56
4.7.2 Vacuum injection moulding-Hoechst process 56
4.7.3 Vacuum injection-British Rail process 58
4.7.4 Monoforming 59
4.7.5 CSI process-Crystic Systems Ltd 59
4.8 Foam Reservoir Moulding 59
4.9 Cold Press Moulding 61
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CONTENTS IX
Chapter 5
COMMON FAULTS FOUND IN GRP MOULDINGS 86
5.1 Introduction. 86
5.2 General Faults with Polyester Mouldings 86
5.3 Spray Moulding Faults. 98
5.4 Faults with Translucent Sheeting 99
5.5 Press Moulding Faults . 101
5.6 Resin Injection Faults . 102
5.7 Vacuum Moulding Faults 103
5.8 Filament Winding Faults 104
5.9 Centrifugal Casting Faults 105
5.10 Faults with Epoxide Resin Systems 105
Reference 108
Chapter 6
BONDING AND JOINTING REINFORCED PLASTICS 109
6.1 Introduction. 109
6.2 Adhesive Bonded Joints. 109
6.2.1 Surface preparation 111
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x CONTENTS
Chapter 7
MAINTENANCE AND REPAIR OF FRP STRUCTURES. 115
7.1 Introduction. liS
7.2 Maintenance. 115
7.3 Repairs to GRP Structures 116
7.3.1 Surface damage . 116
7.3.2 Small impact fractures 116
7.3.3 Holes. 118
7.3.4 Repair of holes where internal access is impossible 119
7.3.5 Repairs to pipes. 120
Reference 121
Chapter 8
SITE APPLICATION OF LAMINATES 122
8.1 Introduction. 122
8.2 Steel Structures 124
8.2.1 Initial preparation 125
8.2.2 Laminate application 126
8.2.3 Alternative laminating procedure 128
8.2.4 Alternative resin systems 129
8.3 Concrete Structures 129
8.3.1 Crack treatment. 130
8.3.2 Preparation of concrete substrate 131
8.3.3 Application of the laminate. 134
8.4 Wooden Structures 135
8.5 Repairs to Pipelines-Concrete, Steel or Thermoplastic. 136
8.6 On-site Tank Production 137
References 138
Chapter 9
POLYESTER RESINS . 139
9.1 Introduction. 139
9.2 Polyester Resins 140
9.2.1 Glycols 141
9.2.2 Unsaturated acids 142
9.2.3 Saturated acids . 143
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CONTENTS xi
Chapter 10
CATALYSTS, ACCELERATORS AND INHIBITORS
FOR UNSATURATED POLYESTER RESINS 204
10.1 Introduction . 204
10.2 The Curing Reaction 206
10.3 Catalysts or Initiators 209
10.3.1 Diacyl peroxides. 210
10.3.2 Ketone peroxides 212
10.3.3 Hydroperoxides . 215
10.3.4 Dialkyl and diaralkyl peroxides 216
10.3.5 Peroxyesters 217
10.3.6 Perketals (peroxyketals) 220
10.4 Accelerators or Promoters 221
10.4.1 Metal compounds 221
10.4.2 Tertiary amine accelerators. 223
10.4.3 Mixed metal salt/t-amine accelerators. 224
10.5 Inhibitors 224
10.6 Commercially Available Materials. 239
References 239
Chapter 11
EPOXIDE RESINS 240
11.1 Introduction 240
11.2 The Resins 242
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XII CONTENTS
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CONTENTS XIll
Chapter 14
REINFORCEMENTS .308
14.1 Introduction . 308
14.2 Surfacing Tissue 310
14.3 Glass Fibre Reinforcements 312
14.3.1 Continuous filament rovings 313
14.3.2 Chopped strands. 315
14.3.3 Chopped strand mat 317
14.3.4 Continuous strand mat 319
14.3.5 Woven glass fabrics 319
14.4 Carbon Fibre. 323
14.5 Aromatic Polyamide (Aramid) Fibres 327
14.6 Other Reinforcing Fibres 329
14.6.1 Polyester fibres 329
14.6.2 Polyacrylonitrile fibres 330
14.6.3 Nylon. 330
14.6.4 PVC and PVDC . 330
14.6.5 Cotton 330
14.6.6 Sisal 330
14.6.7 Asbestos 330
14.6.8 Paper. 331
14.6.9 Jute 331
14.6.10 Boron fibres 331
14.7 Commercially Available Reinforcements 348
References 348
Chapter 15
DOUGH AND SHEET MOULDING COMPOUNDS
AND PREP REGS . 349
15.1 Introduction . 349
15.2 Dough and Bulk Moulding Compounds (DMC, BMC). 350
15.3 Sheet Moulding Compounds (SMC) 352
15.3.1 Manufacture of SMC . 352
15.4 Prepregs. 355
15.4.1 Manufacture of prepregs 356
15.5 Commercial Products 358
References 371
Chapter 16
FILLERS AND PIGMENTS. . 372
16.1 Introduction . 372
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XIV CONTENTS
Chapter 17
MISCELLANEOUS MATERIALS 389
17.1 Internal Lubricants 389
17.2 Skin Formers. 389
17.3 Light Stabilisers 390
17.4 Release Agents and Sealing Compounds 390
17.4.1 Wax release agents 390
17.4.2 Polyvinyl alcohol (PV A) 391
17.4.3 Spray release agents 391
17.4.4 Silicone release agents. 391
17.4.5 Sheet release agents 392
17.4.6 Cellulose acetate. 392
17.4.7 Nitrocellulose 392
17.4.8 Shellac 392
17.5 Core Materials 393
17.5. I Balsa wood. 393
17.5.2 Firet Coremat 394
17.5.3 Intercel 395
17.5.4 Honeycombs 396
17.6 Coupling Agents 396
References 398
Some Suppliers 398
Chapter 18
LAMINATING EQUIPMENT 399
18.1 Introduction . 399
18.2 General Equipment 399
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CONTENTS XV
Chapter 19
HANDLING AND SAFETY PRECAUTIONS 411
19.1 Introduction . 411
19.2 General Precautions 411
19.2.1 Remedial measures 412
19.3 Epoxide Resins 414
19.4 Curing Agents 415
19.4.1 Aliphatic amines .' 415
19.4.2 Aromatic amines. 415
19.4.3 Cycloaliphatic amines . 415
19.4.4 Polyamide curing agents 415
19.4.5 Anhydride curing agents 416
19.4.6 Other curing agents 416
19.5 Furane Resins 416
19.6 Polyester Resins 416
19.7 Peroxide Catalysts. 417
19.8 Fillers and Pigments 419
19.9 Barrier and Cleansing Creams 420
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XVI CONTENTS
Chapter 20
TEST SPECIFICATIONS 421
20.1 Introduction . 421
20.2 Chemical Properties 421
20.2.1 Acid value of unsaturated polyester resins 421
20.2.2 Chemical resistance 422
20.2.3 Acetone extractables 422
20.2.4 Chlorine content. 422
20.2.5 Epoxide content . 422
20.2.6 Hydroxyl content of unsaturated polyester resins 423
20.2.7 Organic peroxides 423
20.2.8 Water resistance. 423
20.3 Fire and Smoke Tests 424
20.3.1 Flammability tests 424
20.3.2 Smoke evolution tests. 425
20.4 Mechanical Properties 425
20.4.1 Compressive strength and modulus 425
20.4.2 Flexural strength and modulus 425
20.4.3 Tensile strength and modulus 426
20.4.4 Interlaminar shear strength (lLSS) 426
20.4.5 Impact strength 426
20.5 Physical Properties. 427
20.5.1 Density and specific gravity. 427
20.5.2 Gel time 427
20.5.3 Hardness-indentation 427
20.5.4 Shrinkage 428
20.5.5 Viscosity 428
20.6 Thermal Properties 428
20.6.1 Heat deflection temperature 428
20.6.2 Martens heat deflection temperature 429
20.6.3 Coefficient of expansion 429
20.6.4 Flash point. 429
20.7 Electrical Properties 430
20.7.1 Arc resistance 430
20.7.2 Dielectric constant (permittivity) and power factor 430
20.7.3 Dielectric breakdown voltage and dielectric strength 430
20.7.4 Dust fog tracking and erosion 431
20.7.5 Volume and surface resistivity 431
20.8 Miscellaneous Test Specifications 431
20.8.1 Colour 431
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CONTENTS XVlI
Appendices
1 Trade Names 434
2 General Material Suppliers 439
3 Company Names and Addresses 440
4 Units, Prefixes and Conversion Factors 448
Index 451
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Chapter 1
GENERAL INTRODUCTION
1.1 INTRODUCTION
During the past thirty years and more, vast strides have been made in the
use of fibre reinforced thermosetting resins until today their use is
commonplace.
Only a few years ago one would hear that such-and-such an object was
made from 'Fibreglass'. Today, whilst this term is still used, a much more
common term is GRP and one frequently hears of someone who owns a
GRP boat. GRP mostly stands for Glass Reinforced Polyester, although it
is also used to describe other glass reinforced plastics. With the increasing
use of fibres other than glass as reinforcing materials, a new term has been
coined and that is FRP. This stands for Fibre Reinforced Plastics and can
cover both thermoplastics and thermosets. In the context of this book,
FRP has been used to cover just the thermosetting resins reinforced with
fibrous materials, and then not every material, as will become apparent on
reading through the book.
A fibre reinforced resin system is a composite material consisting of a net-
work of reinforcing fibres embedded in a matrix of thermosetting resin. Other
materials such as fillers and pigments may also be present, although they
are not an essential part of the composite. In general, the resin used consists
of a syrupy liquid which, when combined with a suitable catalyst or
hardener, can be cross-linked into a hard infusible solid. By impregnating
the fibrous material, frequently in the form of a cloth or mat, with the
catalysed resin and allowing the resin to cure, the composite material or
laminate is formed. This process is carried out in a mould which may be
open or closed. The resultant product is a fully cured moulding which is an
exact replica in reverse of the original mould surface.
In general, where glass is used as the reinforcing fibre the product is
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2 FRP TECHNOLOGY
The answers to this question are many and varied and may be simple or
complex. Indeed, with the family of materials which can be classified as
FRP, one should not expect a simple answer.
If we consider firstly glass reinforced polyester resins, then it is possible
to summarise the advantages as follows:
1. Thermoset.
2. Advantageous strength/weight ratio and rigidity.
3. Moulding size virtually unlimited.
4. Ease of fabrication.
5. Wide range of manufacturing techniques.
6. Low capital outlay-for hand lay-up.
7. One-off or few-off mouldings are possible at reasonable cost.
8. Considerable design versatility.
9. Can be combined with other materials, e.g. foams for buoyancy.
10. Excellent water resistance.
11. Resistant to a wide range of chemicals.
12. Resistant to weathering and UV exposure.
13. Can be coloured to give a maintenance-free finish.
14. Fire retardant-if required.
15. Transparent/translucent-if required.
16. Good electrical and thermal properties.
Similar comments apply to glass reinforced epoxide resin systems
although cure and handling characteristics and cured properties are a little
different.
With carbon fibre reinforced resin systems the composites are, of
necessity, black and so some of the above advantages do not apply.
However, in this case specific strength and modulus are sufficiently greater
than those of most other materials, including metals, that such composites
are highly attractive to designers for applications where weight is of prime
concern.
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GENERAL INTRODUCTION 3
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4 FRP TECHNOLOGY
The third class of resins encountered are the vinyl ester resins. These
combine part of the chemical backbone of an epoxide resin with the curing
mechanism of a polyester resin. Essentially an epoxide resin is converted to
a polyester resin by reaction with a suitable unsaturated organic acid. The
resultant polymer is then dissolved in styrene and used in a similar manner
to a polyester resin. The advantages gained are the ease of processing of a
polyester resin coupled with improved chemical resistance due to the
reduced number of ester linkages present in the molecule.
Fourthly we have the furane resins. These were first used in the
preparation of acid resisting cements but, with the development of
improved catalyst systems, can now be used for laminating. Furane resins
comprise a furfuryl alcohol polymer blended with furfural as reactive
diluent. Cross-linking is by means of an acid catalyst. The resultant
polymer is black. The main advantage that a cured furane resin offers over
other laminating systems is exceptional chemical resistance, even to such
materials as perchlorethylene and glacial acetic acid. Cured furane resins
also exhibit very low smoke emission under fire conditions.
Finally, as far as this book is concerned, come the Friedel-Crafts
polymers--typified by the 'Xylok't resins. These are condensation products
of aralkyl ethers and phenols and are similar in structure to phenolic
novolac resins. They require heat cure with a controlled post cure, using a
curing agent such as hexamine. When fully cured they give composites with
good thermal stability and excellent electrical properties.
Other resins such as phenolics, silicones, polyimides and melamine- or
urea-formaldehyde resins are also used with reinforcements and, while
some of these are mentioned briefly, few details have been included in this
book. These resins are all processed by hot press moulding techniques. A
typical example of a melamine-formaldehyde faced phenolic laminate
would be one of the many decorative laminates used on kitchen furniture,
etc.
1.4 REINFORCEMENTS
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GENERAL INTRODUCTION 5
One type of fibre predominates and that is glass fibre. The bulk of all
glass fibres used for laminating are made from E-glass or electrical grade
glass. This is a high strength, low alkali content glass and is discussed in
more detail in Chapter 14.
Another fibre which is becoming increasingly important, particularly
where high strength or rigidity is required, is carbon fibre. The availability
of continuous strand carbon fibre filament has extended the areas in which
reinforced resin systems can be used and, although the price is much higher
than that of glass fibre, the considerably superior specific strength and
modulus of carbon fibre composites make them extremely attractive for
many applications. One important area is in the manufacture of high speed
reciprocating parts, where any weight reduction without loss of strength or
rigidity, enables a machine to be operated either faster or more efficiently at
the same speed.
Whilst various synthetic polymer fibres based on acrylics and polyesters
find application as surfacing tissues, the recently developed aramid fibres
are finding increasing application in the preparation of high strength/high
modulus composites, the aramid fibre acting as the sole reinforcing fibre.
Other fibres which find some application as reinforcing materials include
asbestos, cotton, sisal, rayon and wool.
When polyester resins were first used for the manufacture of glass reinforced
composites, the hand lay-up or bucket and brush technique was all that was
available. Gradually this situation has changed until today very many
different fabrication processes are in use. These various processes were
developed to improve laminate consistency, reduce labour content, reduce
mixing errors, increase production rate and for various other reasons. Each
of these processes has an important part to play in the further development
of the industry.
In recent years the trend has been away from the labour intensive hand
lay-up technique towards more automated techniques. This situation is
likely to continue in the future, particularly towards closed mould
processes, to combat the likelihood of increasingly stringent legislation
being introduced to control styrene levels in workshop atmospheres and
general contact with resin systems.
Whilst some may see this as the start of the decline of the FRP industry,
others will see it as just another development problem. Whichever way
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6 FRP TECHNOLOGY
REFERENCES
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Chapter 2
DESIGNING IN FRP
2.1 INTRODUCTION
Fibre reinforced plastics offer almost unlimited possibilities for shape, size
and colour and can be produced with a variety of surface finishes.
Sandwich construction can be used to produce rigid lightweight mouldings,
whilst if unidirectional carbon fibre is used as reinforcement, exceptional
strength to weight ratios can be achieved. However, before any object can
be made it has to be designed. With FRP, whilst considerable scope exists
for designers and architects, due consideration must be given to the
processing and cured properties of the material to be used. In this chapter
an attempt will be made to indicate some of the criteria which need to be
considered during the design of an FRP object. It will be assumed that
other materials such as wood, metal or concrete have been ruled out.
2.2 DESIGN
In the first instance the customer or designer will produce a rough sketch of
an idea for a component. This sketch will then slowly be developed into the
final design, with material parameters and design tolerances specified.
Factors which influence design are resin selection, reinforcement selec-
tion and moulding process. The choice of moulding process will be affected
by the number of mOUldings to be produced, production rate, moulding
complexity and size of moulding. Another factor which may need to be
considered is the means by which the finished moulding will be transported
to its final destination. In the case of very large objects this may mean that
several moulded parts have to be produced for assembly on site.
In many cases the final design will be a compromise between the
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Table 2.1 Typical properties of various fibre reinforced composites 00
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Carbon
content
Fibre type (% vol.)
Unidirectional carbon Type HTM-S or 1 60 1-6 930 1200 180 70
fibre/epoxy Type HTS-S or 2 60 1·5 1620 1720 131 100
Type A-S or 3 60 1·5 1440 1520 115 110
Hyfil T 130 60 1·5 1300 1600 132 80
Satin weave carbon
fibre/epoxy Toray T 300 65 530 940 63 62
DESIGNING IN FRP 9
requirements of the designer and the moulder. In this respect there should
be considerable liaison between designer and moulder to ensure that the
final moulding meets as many of the original design requirements as is
possible, taking into account production rate and moulding cost. Often all
requirements may be met with no difficulty. Typical composite properties
are shown in Table 2.1.
A useful booklet which describes moulding with GRP from planning
through to production has been produced by Bayer. 1 Useful data may also
be found in literature produced by other polyester resin suppliers and
conference reports. 2 Also, recently published, is an interesting article
describing the design and manufacture of the British Rail high speed train
cab. 3
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10 FRP TECHNOLOGY
5. Electrical properties:
Breakdown voltage, tracking resistance.
Surface and volume resistivity.
Dielectric constant, dissipation factor (tan 15).
6. Outdoor weathering:
UV exposure.
Will the moulding be subjected to tropical, marine, European or
arctic climate and for how long?
7. Clarity and colour:
Transparent, translucent or opaque.
Colour.
Surface finish.
Resistance to yellowing.
8. Which performance specifications have to be met:
Food contact-F.D.A. approval.
Marine-Lloyd's Register of Shipping.
-Det Norske Veritas.
Other approvals.
9. Performance testing and guarantees:
Who carries out testing and to which specifications and under which
conditions if a choice exists?
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DESIGNING IN FRP 11
Are there any undercuts? If there are, then a split mould will be needed.
Are the major surfaces flat, of single curvature or double curvature?
With large flat surfaces, must these be free from shrink marks? If so, then
a hot cured low profile resin system will be needed.
Are there any sharp edges or small radii to be accommodated? If so, then
a press moulding process may be needed.
Is sandwich construction required?
Are ribs or buoyancy panels to be included in the moulding?
Is precise fibre alignment required to obtain design strength in any
particular direction?
Is heat cure required to achieve maximum chemical or thermal
resistance? If the moulding is large, is there a suitable press or post
curing oven available or must a heated mould be used?
Once these questions and perhaps others have been answered it is
probable that the choice of manufacturing process will have been narrowed
down to just one or two processes, in which case design can then proceed.
Alternatively the production process may have been selected at an early
stage and design and material selection geared to this.
Whichever process and materials are selected for a particular moulding,
consideration must be given during mould design to demoulding and lay-
up. For ease of demoulding, components should be designed with an
adequate taper and without undercuts, unless a split mould is used. Mould
preparation, lay-up and demoulding is more complicated if a split mould is
used.
A summary of the various moulding processes available can be found in
Table 4.1.
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12 FRP TECHNOLOGY
2.2.5 Inserts
Inserts for the subsequent assembly of panels can be incorporated with
little difficulty, particularly with hand or spray lay-up techniques.
Generally the laminate will be increased in thickness around the insert to
hold it in place and to provide adequate stress distribution. Many different
threaded inserts are available with large perforated heads to ensure
adequate bonding and to prevent them from being pulled out during use
(see Fig. 6.2).
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DESIGNING IN FRP 13
~~~~~~-:::: Lam; na te
These may consist of structures open on one side only, such as tanks,
troughs and boats, all of which can be produced by conventional
techniques. Alternatively they may consist of structures open on two sides,
such as pipes. Here, filament winding or centrifugal casting can be used for
production. With filament winding, pipes of up to about 400 mm diameter
can be made on a solid mandrel; above this size a split or collapsible
mandrel should be used. The mandrel predetermines the inside diameter of
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14 FRP TECHNOLOGY
the pipe. With centrifugal casting the mould determines the external
diameter.
With filament winding, where greater chemical resistance is required
than can be obtained with the resin system alone, a liner may be applied to
the mandrel surface before winding commences. This liner may be a
thermoplastic such as PVC or a synthetic rubber, depending on end use.
Closed hollow structures can be made by filament winding on a water
soluble or low melting wax or alloy mandrel. In this case the mandrel can
only be used once and is removed after winding and cure is completed. Such
structures find application as pressure vessels for storage and particularly
as pressure vessels for rockets and other space activities. Such vessels are
frequently made with epoxide resin systems.
REFERENCES
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Chapter 3
MOULDS
3.1 INTRODUCTION
Process suitability
Press moulding
Number of Hand/spray
Mould material releases lay-up cold hot
15
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16 FRP TECHNOLOGY
These can be divided into two broad categories: those made as master
patterns for GRP mould production or those used directly for moulding.
An example of the latter type can be found in the filament winding of
cylinders and spheres where the mould is used once and then has to be
broken up to extract it from the moulding.
In general, it is unlikely that a solid block of plaster will be used as a
pattern; more probably a wooden frame will be prepared which will then be
covered with plaster. A typical plaster pattern is shown in Fig. 3.1. This
consists of a wooden frame suitably prepared with braces and stringers to
keep it rigid. It must be solid enough to support the weight of plaster to be
used and must not distort during preparation of the GRP mould. Wire
netting is fixed to the frame to act as support for the plaster. Next several
layers of plaster reinforced with hessian are applied, followed by a layer of
plaster roughly shaped to the final pattern. The pattern is finished with a
thin layer of plaster carefully applied to bring it to the correct dimensions
for the mould. This final layer must be accurately finished and well polished
to ensure a smooth surface. It is preferable to use a low expansion type of
plaster for this application. Once the pattern has been completed it should
be allowed to dry for at least 24 h before hardening at between 60 and 80°C
for an hour or two. After the plaster pattern has been hardened its
dimensions should be checked to ensure that no changes have taken place.
Any oversize areas can be very lightly rubbed down.
Since plaster moulds are porous the surface must be sealed with a
solution of shellac, cellulose acetate, nitrocellulose or polyvinyl alcohol
before waxing and polishing. More than one coat of sealer may be
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MOULDS 17
hessian
Iransnrsc ribs
Fig. 3.1. Construction of a plaster pattern. (Courtesy of Scott Bader Co. Ltd.)
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18 FRP TECHNOLOGY
These may be carved from solid blocks of wood or constructed from several
pieces stuck together. Plywood or block board can be used for flat surfaces.
Whichever procedure is adopted the quality of the mould affects the quality
of the moulding. The skills required for mould making are those needed in
coach building or cabinet making.
By the use of split moulds, undercuts and return angles can be
incorporated in mouldings. However, where split moulds or ones with
movable parts are to be used great care must be taken in their construction
and in the fixing of locating pins. By careful design, moulds can be
constructed in such a way that minor modifications can enable a series of
mouldings of different length to be produced, as might be required for G RP
cladding units.
After completion the mould surface must be rubbed down until it is
completely smooth and then sealed with an appropriate sealing compound
such as shellac, cellulose acetate, polyester or epoxide resin. This sealer
must be allowed to dry thoroughly before polishing with a silicone-free wax
polish. Several applications of wax are better than trying to apply one thick
coating. The final coat of wax must be polished to a high gloss finish.
In addition to acting as moulds for short production runs, wooden
moulds are also frequently used as patterns for the production of GRP
moulds.
These are made from glass reinforced polyester resin systems by hand or
spray lay-up techniques, on patterns which may be made from wood,
plaster or any other suitable material. One of the main reasons for the
prevalence of such moulds is that moulders have all the necessary materials
readily to hand.
In preparing a pattern for a GRP mould, due account should be taken of
the shrinkage of the resin system during cure. Once the pattern has been
completed, it must be sealed to make it non-porous and then polished to a
high gloss finish using a silicone-free wax polish. This should be applied in
several layers polishing each as it is applied. As many as six coats of polish
may be necessary. Next the pattern should be coated with a release film of
polyvinyl alcohol by cloth, sponge or spray, making sure that this film is
completely uniform with no imperfections and no dust, hairs or other
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MOULDS 19
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20 FRP TECHNOLOGY
Temporary
barrier 1'ilIt-- Laminate 1.It!I-- Laminate
with flange
support 1.~~~I4-1~-- Conti nuous
rovings
Gel coat
;,:.;.;.~_Pattern
Stage 1 Stage 2
Metal plate
Continuous
rovings Laminate
Gelcoat
Pattern
Stage 3
Fig. 3.2. Method of constructing a split mould. (Courtesy of Scott Bader Co. Ltd.)
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MOULDS 21
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22 FRP TECHNOLOGY
mould must be accurately made, allowing for resin shrinkage, so that the
mould cavity is of the correct size. An oversize mould will only waste
expensive materials each time a moulding is made.
For cold press moulding the back of the mould should be filled with a
material capable of withstanding continuous loading in a press. One such
material is concrete, although a filled resin system may also be used. Here,
after the final layer of glass reinforcement has been applied to the mould, a
further layer of resin is applied at a rate of about 400 g/m 2 , into which is
sprinkled a layer of broken stone chips. After the resin has been fully cured
the back of the mould is filled with the concrete or resin mix which bonds
around these stone chips. Both halves of the mould should be similarly
treated.
Where GRP moulds are used for cold press moulding the moulding
cannot be trimmed as part of the moulding cycle. To maintain pressure on
the resin and prevent it from being squeezed out leaving air bubbles in the
moulding, the mould should be constructed with a pinching area. During
Laminate
~_..,.-=---"I- Mould cavity
~\7-I=n=-~ Laminate
Stone chips
Concrete or
Resin
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MOULDS 23
final closure of the mould this allows air to escape but retains the resin. For
mouldings up to about 5 mm in thickness, the pinching area should be
sufficient to compress two layers of glass mat in a gap of 0·4-0·5 mrn. For
thicker mouldings the pinching area should accommodate three or four
mat thicknesses. In addition, it is useful to incorporate a drainage channel
into which surplus resin can drain. An example of such a design is shown in
Fig. 3.3.
When not in use, moulds should be stored flat to prevent distortion and
protected from dust and moisture. In use, continuous scrutiny is necessary
so that any imperfections which occur can be immediately rectified.
Sharp instruments must always be kept away from mould surfaces.
Properly treated, GRP moulds can give excellent service.
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24 FRP TECHNOLOGY
gel time will occur, their effect will be completely negated by the
considerably inferior properties of the 'cured' system which, if usable, will
have a much shorter service life. For example, halving or doubling the
proportion of curing agent will generally result in the formation of a
solvent soluble adduct rather than a fully cross-linked resin system. The
main group of curing agents which tolerate a reasonable variation in
proportion are the polyamides and then only certain ones. However, even
here variation causes marked differences in cured properties. In general,
cure time can be shortened by increasing cure temperature; the alternative
is to use a different hardener. In all cases the resin supplier's recom-
mendations should be followed at all times.
The casting technique can be divided into two categories, single-stage
casting and two-stage casting. These will be described separately although
many features are the same for both. In both cases a master pattern will be
required together with a box to surround it to act as a mould for the casting.
This mould box should allow sufficient space around the pattern to prevent
damage to the sides of the mould during use. Too large a box will only
waste resin.
The pattern can consist of a wooden, plaster, metal, plastic or epoxy
former made to the shape of the final production moulding. If a porous
pattern is used this must be sealed with an appropriate sealer, such as a
nitrocellulose lacquer or polyvinyl alcohol. As with other moulding
processes the use of a release agent is essential. The pattern and mould box
should be polished to a high gloss with a wax polish and then coated with a
film of polyvinyl alcohol. Alternatively a silicone grease or spray applied
silicone release agent can be used. However, if any modification to the
epoxy mould is at all likely, a non-silicone release agent is preferred, since
then no contamination of the epoxy surface will occur to prevent adhesion
of any further resin.
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MOULDS 25
Mould box
Cast resin
Release agent
Pattern
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26 FRP TECHNOLOOY
equipment is not available then the mix should be stirred slowly, with the
blade of the mixer well below the surface. Any entrained air may then be at
least partially removed by low to medium frequency vibration or by
pouring the mix through a fine mesh sieve. Just standing the mix is rarely
effective. An alternative procedure is to heat the epoxide resin and filler to
between 50 and 80°C before mixing. Once this blend has cooled to about
30°C the hardener can be added. Some stirring whilst the blend cools may
be necessary to prevent the filler from settling out into a solid mass.
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MOULDS 27
~~---------Vent tubes
~I~H+---Plasticine
---tW~-- Pattern
.~~~~~~~~~~
Mould box
Stage 1
_ - - - Vent tube
Stage 2
Fig. 3.5. Two-stage casting.
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28 FRP TECHNOLOGY
blasting. Any mix which has penetrated the air release tubes must be
removed. A coat of the facing resin mix is then painted onto the surface of
the core before it is relocated in the box over the pattern. Unless the core is
relocated in exactly the correct position there will be insufficient gap
between the core and the pattern to accommodate the facing resin.
The facing resin mix is prepared and poured carefully into the gap
between the mould box and the core down one of the tubes, ensuring that
all air is displaced and the gap between the core and the pattern is
completely filled with resin mix. The resin system should be allowed to cure
at least overnight before giving a gentle post cure. Once the casting has
cooled to ambient temperature it can be demoulded and mounted ready for
use.
An alternative procedure which may be used is to pour the facing resin
system into the mould box and then carefully lower the core into position,
ensuring that it is accurately located over the pattern.
Lightweight fillers such as vermiculite or phenolic micro-balloons can
be used as alternatives to sand for large castings where mould weight may
give rise to handling problems. These will, however, result in a decrease in
the compressive strength of the system, which may be unimportant.
Where matching moulds are required, the first half maybe constructed as
described above and used as the pattern for constructing the second half. In
this case either a pattern of the object to be moulded must be placed over
the first half or sheet wax must be used to construct a pattern on top of the
first half. The second mould can then be made in the same way as the first
half.
These are required for hot press, centrifugal, transfer and injection
moulding and pultrusion. They may also be used with other moulding
processes. The fabrication of steel moulds is a highly skilled operation best
left to experienced tool makers and so will only be considered briefly here.
Tool steel and Meehanite, flame hardened and hard chrome plated are
undoubtedly the best materials, although other metals such as zinc and
aluminium may also be used. In designing the mould, an adequate taper
must be incorporated to permit easy removal of the moulding.
The use of mould release agents is essential with all metal moulds,
silicones being the most popular. Either spray or bake-on types may be
used" and several mouldings may be obtained from one application.
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MOULDS 29
Fig. 3.6. Mould with cutting edge. Fig. 3.7. Mould with pinching edge.
(Courtesy of Synres International BV.)
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30 FRP TECHNOLOGY
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MOULDS 31
3.6.4 Pultrusion
With pultrusion, heated dies rather than moulds are used. These should be
made from hard chrome plated, hardened tool steel for preference. Two
types of die are used, those through which fibres impregnated with resin
from a resin bath are drawn and those which incorporate injection nozzles
to impregnate the fibres within the die. These need to be designed to suit the
particular equipment being used. As with matched metal moulds an
experienced die maker should be employed.
These are light in weight with high rigidity and provide a good quality
finish. They are not as hard wearing as steel moulds and can therefore be
more easily damaged. They are, however, easier to machine.
One example of a large aluminium alloy mould was that used for the
manufacture of HMS Brecon, a 60 m long mine sweeper.
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32 FRP TECHNOLOGY
A nickel shell backed by a resin core can give a life similar to that achieved
with steel but at reduced mould cost. Such moulds can be used for the resin
injection moulding process. 2
REFERENCES
SUPPLIERS
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Chapter 4
MOULDING PROCESSES
4.1 INTRODUCTION
33
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w
~
Table 4.1 Summary of moulding processes
Contael moulding
------
Process Hand lay-up Spray lay-up Vacuum bag/pressure bag
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Equipment needed Rollers and brushes Spray and chopper gun. Hand/spray lay-up, automatic tape
rollers laying machine, autoclave/vacuum
pump/compressor
Number of mouldings
to justify mould cost From one upwards From one upwards From one upwards
Production rate Low Low Low
Labour content High High High
Quality of moulding Dependent on opera- More dependent on Two smooth surfaces
tor, one smooth operator, one smooth
surface surface
Typical products Boats, building Boats, building Aircraft sections, various panels, general
panels, general panels, general
Resin injection/ Compression moulding
Foam reservoir resin transfer Vacuum
Process moulding moulding impregnation Cold press Hot press
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t'!'I
(/J
-inserts for fixing Generally no Generally no Generally no Yes Yes
-foam panels Yes Yes Yes Generally no No
Equipment needed Hand equipment Resin injection Vacuum pump Hydraulic press Hea ted press
pump
Number of mouldings
to justify mould From one upwards Generally 100- Generally 100 100-1000 1000 upwards
cost 1000
Production rate Moderate Moderate Low High High
Labour content Moderate to high Moderate Moderate Low Low
Quality of moulding Good, two smooth Good, two smooth Good, two smooth Good Excellent
surfaces surfaces surfaces A II surfaces smooth
Typical products Automotive, fur- Boats, various Radomes, aircraft Automotive, industrial,
niture, various nose cones, electrical
various VJ
'-"
V.J
0\
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Equipment needed Transfer moulding Injection moulding Filament winding Centrifugal moulding
press machine machine machine
Number of mouldings to
justify mould cost Over 1000 Over 1000 From one upwards 100 upwards
Production rate High Very high Moderate Moderate
Labour content Low Low Medium Low
Quality of moulding Good, all smooth Good, all smooth Good, inside smooth Good, both surfaces
faces faces smooth
Typical products Small-to-medium Small-to-medium Tanks, pipes and Pipes and tubes
sized components sized components tubes
Continuous sheet
Process moulding Pultrusion
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f}1
Number of mouldings to
justify mould cost Continuous output Continuous output
Production rate Up to 12 mlmin Up to I mlmin
Labour content Low Low
Quality of moulding Good Good
Typical products Roofing lights, etc. Variety of cross-sec-
tions, rods, tubes,
etc.
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-...J
38 FRP TECHNOLOGY
Contact moulding is the most commonly used method for the manufacture
of both small and large reinforced polyester products such as boat hulls,
vehicle bodies, GRP building panels and cladding, ducts and tanks and
many other mouldings where small production runs are required. A single
mould is used, with the laminate applied to the suitably released mould
surface. The result is a moulding with only one smooth surface, that in
contact with the mould. Moulding thickness is generally in the range
2-10 mm although there is no basic upper limit; indeed for large boat hulls
3~~~~~~~~~~~~~----Topcoat
--Chopped strand mat
_____ CSM or woven ravings
--;:0;;;;:;:;;;;;;;;;;;;:;:;:;:::;;;;;:;;;;::;;:;::;;;;:::::::: R1 f· 1
§4~~~?~~lttl""~~J\*~f4 e ease 1 m
~~~~~ ~~l
Fig. 4.1. Typical laminate construction.
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MOULDING PROCESSES 39
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40 FRP TECHNOLOGY
uniform over the whole mould surface. Gel time of the gelcoat in bulk
should preferably be about 15 min. Styrene fumes should be extracted from
the mould using a suitable extraction system to ensure even gelation of the
gelcoat.
The condition of the gelcoat can be determined by touching it. If it feels
tacky but is not easily removed by the finger, then it is ready for application
of the next coat of resin system.
In some cases a surfacing tissue may be used to reinforce the gelcoat. This
is applied immediately after the gelcoat while the resin is still wet and lightly
rolled to displace all air bubbles outwards. This procedure does, however,
result in a lower quality surface finish. Also, since the durability of the
moulding depends on the quality of the exposed surface, this procedure is
not recommended where the moulding is to be subjected to wet or chemical
environments. A surface tissue may, however, be applied with the first coat
of laminating resin where it is beneficial in protecting the reinforcement,
particularly when the moulding is used in wet or chemical environments. In
this way the resin-rich surface provided by the gelcoat is preserved.
Most moulding faults can be traced back to insufficient care during
application of the gelcoat. Insufficient film thickness can result in excessive
evaporation of styrene monomer from the gelcoat so that it dries instead of
cures. Too rapid an application of the second layer of gelcoat or the
laminating resin, before the first layer has cured, can result in a wrinkled
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MOULDING PROCESSES 41
finish. Too thick a gelcoat can, even several months after demoulding,
crack and craze and is also more sensitive to impact on the reverse side of
the moulding, when cracks and other damage may occur.
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42 FRP TECHNOLOGY
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MOULDING PROCESSES 43
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44 FRP TECHNOLOOY
Epoxide resins
With epoxide resin systems similar laminating procedures are used.
However, since volatile monomers are absent, cure of gelcoats in very thin
films will still take place, but relatively slowly. This does not mean that very
thin gelcoats are recommended. Whilst some gelcoats are available
commercially, these mostly have to be formulated by the moulder. Most of
the other comments given under polyester resins are equally applicable to
epoxide resin systems. However, gel times are generally longer and post
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MOULDING PROCESSES 45
Furane resins
Furane resins can be processed in a similar way to polyester resins.
Generally those reinforcements recommended for use with epoxide resins
are also suitable for use with furane resins.
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46 FRP TECHNOLOGY
Fig. 4.4. A typical spray gun and chopper unit in use. (Courtesy ofK & C Mouldings
(England) Ltd.)
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MOULDING PROCESSES 47
accelerated resins are thoroughly mixed and the glass completely wetted out.
Care should be taken to ensure that no air bubbles are trapped in this layer
and that the resin/glass mixture completely wets the gelcoat with no
bridging in the corners. This layer oflaminate should preferably be allowed
to gel before further application of resin or glass. Figure 4.4 shows a typical
spray gun, fitted with a chopper unit, in use.
Subsequent layers of resin/glass can be built up at about 2 mm per time,
rolling thoroughly as before between each application to disperse all air
inclusions. If thicker layers are applied between rolling, difficulty will be
experienced in removing all trapped air and an inferior laminate will result.
This procedure is continued until the required laminate thickness has been
achieved. A stronger laminate can be produced if alternate layers are
sprayed at 90° to each other.
As with hand lay-up, woven rovings can be incorporated into the
laminate to increase stiffness and to strengthen it. If these are to be used
sufficient resin system must be sprayed into the mould prior to applying the
woven rovings so that on rolling the resin system displaces the air outwards
as the resin is forced through the reinforcement. Resin sprayed on top of
poorly wetted rovings will result in air entrapment. The woven rovings
should be cut to size prior to laminating and should always be alternated
with sprayed laminate to give a strong composite structure. Without this
layer of sprayed laminate in between each layer of woven rovings, there is a
risk that the laminate will fail in shear when flexed in service.
The largest area practicable should be sprayed at anyone time prior to
rolling, to minimise overspray. Care should be taken to ensure that each
sprayed layer is thoroughly consolidated before the resin begins to gel.
Where very thick laminates are to be made, it may be desirable to build
the laminate up in several stages, allowing the resin to gel after each stage.
In this way excessive exotherm can be prevented and the laminate remains
controllable during application.
Reinforcing core materials, pre-formed ribs and 'Bighead' fasteners may
be built into the laminate during its construction. These are placed in wet
resin once most of the laminate thickness has been built up and further resin
and glass sprayed over to complete the moulding.
Spray rates can generally be varied between 2 and 10 kg oflaminate per
minute with most spray equipment.
With deep moulds styrene fumes should be removed from the mould
using an appropriate extraction system to ensure uniform cure of the
laminate.
As with hand lay-up, a surfacing tissue may be applied to the final layer
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48 FRP TECHNOLOGY
Epoxide resins
A similar spray technique can be employed with epoxide resins.
However, due to the different mixing ratios of resin to curing agent,
polyester spray equipment is generally unsuitable. The resin and curing
agent can either be pre-mixed and sprayed through a single-component
spray gun or used separately with a two-component gun fitted with
appropriate metering pumps to ensure that the correct resin/curing agent
ratio is maintained. This will generally vary from 4: 1 up to 5: 3. With some
resin systems heated two-component spray equipment may have to be
used. All other laminating procedures are the same as for polyester resins.
Furane resins
Equipment has recently become available for spray lay-up with furane
resin systems. Procedures are similar to those used with polyester resin
systems.
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MOULDING PROCESSES 49
Vacuum bag moulding can be used both with wet lay-up systems and
prepregs. It is suitable for limited production runs and for the manufacture
of complex components which cannot be made practically by compression
moulding. Both large and small components can be made and it is
frequently used for the production of aircraft parts. One advantage that
prepreg systems have over wet lay-up is that unidirectional prepregs can be
used and accurate fibre alignment achieved. This can be essential for
aerospace applications where strength to weight ratio is of prime impor-
tance.
Epoxide and polyester resin systems are equally suitable for processing
by vacuum bag moulding as are glass, carbon and synthetic fibre
reinforcements.
GRP lay-up
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50 FRP TECHNOLOGY
,. .....~__, ~~9~~
~
· ~"'-~··lil. I~.'I~"'I.:~·~·~<~·II~I·~~~~~B~I:ee~der
Clamp
cloth
~ Vacuum Ii ne
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MOULDING PROCESSES 51
This is similar to vacuum bag mOUlding. Both prepreg and wet lay-up
systems can be used, with pressure applied to the outside of an inflatable
bag placed over the laminate. The advantage of this technique over vacuum
bag moulding is that a higher pressure can be applied to the laminate.
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52 FRP TECHNOLOGY
Air pressure 1; ne
1 Pressure plate
1 Clamp
... To resin trap
- GRP lay-up
Mould
However, where pressure is applied to one side of the mould only, then a
very strong mould must be used. The alternative is to use an autoclave,
whereby heat and pressure can be applied simultaneously and to all sides of
the mould. Higher pressures can be achieved using an autoclave than are
possible with a pressure bag alone.
Lay-up is more or less identical to that used for vacuum bag moulding
except that the perforated release sheet is replaced by a solid release film
and bleeder fabric is unnecessary since excess resin is squeezed to the edge
of the mould (Fig. 4.7).
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MOULDING PROCESSES 53
clamps. Injection points, usually more than one, are situated at the lowest
part of the mould and vent points at the highest part to allow air to escape.
An overspill area is built into the mould to ensure that after trimming, a
good quality moulded edge is left. This is shown schematically in Fig. 4.8.
Accurate mould design is essential to ensure that mouldings of the
correct weight and dimensions are produced. Any excess moulding
thickness will only waste expensive materials. Since injection pressures of
up to 2 MPa are used the mould must be designed accordingly.
As with other moulding processes both mould halves are cleaned,
polished and coated with release agent. A gelcoat is then applied to both
halves and allowed to cure. Reinforcement, cut to shape, is placed in one
half of the mould and the mould closed. The reinforcement most often used
is continuous filament mat although chopped strand mat and woven
rovings, with a layer of continuous filament mat or chopped strand mat in
contact with the mould surface, may also be used. If chopped strand mat is
used it must have a styrene insoluble binder to prevent the fibres from being
washed away as the resin is injected. If desired, a surfacing tissue can be
used between the gelcoat and the reinforcement. The total weight of
reinforcement used is generally of the order of 30% by weight of the finished
mOUlding.
If ribs, stringers, frames or foam buoyancy panels are to be included in
the moulding these are placed in appropriate positions within the mould
before closure. They are usually wrapped with glass mat prior to insertion.
Resin is injected under pressure, starting with the lowest injection point,
making sure first that all vents are open. Injection pressure can be up to
2 MPa, with volume ranging from o· 5 to 10 kg/min, depending on mould
Mould
. """o---Continuous filament
mat
+ Injection point
Fig. 4.8. Resin injection.
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54 FRP TECHNOLOGY
size and equipment available. Either twin pot or catalyst injection systems
are available, both offering different advantages for different types of
operation.
Vent holes are closed once the resin starts to exude from them. Similarly
injection points are sealed once they are finished with, the final one being
sealed when the mould has been completely filled. The injection nozzle can
then be removed and the equipment used on another mould, thus making
full use of it.
The moulding is generally allowed to cure at room temperature,
although it may be transferred to an oven if required. Minimal trimming is
necessary after cure. Demoulding is the same as for contact moulding,
except that both halves of the mould have to be removed.
Resin systems should be designed for injection and should have low
viscosities to ensure adequate penetration through the reinforcement. A
high reactivity low exotherm system is preferred, with a pot-life long
enough to permit the mould to be completely filled before gelation of the
resin and preferably before any noticeable viscosity increase occurs. The
system used should also have low shrinkage on cure to prevent shrinkage
marks from marring the surface of the moulding. Care must be taken in
selecting the catalyst/accelerator system, taking into account moulding
thickness, to ensure that excessive exotherm does not occur. If this
happens, distortion of the moulding may occur and certainly mould life will
be shortened. Acetylacetone peroxide is often used as catalyst with a cobalt
octoate accelerator. Reactivity can be boosted by using dimethylaniline as
additional accelerator.
The advantages of the resin injection process over contact moulding are
summarised below.
Advantages
1. Two smooth moulded surfaces.
2. Constant shape and weight mOUldings.
3. Higher moulding quality than can be achieved with a one-part mould.
4. Ribs and other parts can be moulded in one operation.
5. Styrene emission is reduced since it is a closed mould process.
6. Cure is less susceptible to draughts and changes in workshop
temperature.
7. Lay-up is cleaner and less wasteful.
8. Labour costs are reduced.
9. Rapid mould tum-around can be obtained. Cycle times of 1· 5 h have
been claimed for small mouldings.
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MOULDING PROCESSES 55
Disadvantages
1. Accurately made matched moulds are needed and several may be
required to keep the injection equipment fully utilised.
2. Capital costs of equipment and moulds are higher.
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56 FRP TECHNOLOGY
the manufacture of nose cones, radomes and circuit breaker tubes from
heat cured epoxide resin systems.
An alternative process, used with polyester resins, is vacuum injection.
The only real difference is the way in which the resin is drawn into the
mould. Various processes are in use and are described below. These
processes can be used for the manufacture of a wide range of products,
including boats and train cabs.
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MOULDING PROCESSES 57
for the production of boat hulls as well as many other types of moulding.
Moulds are made from GRP, the lower half being of rigid construction
6-8 mm thick, whilst the upper half is more flexible and only 3-6 mm
thick. It is this flexible half which is the essence of the process. A vacuum
channel is built into the mould around the periphery for mould closure
(Fig. 4.9).
A resin with a viscosity of about 200 mPa s at 20 e is needed for this
0
process.
As with other moulding processes the mould surfaces are waxed,
polished and coated with PVA release agent. If a ge1coat is to be used, this is
applied to the mould surface and allowed to cure prior to filling the lower
Vacuum
Fig. 4.9. Construction a/two-part vacuum injection mould/or the Hoechst process.
(Courtesy 0/ Hoechst AG.)
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58 FRP TECHNOLOGY
half of the mould with reinforcement. The use of a gelcoat does, however,
increase production time.
The reinforcement is cut to shape and fitted into the lower half of the
mould. Gasket material is placed around the edge of the mould to form a
channel and the top half of the mould lowered into position. The
reinforcements used may be chopped strand mat with a styrene insoluble
binder, continuous strand mat or a combination of chopped strand mat
and woven rovings. Glass content of the finished moulding can range from
25 to 50% depending on the type of reinforcement used. Surface tissue may
be included if desired. As with other moulding processes, foam panels,
balsa wood and ribs can be moulded in.
Once the upper half of the mould is in position, vacuum is applied to the
gasket channel to close the mould and render it airtight. Catalysed resin is
next injected, either under pressure (0·05-0·2 MPa) or by gravity feed (1 m
head), until the calculated amount has been added. The resin feed is then
shut off. More than one injection point may be used on large moulds.
Finally the air remaining in the mould is sucked out, when the flexible top
half forces resin to flow through the reinforcement until the mat is
thoroughly impregnated and compacted. Vacuum is maintained until the
resin has cured. Demoulding and trimming is carried out in the normal
way.
Advantages
1. Relatively low capital cost (similar to resin injection).
2. Fast mould turn-round.
3. Low labour costs.
4. Two smooth moulded surfaces.
5. Suitable for large mouldings.
6. Undercuts are possible.
7. Reduced styrene emission through the use of a closed mould process.
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MOULDING PROCESSES 59
4.7.4 Monoforming 9 • 10
This system is offered by J. Coudenhove GmbH, for use with polyester
resin systems. Lightweight matched moulds are used with positive pressure
resin injection and vacuum to hold the mould halves together and aid in
consolidation of the laminate. The lower half of the mould is of rigid
construction, supported on a suitable framework. The upper half is
generally a sandwich of glass reinforced epoxy with a balsa wood core.
Mould costs are claimed to be about three times those of a mould used for
hand lay-up, but only one-fifth to one-half of the cost of moulds needed for
resin injection. Resin viscosity for use with the process should be of the
order of 200-400 mPa s.
t A patented process.
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60 FRP TECHNOLOGY
Mould
Fig. 4.10. A typical FRM composite.
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MOULDING PROCESSES 61
produced. Typical ranges for some properties are shown in Table 4.2. Full
details can be obtained from Shell Chemicals UK Ltd who license the
process.
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62 FRP TECHNOLOGY
This process is one of the most economical for the high volume production
of small-to-medium sized components from either polyester or epoxide
resin systems. Mouldings have two smooth surfaces and can be made to
relatively high tolerances. Due to high tooling costs, this process cannot
generally be justified for short runs.
Heated matched metal moulds are used, mounted in a hydraulic press
fitted with automatic opening and closing and accurate speed control.
Moulds are generally fabricated from tooling steel with flame hardened
edges to trim the moulding during the press cycle (see Fig. 3.6). Moulds
used with sheet moulding compounds often have ejectors fitted but these
are rare on moulds used with liquid resin systems. The mould surface
should be highly polished and may be chrome plated to ease removal of the
moulding. Such moulds generally have a life of about 100 000 releases. To
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MOULDING PROCESSES 63
prevent warping of the moulding the temperature difference over the whole
mould surface should not exceed 2· 5°C.
Mould design is of great importance for efficient production cycles and
must take into account the material to be used. Also an adequate taper
must be built into the mould to permit easy ejection of mouldings. This is
described in more detail in Chapter 3.
A high production rate can be achieved with cycle times ranging from 1
to 8 min. This is governed by moulding temperature and pressure, type of
resin/catalyst system used and moulding wall thickness. As a general guide
a press time of 2 min is used for a wall thickness of 2 mm or less, above this
it is general to allow 1 min per millimetre of wall thickness. Press
temperatures are usually in the range lOO-170°C, with temperatures of
I OO-130°C being more common with polyester resins. Pressures used vary
between O' 5 and 15 MPa depending on mould dimensions and the material
being processed.
Silicone release agents may be used to facilitate demoulding, although
generally, once a mould has been 'run-in', particularly with moulding
compounds where metallic soaps are used as internal release agents, further
application becomes unnecessary. If a moulding is to be subsequently
painted, great care must be taken in choosing a release agent that will not
interfere with adhesion of the paint. This is also true if adhesives are to be
used on the moulding.
Several methods exist for producing mouldings by the hot press
technique; these are: liquid resin/chopped strand mat; liquid resin/
preform; sheet moulding compounds or prepregs; dough moulding
compounds. Each of these will now be described in turn.
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64 FRP TECHNOLOGY
dimensions, the excess glass acts as a filter to allow air to escape whilst
retaining the resin. With correct mould design this excess is cut off during
the final closure of the mould. Mould closure is usually regulated by stops
to predetermine the moulding thickness and prevent too much resin from
being squeezed out. Since a liquid resin system is used, a relatively low
moulding pressure is all that is necessary (0·5-2·5 MPa).
To reduce moulding costs, increase the rigidity of the moulding and
reduce shrinkage and hence improve surface finish, fillers such as calcium
carbonate, china clay or talc may be added to the resin system.
For preference the resin system should be of high reactivity and medium-
to-high viscosity at 25°C, to prevent it from running through the
reinforcement and polymerising at the mould surface before the mould has
been closed. With polyester resin systems, benzoyl peroxide is frequently
used as catalyst without an accelerator. With this catalyst a large batch of
resin can be prepared at anyone time, since shelf-life at room temperature
is of the order of one week. Fibre content of the finished moulding is usually
within the range 25- 50%.
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MOULDING PROCESSES 65
preform is removed from the screen and is ready for use. To aid production
a large batch of preforms may be prepared first and stored ready for use.
An alternative method of making a preform is to prepare a slurry of
chopped fibres and emulsion binder and draw the screen through this until
the required thickness of fibres has been deposited. The screen is then
removed from the slurry, drained and the preform dried as before.
To prepare a moulding, the preform is placed in the suitably released
mould and the correct amount of catalysed resin poured over it. The mould
is then closed and excess resin squeezed out. The procedure used is then the
same as that for liquid resin/chopped strand mat moulding. Cure
temperature and cure time depend on moulding size and resin formulation.
With deep mouldings it is preferable to invert the mould to prevent the
fibres from being squeezed into the bottom of the mould as closure takes
place (Fig. 4.11). With correct mould design, trimming takes place in the
mould.
Fig. 4.11. An inverted mould for hot press moulding. (Courtesy of Synres
International BV.)
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66 FRP TECHNOLOGY
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MOULDING PROCESSES 67
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MOULDING PROCESSES 69
mould but today horizontal machines are mostly used. Since thermosetting
materials are liquid until gelation occurs, clamping pressure has to be
maintained on the mould until the resin has cured. Unless this is done,
excessive flash will form. Heated matched metal moulds are used, which
may be of multi-cavity design. These moulds must be designed for use with
thermosetting resins, taking into account the fact that thermoset mould-
ings are harder, more rigid and less easily deformed than thermoplastics.
A typical temperature sequence for injection moulding DMC would be:
feed hopper and feed zone-ambient temperature; metering section
50~60°C; nozzle 80~90°C; mould temperature 135~ 185°C for polyester
DMC or 160~220°C for epoxy DMC; injection pressure 80~160 MPa.
Cure time is generally of the order of I o~ 20 s per millimetre of wall
thickness. Very little finishing of mOUldings is necessary.
Where fully automatic moulding machines are used, hydraulic ejection
with perhaps a 'joggle' facility is necessary, since thermosets have a
tendency to stick in the mould.
A survey of injection moulding equipment for use both with thermo-
plastics and thermosets has been compiled recently.14
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70 FRP TECHNOLOGY
Fig. 4.12. Large diameter 'Fibajio 'filament wound GRP pipes moulded by Red/and
Pipes Ltd using Crystic polyester resin/rom Scott Bader. (Courtesy 0/ Scott Bader
Co. Ltd.)
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MOULDING PROCESSES 71
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72 FRP TECHNOLOGY
Hel i cal
Longitudinal
which has a woven glass cloth partially rolled into one side to improve
adhesion of the resin system (Celmar).
Dunlop has recently developed a new process for pipe production to
produce pipes in the range 200-2000 mm diameter. 16 Essentially the
process is similar to conventional filament winding. A mandrel, suitably
coated with release agent, is wrapped with an epoxide resin impregnated
glass tape. Over this is wound a 150 mm high-strength steel strip angled to
give 50% overlap. Epoxide resin system is applied to the steel strip to ensure
that each layer is fully encapsulated. From three to 13 layers of steel may be
applied to satisfy different pressure ratings. The pipe is finished by
wrapping with further resin impregnated glass tape and the resin system
cured. Pipe produced in this way has excellent corrosion resistance coupled
with a high strength/weight ratio. It is said to provide up to 50% weight
saving over conventional steel pipe.
Various processes are available for the 'on-site' construction of large
filament wound storage tanks. By manufacturing these on site, transport
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MOULDING PROCESSES 73
problems are overcome and integral structures can be produced. With the
various processes either horizontal or vertical mandrels are first con-
structed from preformed GRP sheets. These are then wrapped with resin
impregnated glass rovings. Further details of these processes can be found
in Chapter 8.
4.13.2 Prepregs
Filament wound vessels can be produced from prepreg tapes and rovings.
This technique is often used with carbon fibre to reduce fibre damage
during the winding operation and to permit the use of resin systems which
cannot be handled by wet lay-up techniques. Here, it is essential to use a
heated mandrel to melt the resin and hence displace air and consolidate and
cure the laminate. Resin content of the laminate can be controlled more
accurately with prepreg since the prepreg can be made with exactly the right
resin content. The use of prepregs also makes for cleaner operation.
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MOULDING PROCESSES 75
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76 FRP TECHNOLOGY
Mr-~n---GRP
the required shape once the preform has been placed in position. It is also
claimed that base plates can be simultaneously moulded on by this method.
These base plates are first preformed and then inserted into the mould
where they become firmly bonded into the pole. Typical applications
include poles for street lighting, flag poles and aerials.
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MOULDING PROCESSES 77
~Reinforcement
I
Resin Cutter
o
, 0 / \
o 00 Curing oven
----Cellulose film
000 I
'---------'
o
Fig. 4.16. Continuous sheet manufacture.
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78 FRP TECHNOLOGY
since gel time and viscosity must suit the particular operating conditions of
the machine. Resin systems used include those suitable for producing clear
fire retardant sheeting.
By the correct choice of resin system, sheeting can be manufactured
which will not yellow to any extent after exposure to tropical weather
conditions for several years. However, to ensure that this is the case the
resin system must be chosen with care and must be fully cured. Also the
release film must be removed before installation and the laminate should
contain not less than 75% by weight of resin. In other cases the resin content
of the laminate may fall between 65 and 75% by weight.
Decorative sheeting can be produced with an attractive printed pat-
terned surface by incorporating a suitably patterned surfacing sheet. This
surfacing sheet can consist of a glass surfacing tissue onto which the pattern
has been specially printed or alternatively a dress fabric may be used. In
both cases the colours used in the printing process must be compatible with
the resin and must not run. Many dress materials are suitable but, since
they often do not wet out as thoroughly as glass fibre, the material should
be ironed fiat first.
4.16 PULTRUSION
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MOULDING PROCFSSFS 79
Rei nforcement
n injection
Rei nforcement
Fig. 4.17. Pultrusion (aJ using a resin bath; (bJ by resin injection.
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80 FRP TECHNOLOOY
Expanded PVC
This is available in several different grades, both plasticised and
unplasticised. If the foam has a surface skin this should be roughened to
improve adhesion. Apart from this,qnplasticised PVC foam requires no
special treatment. With plasticised PVC foam, prolonged contact with
polyester resin may cause attack and so the foam may require sealing first.
Expanded polystyrene
This is severely attacked by the styrene present in polyester resins and
must be sealed before use. This can be done with a solvent-free epoxide
resin system, preferably reinforced with one layer of woven glass cloth. For
maximum bonding of a polyester to an epoxide resin system, the polyester
Laminate
11I1I1I1I1I1I1I1i1l1l1l1t~Topcoat
;~~;:;;:~g~;;;;;;.~;;;;;;;;.;::::=:
;
Core ma teri a1
Laminate
Surf acin9 tis sue
Gelcoat
Re 1ease film
Typical sandwich construction.
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MOULDING PROCESSES 81
should be applied soon after the epoxy has gelled. If this cannot be done
then the epoxy surface should be abraded before application of the
polyester resin. Most solvent-free epoxide resin systems cause little or no
attack on polystyrene foam, but it is always advisable to check the system
out on a small piece of foam first.
Phenolic foam
This is usually of open cell construction and hence will absorb a low
viscosity resin system into its pores. It is not attacked by either polyester or
epoxide resins but should be sealed with a thixotropic resin system before
use.
Polyurethane foam
This is available both as rigid and flexible foam. Generally the rigid foam
is used as core material, since the purpose of the core is to increase rigidity.
Pre-moulded slabs and blocks can be used, the only pre-treatment
necessary being the removal of dust from the surface, providing that a
closed cell foam is used. If an open cell foam is used this must be sealed with
a thixotropic resin system first. If the foam has a skin on the surface this
should be abraded before use.
Where blocks or slabs of foam are to be bonded to a pre-moulded
laminate, an epoxide resin adhesive should be used, preferably abrading the
laminate before application of the adhesive.
Urethane foams can also be foamed in situ, in which case no special
surface treatment of the laminate is necessary except to ensure that it is
clean, dry and grease-free.
Fabrication techniques
These include contact moulding, resin injection and compression
mOUlding. Depending on the process and the type of core material used
either liquid resin systems or prepregs may be used. Reinforcements used
include glass, carbon and aramid fibres and may be in the form of chopped
strands, woven fabrics or unidirectional fibres, depending on strength and
rigidity requirements.
Two processes have been developed to speed boat building without the
need for expensive moulds and patterns. Both processes use lightweight
wooden frames on which to construct the boat hull.
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82 FRP TECHNOLOGY
t A patented process.
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MOULDING PROCESSES 83
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84 FRP TECHNOLOGY
cutters should be used. Drilling should be started from the gelcoat side,
with a block of wood or similar material firmly clamped to the back of the
moulding.
For tapping and threading, high-speed nitrided and chrome plated taps
are suitable. Holes and blanks can be punched in a similar manner to that
used with sheet metal.
All surfaces exposed by machining or drilling should be sealed with a
suitable lacquer to prevent ingress of water or chemicals.
Most FRP products will be self-coloured and will not therefore require
painting. However, occasions may arise when this is necessary, for example
to repair scratches or other blemishes, or to add a pattern or lettering, or
with boats, to apply an anti-fouling paint. In all of these cases the moulding
must be thoroughly cleaned to remove all traces of release agent or polish.
PVA release agent can be washed off with warm water. Normal wax
release agents and polishes require washing off with white spirit or a similar
proprietary cleaner. If a silicone containing release agent has been used
then an abrasive cleaner will be required. Similarly, if the moulding has
been contaminated with oils or greases, then an abrasive cleaner may be
required. In each case the final rinse should be with clean, fresh water.
A good check for the presence of a release agent is to apply clean, fresh
water to the surface of the mOUlding. If the water breaks into small
globules, there is a release agent present. If the water remains in a fairly
uniform sheet, the surface will take a fresh coat of paint. In all cases
cleaning must be continued until the water no longer breaks into small
globules.
Once the surface is thoroughly dry it can be painted. The first coat should
be a suitably formulated primer. This may be epoxy or polyurethane based
and will be in either case a two-pack system. After this the undercoat and
topcoat can be applied, allowing the correct cure time between coats.
Various suppliers offer paints designed for use on FRP mOUldings. In all
cases the paint manufacturer's recommendations should be followed
completely to obtain a satisfactory finish.
REFERENCES
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MOULDING PROCESSES 85
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Chapter 5
5.1 INTRODUCTION
In this chapter, many of the faults found in GRP mouldings are described,
together with an indication of their possible causes and remedies. General
faults are described first, followed by those faults associated with specific
processes. Although the faults described in Section 5.2 are those found
with polyester resin based laminates, similar faults may occur with epoxide
resin based laminates, which are also covered in Section 5.10.
In this section, those faults applicable to both hand and spray applied
laminates are covered. Other faults associated specifically with spray
application are dealt with in Section 5.3.
86
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COMMON FAULTS FOUND IN GRP MOULDINGS 87
Fig. 5.1 Wrinkle finish on a GRP moulding. (Courtesy of Scott Bader Co. Ltd.)
6. Delay application of the laminating resin system until the gelcoat has
cured sufficiently.
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88 FRP TECHNOLOGY
Variations in gloss
This can show up as either patches of matt finish or an overall matt finish.
Causes are either premature removal of the laminate from the mould or
poor application of the wax release agent.
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COMMON FAULTS FOUND IN GRP MOULDINGS 89
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90 FRP TECHNOLOGY
Fig. 5.5. An internal dry patch. (Courtesy of Scott Bader Co. Ltd.)
2. Resin applied to dry mat rather than the mat being correctly laid into
wet resin.
3. More than one layer of mat applied before consolidation. Only one
layer should be applied at a time.
4. Resin system has too high a viscosity to adequately wet out the
mat-reduce the viscosity of the resin system by adding a small
amount of styrene.
5. Gel time is too short to permit adequate consolidation before
gelation. Reduce accelerator level, change catalyst, or add an
inhibitor to extend gel time.
Delamination
This can occur between two layers of reinforcement, particularly if two
layers of woven rovings are used without chopped strand mat between
them.
1. Insufficient resin system applied to the laminate-ensure even and
adequate resin application.
2. Poor wetting of the glass mat-use a lower viscosity resin system.
3. Contamination at the interface. This may occur where the first layer
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COMMON FAULTS FOUND IN GRP MOULDINGS 91
Spotting
Small spots appear all over the gelcoat surface. This can be due to poor
dispersion of pigments, fillers or thixotropic additive, or dust on the mould
surface.
1. Ensure that the mould surface is clean and well polished before
application of the gelcoat.
2. Check mixing efficiency.
3. Use a triple roll mill, high speed shear stirrer or equivalent method to
disperse pigments.
Colour variations
Colour variations can become apparent as bands or streaks of colour or
changes in colour intensity. There are several possible causes.
1. Pigment flotation due to poor pigment dispersion, or the use of a
mixture of pigments. Mix more thoroughly or change pigment paste
(see also spotting, above).
2. The use of excessive atomising pressure.
3. Spray gun too close to the mould surface.
4. Gelcoat applied too thickly on vertical surfaces, resulting in runs and
sags and hence uneven thickness. Increase the amount of thixotropic
additive used.
5. Uneven gelcoat thickness-apply more evenly.
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COMMON FAULTS FOUND IN°GRP MOULDINGS 93
Fig. 5.7. Fish eyes and craters. (Courtesy of British Industrial Plastics Ltd.)
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COMMON FAULTS FOUND IN GRP MOULDINGS 95
Sink marks
Sink marks can occur over ribs or inserts due to shrinkage of the resin
system during cure. They can be overcome by allowing the laminate to
partially cure before moulding in the ribs or inserts.
Chalking
Excessive chalking of the surface can occur during service life due to
several causes.
1. Insufficient cure of the gelcoat-check thickness and accelerator and
catalyst levels.
2. Use of an unsuitable filler or pigment.
3. Use of excessive filler or pigment.
4. Wrong choice of resin formulation for the service conditions
involved.
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96 FRP TECHNOLOGY
Yellowing
Yellowing of the gelcoat may occur on exposure to light. This can be
caused by any of the following:
1. The presence of moisture during laminating-ensure that all ma-
terials used are dry. Keep the working area dry.
2. Wrong choice of resin-use a UV stabilised resin.
3. Use of benzoyl peroxide/amine accelerator system-change to a
different catalyst system, i.e. one less prone to yellowing.
4. Insufficient cure of the laminate.
Tackiness
The surface of the laminate exposed to the air remains tacky due to
undercure of the exposed surface.
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COMMON FAULTS FOUND IN GRP MOULDINGS 97
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98 FRP TECHNOLOGY
Apart from those faults already described in Section 5.2, the following may
occur with spray lay-up.
Undercure
This can be caused by variable output from the spray gun due to
malfunctioning of the equipment, blocked or dirty hoses and blocked or
dirty nozzles.
I. Service the equipment regularly.
2. Check the hoses.
3. Check and clean the nozzles.
4. Check that correct levels of accelerator and catalyst have been used.
5. Check that the correct output is being delivered to the spray head.
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COMMON FAULTS FOUND IN GRP MOULDINGS 99
These show up as fibre pattern, speckling and flecking (Figs. 5.13- 5.15).
They may have several different causes.
1. Poor consolidation of the laminate (Fig. 5.16) through insufficient
rolling.
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Fig. 5.14. Speckling due to undissolved binder. (Courtesy of Scott Bader Co. Ltd.)
2. A resin system with too short a gel time was used-decrease the
accelerator level, change the catalyst or add an inhibitor to the system
to lengthen gel time.
3. The wrong type of chopped strand mat was used so that the binder
dissolved too slowly in the resin system.
4. The wrong resin system was selected. Choose a resin system with a
cured refractive index similar to that of E-glass.
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COMMON FAULTS FOUND IN GRP MOULDINGS 101
Fig. 5.16. A poorly consolidated laminate (left) compared with a correctly prepared
laminate (right) .
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102 FRP TECHNOLOGY
Surface blisters
1. The mould is locally too cool-ensure uniform heating.
2. Trapped air-ensure that the mould is correctly vented.
3. Damp moulding compound-store in a dry place.
Spotty surface
1. The mould is too hot-reduce mould temperature.
2. Pigment decomposition due to overheating-reduce cure tempera-
ture.
3. Contamination of the moulding compound.
Matt surface
1. The mould surface is insufficiently polished.
2. Excess release agent has been applied-mop up surplus.
3. The moulding compound was damp-store in a dry place or pre-heat.
4. The mould surface was too cold-increase temperature.
5. Moulding under cured-increase moulding time or cure temperature.
Moulding distorts
1. Mould temperature uneven-ensure uniform temperature over the
whole mould surface, with not more than 2·5°Cdifference on any part
of the mould.
2. Excessive exotherm-reduce cure temperature.
-change moulding compound.
-reduce moulding thickness.
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COMMON FAULTS FOUND IN GRP MOULDINGS 103
dissolves too readily in the resin system. Two alternatives exist, either to use
a mat with a less soluble binder or to use continuous filament mat.
Trapped air
1. Injection pressure too high-reduce pressure.
2. Too little resin injected-increase resin quantity.
3. Feed pipe is in the wrong position-place feed pipe at lowest point in
the mould.
4. Vent pipes in the wrong position-place vent pipes at the highest
point in the mould.
5. Resin leakage through poor seal-ensure that the mould seal is tight.
Insufficient impregnation
1. Resin viscosity is too high-use a lower viscosity resin system.
-increase resin temperature.
2. Flow path is too long or too narrow
-modify mould.
-modify equipment feed pipe.
-increase the number of feed points.
Insufficient impregnation
1. Mould not sealed properly-check mould seals.
2. Resin viscosity too high-use a lower viscosity resin system.
Trapped air
1. Insufficient evacuation-increase evacuating time.
-modify mould design to eliminate blind
holes.
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Bubble formation
1. Vacuum too high causing styrene to boil-reduce vacuum.
These comments apply equally well to polyester and epoxide resin systems
used for filament winding.
Insufficient impregnation
1. Resin viscosity too high-reduce viscosity or change system.
2. Unsuitable roving-change to a more suitable roving.
3. Impregnation time too short-reduce winding speed or enlarge resin
bath.
Trapped air
1. Poor impregnation-enlarge resin bath or reduce winding speed.
2. Resin system cures too fast-reduce accelerator level.
-use an alternative system.
Fuzz formation
1. Roving tension is too high-reduce tension.
2. Poor guiding of fibres-use a guide ring or comb.
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COMMON FAULTS FOUND IN GRP MOULDINGS 105
Wrinkling
1. Poor insertion of reinforcement-take more care in positioning mats
and cloths.
Dry spots
1. Too little resin-check resin/glass ratio.
2. Too Iowa rotation speed-increase.
Tacky surface
1. Air inhibition-finish with a correctly formulated topcoat.
-add paraffin or wax to the topcoat.
- increase cure temperature.
Pipe warps
1. Non-symmetric glass distribution-improve lay-up.
Pipe sags
1. Pipe withdrawn from the mould before the resin was fully cured.
2. Resin system too flexible-reduce the level of flexibiliser.
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Pinho ling
Pinho ling occurs when small air bubbles are trapped in the ge1coat before
gelation, or if the mould surface is coated with dust.
1. Ensure that the mould surface is dust free.
2. Use heated two-component spray equipment or heat the mould
surface prior to application of the ge1coat.
3. Wrong choice of release agent can lead to poor wetting by the ge1coat.
This should not happen if PVA is used as release agent.
4. A void mixing air into the resin system when stirring in the curing
agent.
Flaking
Poor mould release due to adhesion of the resin to the mould.
1. Ensure that the mould surface is thoroughly coated with release
agent.
2. Use a suitable release agent-PYA or silicone.
3. Poor consolidation of the laminate so that air bubbles are trapped
between the laminate and the ge1coat.
4. Contamination of the ge1coat before application of the laminate.
Tacky surface
With polyamide, aliphatic amine and some alicyclic amine curing agents,
used under cold or high humidity conditions, amine bloom may occur on
the surface. This is caused by reaction between the amine and carbon
dioxide and moisture in the air. Several possible solutions exist.
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COMMON FAULTS FOUND IN GRP MOULDINGS 107
1. Wait at least half an hour after mixing the resin system before using it,
to allow some pre-reaction to take place in the mixing pot. This can
only be done with long gel time systems.
2. Partially adduct the amine with either an epoxide resin or a reactive
diluent before use. This will give a curing agent with a different mixing
ratio and possibly different cured properties.
3. Change to a different resin/curing agent system.
4. If the laminate is tacky in patches, this is probably due to poor
mixing~ensure that the resin and curing agent are thoroughly mixed
before use. This may be more difficult than with a polyester resin
system, due to the higher viscosity of the epoxide resin system.
Blistering or bubbling
This is shown in Fig. 5.17. There are several possible causes.
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REFERENCE
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Chapter 6
6.1 INTRODUCTION
As applications for fibre reinforced plastics increase, so does the need for
reliable methods of joining them to each other and to other materials. Since
FRP composites are often markedly anisotropic, simple bonding tech-
niques are often inadequate.
With FRP composites, many of the elements which go to make up a
structure, such as beams and plates, can be moulded into one item, thus
reducing the number of joints needed. However, these sections may have to
be joined together in such a way that any applied load is safely transmitted
through the joint. Examples of such joints are to be found in pipelines and
chimney stacks, cladding panels for buildings and marine structures.
In general terms two broad methods of jointing FRP composites are
used. These are by means of an adhesive bond or by mechanical means
using bolts or screws. Load transfer is best achieved through adhesion
rather than through mechanical interlocking, thus often both methods will
be used on a single joint. These methods are discussed briefly in the
following sections. Further information may be found in conference
reports 1 , 2 and other publications. 3 • 4
With bonded joints some form of adhesive is used to bond two or more
items together. These items may be of similar FRP construction or may be
FRP bonded to some other material such as metal, wood or concrete.
In all cases consideration must be given to the design of the joint, with
special care being taken to ensure efficient load transfer through the joint.
109
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Bonded joints are most efficient when subjected to shear loads and least
efficient when subjected to peel loads, thus joints should be designed so tha t
they are only subjected to shear loads wherever possible. In practice pure
shear loads can rarely be achieved and peel forces have to be allowed for.
With peel forces, the highest stress loading is found at the edge of the joint
and is affected by the design of the joint, the relative rigidity of the
adherends and the properties of the adhesive.
Work has been carried out on the efficiency of various joints used in G RP
boat hulls by Smith and Pattison. 2 They have shown that with a simple lap
joint, efficiency is only 30% but this can be increased to 60% with a butt
strap joint, 70% with a scarf joint and 90% with a stepped joint. Thus,
wherever possible, a scarf or stepped joint should be used rather than a
simple lap joint. The efficiency of double-lapped composite joints in
bending has also been investigated. 5 Configurations of various joints are
illustrated in Fig. 6.1.
Double lap
Tapered lap
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BONDING AND JOINTING REINFORCED PLASTICS III
GRP
Wherever possible bonding to GRP should be carried out while the
laminating resin is still in the 'green' stage. At this time the surface may just
require wiping with an acetone soaked rag, although some abrasion of the
surface may be desirable. Once the laminate is fully cured the following
procedure should be adopted.
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Stainless steel
1. Degrease.
2. Abrade-by sand/grit/shot blasting or etch with an oxalic acid/
sulphuric acid mixture.
Thermoplastics
1. Degrease.
2. Most thermoplastics only require abrading followed by a wipe with
methanol or acetone.
Polyolefines require oxidising by flame or chromic acid.
Polyester films (polyethylene terephthalate) require etching with hot
concentrated caustic soda.
Fluorocarbon polymers require etching with a solution of sodium in
liquid ammonia or sodium in naphtha.
Wood
1. Abrade.
2. Dry the surface.
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BONDING AND JOINTING REINFORCED PLASTICS 113
CFRP
1. Degrease.
2. Abrade.
Note In all cases, dust and other contaminants must be removed from the
surface prior to application of the adhesive. A solvent wipe can be
beneficial in removing dust.
Degreasing may be carried out with proprietary degreasing solvents
or by detergent wash.
All substrates should be thoroughly rinsed with distilled water and
dried after etching unless otherwise specified.
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114 FRP TECHNOLOGY
can be used. 8 • 9 Such connections are unsuitable where high loads are likely
to be exerted around the bolts. In these situations the large washer headed
fixings are invaluable.
Where rivets are used, these may have to have a washer placed between
the rivet head and the laminate to reduce local damage caused by digging-in
of the head.
Care needs to be taken in the design of bolted joints to ensure adequate
stress distribution around the bolt heads. Some work has been carried out
on this subject with particular emphasis in recent years on the bolting and
riveting of carbon fibre composites for aircraft structures. 1 Further work is
necessary, particularly to correlate data in such a way that they are of use to
designers.
With pipe joints, some success has been met by using well tried concrete
and steel pipe jointing techniques. These may be of the butt/strap type,
socket and spigot type with sealing rings, or flange type. Which type of joint
will best serve a particular application must depend on installation and
operational factors. Design guidelines on jointing are given in BS 4994 but
since this was compiled (1973) various improvements in joint design have
been made. Further improvements are likely to come as pipe manufac-
turers and end users gain more experience in the handling and installation
of FRP pipes.
REFERENCES
[email protected]
Chapter 7
7.1 INTRODUCTION
Fibre reinforced thermosets, although strong and hard wearing, can
become damaged during use. This is particularly true of GRP boats. In
many cases such damage can be adequately repaired, providing that the
correct procedures are followed. However, regular maintenance of GRP
structures can prevent some of this damage from occurring. A useful
booklet on maintenance and repair has been published by International
Paint, Yacht Division. 1
7.2 MAINTENANCE
In the main, regular maintenance of FRP structures is unnecessary; indeed
it is for this reason that FRP composites find such wide application as
building panels, for marine applications and in chemical plant. However,
with GRP boats, regular maintenance can preserve the gelcoat and prolong
the life of the boat. Similar comments apply to GRP vehicle bodies and
other components likely to be subjected to continuous wear and tear.
Generally all that is required is to wash the boat once a year with warm
water containing a mild detergent. Oil stains and old polish can be removed
with proprietary cleaners formulated for such applications. Paint strippers
should never be used since these will damage the gelcoat. When the surface
is clean and dry, the application of a suitable wax polish will ensure that the
high gloss finish of the gelcoat is maintained. With vehicles these
procedures may have to be adopted at more frequent intervals.
Whilst maintenance is being carried out the surface should be thoroughly
inspected for scratches, abrasions and any other damage. Such damage can
usually be repaired.
115
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116 FRP TECHNOLOGY
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MAINTENANCE AND REPAIR OF FRP STRUCTURES 117
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118 FRP TECHNOLOGY
Stage 1
of CSM
Stage 2
lr-------- Chopped strand mat
Stage 3
~~liliil~O=II~i=:
.; New ge 1coat
Ce 11 ophane
7.3.3 Holes
This repair technique can be used where the laminate has been severely
damaged and access can be obtained to both sides. If not, then the
procedure described in Section 7.3.4 should be used.
A hole should be cut around the damaged area making sure that all
damaged laminate is removed. The edges of the hole should be filed down
to a wedge shape, preferably working from both sides, to give the shape
shown in Fig. 7.2. The back of the laminate should be sanded down at least
75 mm all round the hole and all dust and loose particles removed.
For large holes a temporary mould should be built around the hole on
the gelcoat side, contoured to the shape of the original moulding. For small
holes a sheet of metal or hardboard will suffice. This temporary mould may
be fixed to the laminate with bolts, using large washers where contact with
the laminate occurs. The bolts should be close to, but clear of, the repair
area. Before fixing in position, the temporary mould should be polished to a
high gloss finish with several coats of silicone-free wax polish and finally
coated with PVA release agent.
A layer of suitably pigmented gelcoat should be brush applied to the
temporary mould surface from the back of the laminate, taking care to
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MAINTENANCE AND REPAIR OF FRP STRUCTURES 119
Laminate repai r
Fig. 7.2. Hole repair where access can be obtained to both sides of the damaged
laminate.
work it well into the cut edges of the laminate at the mould surface. Once
this has cured a second layer of gelcoat should be similarly applied and
allowed to cure.
Meanwhile, pieces of chopped strand mat should be tailored to fit the
hole, preferably using the same weight as in the original laminate, if known.
When the gelcoat is touch dry, a coat of laminating resin system should be
applied, into which is placed the first layer of mat. Resin should be worked
through the mat using a brush with a stippling action to ensure that all air
bubbles are worked out, particularly at the cut edges of the old laminate.
This procedure should be repeated until the hole has been filled flush with
the existing surface. The resin system should then be allowed to cure before
proceeding further.
Once the resin has cured the temporary mould can be removed and the
bolt holes plugged with a filled resin system. Now the back of the laminate
should be covered with four to six layers of chopped strand mat in exactly
the same way as for small impact fractures. This laminate should preferably
just cover the previously filled bolt holes as well.
Any low spots or blemishes on the gelcoat side can be filled with
pigmented gelcoat and finally sanded smooth and polished. The final finish
is unlikely to be as good as the original moulded finish and the repaired area
will most likely always be just visible.
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120 FRP TECHNOLOGY
the edge filed to a wedge shape. For preference the hole should not be
circular. The back of the laminate around the edge of the hole must then be
abraded with coarse sandpaper and all loose dust particles removed. Next a
piece of strong cardboard or thin plywood should be cut somewhat larger
than the hole but of such a size that it can be manoeuvred through the hole;
hence the reason for not cutting a circular hole. Two pieces of wire are
pushed through the board or wood, positioned so that it can be pulled
firmly against the back of the laminate.
Two pieces of chopped strand mat, fully impregnated with resin system
and cut to about the same size as the wood or cardboard plug are placed on
the plug and the whole assembly tightened against the back of the laminate
by twisting the protruding wires around a rod on the front of the laminate
(Fig. 7.3, stage 1). The resin system is then allowed to cure overnight.
The next morning the wires are cut off as close to the new laminate as
possible. The repair is then completed as for small impact fractures; see
Section 7.3.2.
Stage 1
Temporary support
Stage 3 Cellophane
i~~~i~llieliiiirRepair gelcoat
Fig. 7.3. Repair to hole where access to back of laminate is impossible.
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MAINTENANCE AND REPAIR OF FRP STRUCTURES 121
REFERENCE
[email protected]
Chapter 8
8.1 INTRODUCTION
Apart from the wide and varied use of fibre reinforced resin systems under
factory conditions, where the working environment can be controlled,
these materials are also used under site conditions. Here, frequently the
resin systems have to be applied under prevailing conditions, which may
range from hot dry deserts through to freezing northern latitudes.
Clearly, with such a range of working conditions great care has to be
exercised in choosing the resin system to be used. Under many circum-
stances epoxide resin systems come to the fore in spite of their generally
higher cost. For example, where ambient temperatures reach 40-50°C
under desert conditions the lack of volatile constituents, such as styrene, in
epoxy systems means that they can be handled without undue risk to
operators and without any fear of under cure through styrene loss. In
addition, the shelf-life of epoxide resins and curing agents is not shortened
by storage under such conditions. Indeed it is known that one such system
was stored for three years in an open compound in the Sahara Desert
before use. When examined and used after that time the system showed no
detrimental effect. This does not mean, however, that resin suppliers either
recommend or condone such action.
At the other extreme, where temperatures approach O°C and where
substrates are damp, epoxy systems, if correctly chosen, frequently offer
better adhesion than polyester systems, whilst if a polyester system is used
it will almost certainly be with an amine accelerator and benzoyl peroxide
as catalyst. In general, resin systems are not recommended for use below
DoC unless some form of heat cure can be provided and unless the substrate
is completely free from ice.
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SITE APPLICATION OF LAMINATES 123
Between these climatic extremes both epoxy and polyester systems find
wide application.
One area where epoxide resin systems are frequently used is in the lining
and repair of steel storage tanks, in particular those used for the storage of
crude or refined oil products. The application techniques used can equally
well be applied to a variety of other steel structures and are described
below. In certain areas of the world, notably the United States of America,
polyester resins and latterly vinyl ester resins have been used successfully
for oil tank repairs instead of epoxide resin systems. The basic application
principles are the same and will not be described separately.
Another major area where laminate linings and repairs are used is on
concrete structures. Concrete frequently develops shrinkage cracks and
through settlement of structures major cracks can develop. These permit
either entry or loss of liquids including water and effluent. In addition,
concrete is liable to chemical attack, particularly under acid conditions.
Laminates are frequently used to overcome such problems. The choice of
resin system must depend on circumstances such as application conditions,
temperature~ both applicational and operational ~and chemical environ-
ment. Polyester, vinyl ester and epoxide resin systems are all used for such
applications. A typical example of a concrete structure frequently in need
of repair is a swimming pool. Here a laminate, when properly applied, is
eminently successful.
A third area where site applied laminates are used is in the jointing
and repair of pipelines. These may be GRP, steel or concrete. The general
procedure is to plug the leak and bandage the pipe with a resin impregnated
woven tape. This can serve as a permanent joint or a temporary or
permanent repair.
Apart from lining and repair applications, several companies have
developed processes for the construction of GRP tanks on site. These are
mostly constructed from preformed sections assembled on site and then
wrapped with resin impregnated continuous glass rovings. By this means
very large tanks can be assembled without the problems of transporting
them to site after factory construction.
There are no doubt many other applications where laminates have been
successfully used. Two which come to mind are the DJ.Y. car and boat
repairs. Here kits are available, complete with full instructions on how to
carry out the repair. In all cases a successful repair depends on adequate
surface preparation, correct choice of material for the repair and com-
petent application.
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124 FRP TECHNOLOGY
In the main, resin glass laminates are used either to completely line steel
tanks to provide corrosion protection or to provide a leak tight repair to
corroded tanks. In the first case the laminate will cover the walls and floor,
in the second it may only be required over the floor and about O· 5 m up the
walls. With old riveted tanks the problem is frequently leakage through
rivets which have worked loose over the years. Here a seam repair may be
quite adequate.
To illustrate the procedures necessary to carry out a tank repair let us
consider a large crude oil storage tank of approximately 100 m diameter,
with a floor area of 7854 m 2 (84 540 ftl), located in a desert in the Middle
East, which is leaking through corrosion around some of the seams and
overall pitting of the floor. A typical tank is shown in Fig. 8.1.
Such a tank will be offully welded construction with overlap welds and a
floating roof, supported on numerous legs when the tank is empty. Access
will typically be through two manholes and a sludge port, although it may
be possible to cut a large hole through the side of the tank if this is strictly
necessary. Headroom around the sides of the tank is likely to be about 2 m
reducing to about 1·5 m towards the centre of the tank. Numerous
projections will be found protruding from the roof on the underside,
particularly around the side of the tank. During the summer months the
working temperature inside the tank will reach 40- 50°C or higher,
dropping at night below dew point so that condensation occurs on all
Fig. 8.1. A typical large capacity floating roof crude oil storage tank.
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SITE APPLICATION OF LAMINATES 125
surfaces. This condensation may run down the sides of the tank and carry a
thin film of oil onto the working surface. Due to the prevailing temperature
conditions an epoxide resin system will almost certainly be selected for the
repair.
The following is a typical repair procedure but does not comprise a
working specification.
f
Holes greater than 1 cm in diameter should be covered with a grit-blasted
and primed steel plate, which may be stuck in position with the laminating
. Resi" "hesive Steel plate
I Re""-;tY~~I..",,,~~ l I l
Fig. 8.2. Holes in tank floor filled with resin putty or covered with new steel plate.
f ~eSin putty
I
Fig. 8.3. Overlap weld.
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126 FRP TECHNOLOGY
t
I
6 - 10 em
filled resin fillet
I
.j.
: '
:..G - 10 em .. :
I '
resin system (Fig. 8.2). Smaller holes and pitted areas should be filled with a
resin based putty to give a smooth surface on which to apply the laminate
(Fig. 8.2). Likewise overlap welds (Fig. 8.3) and the curb angle between
floor and shell plates (Fig. 8.4) should be filled, the latter using a sand filled
resin mix. Badly pitted or corroded areas should then be covered with a
laminate so that they receive a double thickness laminate by the time the
tank has been completed.
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SITE APPLICATION OF LAMINATES 127
Surfacing tissue
The mat is then rolled with a laminating roller to ensure thorough wetting of
the glass. Further resin is applied followed by the second layer of mat. Next
the surfacing tissue is applied and the whole laminate rolled to ensure
thorough wetting of the reinforcement and to displace all air bubbles. The
procedures used are similar to those used for hand lay-up contact
moulding. The finished laminate should contain between 70 and 75% by
weight resin, 25~ 30% glass.
Although a surfacing tissue is not essential it does help to ensure that
there are no pinholes in the laminate, particularly since most binders used
on chopped strand mats are insoluble in epoxide resin systems and so the
mat retains its original structure in the laminate. It also covers all the fibres
in the mat and prevents them from sticking up and gives a resin-rich
chemically resistant finish which is easy to clean.
Where roof leg supports are encountered the usual procedure is to jack
them up, apply the laminate to the tank floor and then while the resin
system is still wet, a 12 mm thick, 450 mm square steel plate is placed on top
of the laminate under the leg. The leg is then lowered and the resin system
allowed to cure. The weight of the leg forces the plate into the laminate and
this helps to bond it in position. The purpose of the steel plate is to prevent
the leg from cutting through the laminate each time the tank is emptied
(Fig. 8.6).
Once the laminate has cured it should be checked for pinholes using a
high voltage holiday detector (set at 1O~ 12 kV). Any pinholes found can be
covered with another layer of laminate. Before this is applied the cured
laminate should be sanded down and coated with resin. A layer of chopped
strand mat and surfacing tissue can then be applied in the normal way.
If required, the whole laminate can be coated with a topcoat once all
defects have been rectified. This may consist of a further coat of the
laminating resin system or alternatively a coat of a fully pigmented epoxide
resin based paint. Where the tank is to be used for storage of refined
petroleum products, this topcoat must pass the normal requirements for
gum leaching, etc.
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128 FRP TECHNOLOGY
One point worth noting is that since operators have to walk across the
cured primer and laminate at various stages during the operation, con-
tamination of the surface by oily residues can occur. These residues can be
removed by wiping the surface to be overcoated, with clean rags soaked in a
suitable degreasing solvent, e.g. xylene.
With riveted tanks, in addition to the above procedures, it is necessary to
fill around the rivet heads to ensure a smooth surface is available for
laminating (Fig. 8.7).
putty
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SITE APPLICATION OF LAMINATES 129
widely encountered procedure for tank repairs, spray lay-up is also used.
Here, a resin spray gun fitted with a chopper attachment is used, the
procedure adopted being very similar to that used for factory operations.
The resin and glass are sprayed onto the steel substrate and thoroughly
rolled to ensure complete wetting of the glass and to dispel all trapped air
bubbles. A minimum of two passes with the spray gun is necessary to give
adequate pinhole-free coverage. The resin system may be different from
that used for hand lay-up but choice will still be governed by application
conditions.
With spray application, the quality and particularly the thickness of the
finished laminate is very much more dependent on operator skill than
where chopped strand mat is used. With a final laminate thickness of
between 2 and 3 mm, it is clear that only 1 mm under or over thickness on
an area of 7854 m 2 can result in a very substantial difference in material
consumption. In addition, very careful selection of spray equipment is
necessary to ensure that any cross-winds blowing through the tank do not
deposit the glass in a different position from the resin. This has been known
to occur, resulting in a poor quality, variable thickness laminate. With
modern equipment this should not be a problem.
A further modification is the incorporation of glass flakes into the resin
system. This is claimed to increase the chemical resistance of the resin by
providing a glass-rich surface.
Polyester and epoxide resin systems are equally effective for the lining and
repair of concrete structures. The main criteria for deciding which to use
are: service conditions; application temperature; environmental con-
ditions; and material cost (only applicable if either material is suitable).
Concrete, unlike steel, is prone to cracking. These cracks may be small
surface cracks, static settlement cracks or moving cracks, i.e. ones which
open and close as the load on the structure fluctuates or ones which
open and close with temperature changes. There are also invariably
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130 FRP TECHNOLOGY
expansion joints built into the structure. Surface cracks and static cracks
can invariably be filled and a laminate applied over them. Moving cracks
and expansion joints, however, present a much more difficult proposition
and the use of a rigid laminate may be impractical. Since the sealing of such
cracks can vary widely from one location to the next, the advice of an
experienced contractor should be sought-indeed the solution may lie
elsewhere than with a laminate. Figure 8.8 shows the effect of bridging a
joint between a concrete bottom in a steel tank and the steel manhole.
Temperature fluctuations and movement of the tank wall on filling and
emptying the tank resulted in a split in the laminate. This allowed fuel to
seep into the concrete and subsequently leak from the tank.
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SITE APPLICATION OF LAMINATES 131
(Fig. 8.9). The resin grout is then pumped in under pressure, taking care
that the pressure used is not high enough to cause further damage to the
structure. Once the grout has cured the protruding injection tubes can be
broken off and the whole area made good with a resin putty.
The alternative to grouting is just to chase out the cracks and fill with a
resin putty (Fig. 8.10). This, however, will leave the crack open to the
environment on one side and may give rise to problems at a later date.
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132 FRP TECHNOLOGY
resin
Concrete
Fig. 8.10. Crack in concrete chased out and filled with a resin based putty.
used for surface preparation then the paint must be removed first. In this
case the paint can probably be removed with a wax-free paint stripper.
Concrete less than 28 days old will not have developed 'full' strength,
thus preparation of the surface by any means is likely to cause considerable
damage. Additionally, the curing reaction of the concrete will still be taking
place and since this involves water, application of a laminate will either seal
in the excess water present or deprive the concrete of water if forced drying
techniques have been used. The surface may also be highly alkaline, which
may inhibit cure of the resin system at the interface between the resin and
the concrete. The end result may well be an inferior laminate with poor
adhesion to the concrete. Whilst these remarks are generally true, there
may be circumstances where the concrete can be treated after a shorter cure
period. Here, the advice of an experienced resin contractor is essential.
Where it is known that a laminate is to be applied to a concrete surface at
the design stage, a wood float finish should be specified. This will give a
fairly smooth surface without too deep a layer oflaitance. It should also be
impressed on the contractor that the same care should be taken in finishing
the concrete as would be the case if no laminate was to be applied. Blow
holes and poor compaction of the concrete, particularly on vertical
surfaces, can result in an expensive filling operation before a laminate can
be applied.
Laitance is the fine layer of cement which comes to the surface when
concrete is placed. It has poor cohesive strength and is very weakly bonded
to the body of the concrete.
The concrete surface should be grit-blasted to remove alliaitance and
other loose material, preferably until the aggregate has been exposed. A
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SITE APPLICATION OF LAMINATES 133
light flash blast is rarely sufficient and the degree of blasting may well be
equivalent to that needed for a steel substrate. Alternative techniques,
generally only applicable to horizontal surfaces, include scabbling, scarify-
ing or grinding with a mechanical grinder. Once the surface has been
adequately prepared, all loose material should be removed and the surface
finally cleaned with a vacuum cleaner. If wet scabbling or grinding has been
carried out the surface may be covered with hard packed dust. This must be
removed before any resin is applied.
If the prepared concrete surface is badly pitted it may be necessary to
apply a filled resin system to give a smooth surface on which to apply the
laminate. Where a graded sand filler is available a filler to binder ratio of up
to about 10: 1 may be used, although a finer filler may sometimes be
preferable.
Grit-blasting or other mechanical means of surface preparation ge-
nerates a large volume of grit and dust, which if carried out in a factory,
may result in damage to equipment, particularly if it settles on moving
parts. An alternative procedure is to use acid etching. Here a 10-15%
solution of hydrochloric acid is applied to the concrete at a rate of about O· 5
litre/m 2 using a stiff brush to work the acid into the surface. (Commercial
muriatic acid~concentrated hydrochloric acid~is a 30% solution.) This
should cause bubbling of the surface. If this does not occur then it is
probable that the concrete has been hardened with a silicate treatment or
modified in some other way, in which case mechanical surface preparation
will have to be used. The normal safety precautions applicable to the
handling of acids must be observed while acid etching is carried out. Also
all metal machine parts should be carefully covered with a layer of grease or
strippable coating to protect them from the possible corrosive effects of
hydrochloric acid fumes.
Once bubbling has ceased the surface should be washed thoroughly with
water. If any acid remains this can be neutralised with a dilute solution of
ammonia, followed by washing with water. The concrete must then be
allowed to dry to ensure adequate adhesion of the resin system.
If cracked reinforced concrete is to be etched, it is preferable to flush the
surface with water first to fill the cracks with water to minimise penetration
of the acid. In this case neutralising with dilute ammonia solution after
etching is desirable.
Once the concrete surface has been adequately prepared and is dry, it
should be coated with a primer by brush, roller or spray. This should seal
the surface in readiness for application of the laminate.
With a polyester primer the addition of up to 25% by weight of styrene is
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134 FRP TECHNOLOGY
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SITE APPLICATION OF LAMINATES 135
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136 FRP TECHNOLOGY
gelcoat plus one coat of topcoat, in the case of a polyester laminate, or two
coats of an epoxy paint, in the case of an epoxy laminate.
Care should be taken in finishing off the laminate at the edges. These
should preferably be butted up to a strip of wood or trimmed and feathered
down before applying the topcoats. The resin system should be allowed to
fully cure before being put into service.
Where pipeline repairs are contemplated the factors which need to be taken
into account include the following: accessibility; pipeline operating
temperature and pressure; application conditions; pipeline contents. There
may also be local factors which have a bearing on the choice of material for
the repair.
Whichever type of pipeline is to be repaired, whether it is steel, concrete,
GRP or thermoplastic, the first thing to consider is the choice of resin
system to be used. In principle, epoxide, polyester and vinyl ester resin
systems can all be used. In practice choice will depend on circumstances.
Repairs to G RP pipes are also discussed in Chapter 7.
The second factor to be considered is surface preparation. The best
preparation technique for steel or concrete is grit blasting. However, this is
frequently impractical and so alternatives have to be used. In all cases rust,
paint, tape wrapping, oil, grease and other contaminants must be removed.
The substrate should then be roughened by hand wire brushing, mechani-
cal sanding or hand sanding with an abrasive paper or cloth. Mechanical
wire brushing usually causes polishing rather than roughening and is
therefore usually unsuitable.
If the hole or crack is of a reasonably large size it should be plugged by
some appropriate means. This may be by filling with a fast setting resin
putty, by hammering in lead strips or covering with a sheet of steel or some
other material. Next a coat of resin system is applied by brush or roller and
a woven tape wrapped around the pipe. Resin system and tape are then
applied alternately until sufficient laminate thickness has been built up. By
using fast setting resin systems and applying heater bands around the pipe
rapid cure can be achieved, with the pipe being returned to service shortly
after the repair has been completed.
Modifications which have been used include wrapping the laminate with
aluminium or steel sheet held in place with steel bands and also clamping on
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SITE APPLICATION OF LAMINATES 137
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138 FRP TECHNOLOGY
REFERENCES
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Chapter 9
POLVESTER RESINS
9.1 INTRODUCTION
Polyester resins can be divided into two classes, (i) the so-called saturated
polyester resins such as polyethylene terephthalate or 'Terylene', a
thermoplastic material used for injection moulding and fibre production
and (ii) the unsaturated polyester resins which can be cross-linked, by the
addition of a suitable catalyst, into thermoset polymers. It is only these
latter materials which will be considered here.
Unsaturated polyester resins are variously referred to as UP resins,
polyester resins or just simply polyesters.
Fig. 9.1. Post Office Building, London. Clad with white GRP panels moulded by
Anmac Ltd, with Crystic resin from Scott Bader. (Courtesy of Scott Bader Co. Ltd.)
139
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140 FRP TECHNOLOGY
Unsaturated polyester resins form the bulk of all resins used for
laminating applications and are without doubt the best known for
laminating. They are also used for button manufacture and to a lesser
extent for the manufacture of synthetic marble and as encapsulating resins.
Many different types of resin are now available from a large number of
suppliers. Many of these resins have been developed for specific end use
applications or for use with specific processes such as continuous sheet
production or resin injection.
Some typical applications of polyester resins in buildings are shown in
Figs. 9.1 and 9.2.
The basic materials used to make a polyester resin are a dibasic organic acid
or anhydride and a dihydric alcohol (glycol). To obtain a polymer chain
which can be cross-linked into a thermosetting resin, a proportion of the
dibasic acid must contain an unsaturated group or double bond. This
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POLYESTER RESINS 141
Styrene
9.2.1 Glycols
Many different glycols are commercially available, over a wide price range.
Clearly, from a commercial point of view, the cheapest glycol, providing
that it gives a satisfactory resin, will be chosen.
The simplest glycol is ethylene glycol. This can be used but gives
polyester resins with a marked tendency to crystallise and which have
limited compatibility with styrene. For this reason it is generally used in
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142 FRP TECHNOLOGY
conjunction with other glycols or, if used alone, the resin is acetylated or
propionylated.
The next glycol in the series is propylene glycol (propane-l ,2-diol). This
gives non-crystallising po)yester resins completely compatible with styrene
and is also relatively cheap. Thus it is used in the bulk of all polyester resins
produced today.
Other glycols in use include the following:
Diethylene glycol - This gives resins with improved flexibility.
Dipropylene glycol - This gives some improvement in flexibility
coupled with better chemical resistance.
Neopentyl glycol - This gives resins with improved chemical
resistance, particularly to alkalis, and im-
proved hydrolytic stability. It may need
blending with other glycols to improve the
styrene compatibility of the resin.
Polyester resins with high chemical resistance are frequently made from
bisphenol A [2,2-bis(4-hydroxyphenyl)propane] or its hydrogenated ho-
mologue [2,2-bis(4-hydroxycyclohexyl)propane]. These resins exhibit im-
proved alkali resistance in addition to generally high chemical resistance.
Such resins are usually heat cured to obtain maximum chemical resistance.
In order to produce a glycol suitable for reacting with organic acids, the
bisphenol A may be pre-reacted with ethylene oxide or propylene oxide.
Flame retardancy can be introduced into the molecule by using
chlorinated or brominated diols. One such product is Diol III from U gine
Kuhlmann. This is N N' -bis (ethan-2-0 1) diamino-octachlorodiphenyl.
Resins prepared from this diol not only exhibit flame retardancy but also
high chemical resistance. An example of a brominated diol is dibromo-
neopentyl glycol. This again gives some fire retardancy coupled with
improved chemical resistance.
By incorporating a small proportion of a polyhydric alcohol, say 5%, a
hard heat resistant resin can be produced. Examples of polyhydric alcohols
in use include glycerol, pep.taerythritol and mannitol.
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POLYESTER RESINS 143
affects the reactivity ofthe resin. The higher the degree of un saturation, the
higher the reactivity of the resin.
Reactivity and cured properties can be modified by blending a saturated
dibasic acid with the unsaturated dibasic acid. This procedure is adopted
with most commercially available resins.
The most commonly used unsaturated acid is maleic acid
(m.p. 132-140°C), generally used as the anhydride (m.p. 60°C) due to its
lower melting point. An alternative acid is fumaric acid, the trans isomer of
maleic acid. Although maleic acid isomerises to give fumaric polyester
resins, those prepared from fumaric acid generally have higher softening
points and a greater tendency to crystallise.
Other unsaturated acids, such as chloromaleic acid, itaconic acid and
citraconic acid may be used but are more expensive and therefore polyester
resins based on these acids are uncommon. Problems with stability of such
resins may also arise, particularly with those based on itaconic acid.
Although chloromaleic acid contains 26% chlorine, this is insufficient to
make it an attractive candidate for flame retardant polyester resins, unless
supplemented by other chlorine containing components.
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144 FRP TECHNOLOGY
I
0-.
CO
/0 0-.'
COOH & 0-. COOH ¢ COOH
Phthalic anhydride Ortho- Iso- Tere-
phthalic acids
/""
Cl*CO
/"', "'0
0-. /
o
Cl CO CI CO
CI
CI
Tetrachlorophthalic anhydride HET anhydride
Flexibility can be built into the resin by replacing part or all of the
saturated acid by an aliphatic dibasic acid such as adipic acid or sebacic
acid. Resins made from these acids are generally added to conventional
resins to improve flexibility and impact resistance; such resins are rarely
used alone.
By carefully blending two or more dibasic acids together, resins with a
wide range of intermediate properties can be obtained. Thus resins can be
tailored to suit a wide variety of end uses.
9.2.4 Mooomers
The monomer serves two purposes: (i) to act as solvent for the polyester
resin to produce a liquid with a suitable handling viscosity and (ii) to cross-
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POLVESTER RESINS 145
Refractive
Material index, n~
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~
-
Table 9.2 Properties of some monomers
Explosive
Vapour Refrac- Volume limits
Specific Boiling Flash pressure tive Viscosity shrinkage (% v/v in air)
gravity point point at 25°C index at 25°C TLV on cure
Monomer at 20°C (0C) (OC) (mm Hg) n 25 (mPa s) (ppm) (%) Lower Upper ;il
D "C
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Methyl acrylate 0·952 80 10 1-4020 0·50 10
Methyl meth-
acrylate 0·943 100 10 38 1·4118 0·84 100 21 2·1 12·5
n-Butyl acrylate 0·89 145 48 10 0·9 10
Diallyl phthalate 1·13 290 166 1 1·519 9·0 11·8
Triallyl cyanurate 150 1·5069
POL¥ESTER RESINS 147
9.2.5 Inhibitors
Once the polyester polymer has been dissolved in a monomer, the system
may gel at room temperature in the absence of a catalyst-indeed styrene is
well known for its ability to polymerise on its own in the absence of an
inhibitor. To prevent this from occurring and to obtain an acceptable
storage life for the resin, an inhibitor is added. This is normally added after
the polycondensation reaction has been completed and before the resin is
dissolved in the monomer.
Inhibitors are generally reducing agents which absorb free radicals by
200
2
160
u
0
cv
. 3
So.
......,
~
120
s..
cv
0-
S 80
cv
I-
40
20
0 10 20 30 40 50 6U
Time, minutes
Fig. 9.3. Effect of inhibitor on gel time and cure rate. Formulations: 1, resin
(Vestopa1150) 100, MEK peroxide 2, cobalt accelerator (1% Co) 0·3; 2, resin
(Vestopal 150) 100, M EK peroxide 2, cobalt accelerator O· 3, inhibitor ( 1% solution)
1 ;3, resin (VestopaI150) 100, MEKperoxide 1, cobalt accelerator (1% cobalt) 0·14.
(Courtesy of Hills (UK) Ltd.)
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148 FRP TECHNOLOGY
donating hydrogen atoms and hence prevent those free radicals from
polymerising the resin. Clearly, once an inhibitor has been exhausted, any
further generation of free radicals will cause gelation of the resin.
When a peroxide catalyst is added to a pre-accelerated resin the first
reaction is to neutralise the inhibitor and it is this reaction which accounts
for the initial period of apparent inactivity of the system. Where a longer gel
time is required with no reduction in rate of cure, then additional inhibitor
can be added to the system. This is preferable to reducing the catalyst or
accelerator proportion, since then a slower rate of cure results (Fig. 9.3).
Typical of the inhibitors used commercially are hydroquinone, t-
butylcatechol and substituted benzoquinones. These are used in amounts
ranging from 100 to 300 ppm. The actual amount of inhibitor needed to
stabilise a resin will vary from one resin to another and whether or not the
resin is for tropical use. In practice a mixture of inhibitors may be used to
achieve optimum stabilisation whilst maintaining optimum reactivity.
Where an inhibitor is used to increase gel time, the amount added will be
of the order of 1% of a 1% inhibitor solution. This is equivalent to 100 ppm
of pure inhibitor. The effect of such an addition is to increase gel time from,
say, 18 min up to about 50 min without altering reactivity. This is
illustrated in Fig. 9.3.
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Table 9.3 Typical properties of cured polyester resins
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acid 85 55 3·2 2·9 70 30 150 90 7
Bisphenol A 130 60-75 3·2 2·5-4·0 120-136 30 170 90 7
Chlorinated paraffin 110 50-60 H 1·2-4·8 55-80 30 140 90 7
Isophthalic/chlori-
nated paraffin 90 60 2·0 4·8 50 30 140 100 7
......
.j:>..
\(;)
150 FRP TECHNOLOGY
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POLYESTER RESINS 151
available in two types, (i) for brush application and (ii) for spray
application. These usually only differ in viscosity and thixotropy.
General purpose gelcoat resins are based on orthophthalic or isophthalic
resins, the latter type offering improved water, chemical and impact
resistance. Where superior weathering resistance is required, the gelcoat
will invariably be of the isophthalic type and may contain a blend of methyl
methacrylate and styrene as monomers.
Some manufacturers offer fire retardant gelcoats based on HET acid or
HET acid/isophthalic blends, while others recommend their normal
isophthalic resins. Care has to be taken in selecting a fire retardant gelcoat
for outdoor applications since many of these exhibit inferior weathering
resistance.
Where chemical resistance is required, gelcoats are available based on
isophthalic, isophthalic/HET acid, isophthalic/NPG and bisphenol A
resins. Choice depends on the precise chemical environment and service
temperature.
In addition to gelcoat resins, there is also a range of topcoat resins
available. These are similar to gelcoat resins with one important difference
and that is they do not suffer from air inhibition during cure. This is
generally achieved by adding a wax to the resin which migrates to the
surface during the initial stage of cure.
Topcoat resins serve to protect the underlying laminate, give a tack-free
decorative finish and balance up the laminate by giving a resin-rich surface.
The finish obtained is never of the same quality as the gelcoat finish since it
is not a moulded surface.
Where repairs or ribs, etc., have to be bonded to topcoats, thorough
cleaning of the surface with an abrasive cleaner and roughening must be
carried out prior to application of the new resin, otherwise complete release
of the new resin will inevitably occur.
As an alternative to using a polyester resin as gelcoat, Rohm & Haas
have developed an acrylic moulding powder which can be extruded in sheet
form, thermoformed and used in place of a conventional gelcoat. 2 The
effect is not only to produce a decorative finish on the moulding but also to
rigidise it. The acrylic 'gelcoat' can be used in most processes where a
conventional gelcoat is at present employed.
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152 FRP TECHNOLOGY
Fig. 9.4. The first all-G RP offshore lifeboat moulded by Halmatic Ltd,from Crystic
resin supplied by Scott Bader, for the Royal National Lifeboat Institution. Length
16·5 m. (Courtesy of Scott Bader Co. Ltd.)
tion of the latter. Lloyd's Register of Shipping have stated that it is their
intention to phase out orthophthalic polyester resins from their list of
approved resins in due course. A typical GRP boat is shown in Fig. 9.4.
Many different orthophthalic polyester resins are available, designed for
a variety of application and processing techniques. They cover a wide range
of viscosities, reactivities and gel times and can vary from relatively soft to
hard rigid cured resins.
Other resins which fall into the general purpose class are the terephthalic
acid and some isophthalic acid based polyesters, although this latter group
also come under the heading of chemical resistant resins.
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POLYESTER RESINS 153
Table 9.4 Some chemical resistance data for polyester and vinyl ester resins
"
~ "1"
t-
N 0
0 ~ t2 b;
~ "1"
0"\
"1"
0"\
r<) \.Q
N
00
0
00 ~
00
:: 0"\ .....
0
0"\
'-
.::l .::l r<) on ..c:, ___
(;)..... ::
(;) ::
:: .~ .~
" ~"
';;; ~ \0 ...... ....
(;)
" '"
::
';;;
'" t- ~
~
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154 FRP TECHNOLOGY
.::l
0
0
\0
-1:.,
N
00
('f'l
0
00
\f")
~
00
~~
;:0-
<::>-
r-
0-
;:
-
0
0-
;:
-;;; -;;; -;;;
..C)~
<::>
t- ~"
~ ....
" <::>- ~
a
;: ~
~
~\O
t- t- t-
\,,) \,,) \,,) \,,) ~ ~ ~ \,,)< ~
~N
~
Chloroacetic acid 25 30 40 60 70 104 93 30
50 NR 25 40 60 60 60 30 30 60
Chlorine water Sat. NR 25 50 55 25 25 90 70
Chromic acid, aq. 10 45 45 60 55 25 25 30 60
30 NR NR 30 30 NR NR 25
Diallyl phthalate 100 50 50 50 70 82 82 100 60
Diesel fuel 100 40 35 30 40 50
Dimethyl phthalate 100 50 50 50 70 66 66 60
Ethylene glycol 100 70 55 75 95 104 93 100 100 120
Ferric chloride, aq. Sat. 50 45 70 90 104 93 100 80 90
Formic acid, aq. 20 30 35 60 70 30 30 25 45
50 NR 25 50 55 25 25 25
75 NR NR 35 40 NR
Furfural 15 NR NR 35 25 25 NR
Heavy aromatic
naphtha 100 40 NR NR 25 25 25 30
Heavy plate
solution 65 50 75 80
Hydrochloric acid 20 45 35 60 70 104 93 80 60 110
35 35 25 35 30 25 25 65 30 30 75
Hydrogen peroxide
20 vol. NR NR 65
65 30 30
100 vol. NR NR 25
25 NR
Industrial meths. 100 25 2525 25 25 25 30 40
Kerosene (domestic) 100 50 3530 30 66 66 100 80 60
Lactic acid, aq. 44 55 9550 75 104 93 100 80 90 90
Lubricating oil 100 95 9050 45 104 93 110
Methyl alcohol 100 35 3025 30 25 25 30 50 30
Nitric acid 10 45 6025 60 66 66 60 90 70
40 NR NR NR
25 25 25 25
Perchloric acid, aq. 10 NR 5025 55 30 30
25 NR NR 35
30 30 NR
25 35
Petrol, 98 octane 100 30 2525 NR 25 25 30 40
Phenol I 25 25 25 80 80
Sat. NR NR NR NR NR NR NR NR
Phosphoric acid 85 55 50 75 95 104 93 80 60 120 25
Plating solutions
Cadmium cyanide NR NR 80 104 93 NR
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POLYESTER RESINS 155
--- ° E
s::
s::
-
0
0\
~
s::
..,
.~ .~
.., .~
t;
.~
t; '-' '-' ~ ~
~~ ~
t> t> t> t> ~ ~ ~
1;N
d ~ ~ ~ ~ ~ ~ ~ ~< ~ ~
Chrome NR NR 30 25 NR NR 90
Gold 50 45 70 90 104 93 90
Lead 50 45 70 90 104 93 90
Nickel 50 45 70 90 104 93 80
Platinum 80 82 82
Silver 40 30 50 90 104 93
Potassium
carbonate, aq. 10 NR NR 30 80 66 66 30 40
40 NR NR NR 30 25 25 30 40 45
Potassium
ferricyanide Sat. 55 50 75 95 104 93 80 90 80
Potassium
hydroxide, aq. 30 NR NR 40 50 25 25 25 NR
Potassium
permanganate Sat. NR NR 30 35 104 93 60 65 70
Sea water 55 50 75 95 104 93 100 80 80 80
Sodium carbonate, aq. 10 NR 25 35 80 82 82 30 50 50
25 NR NR 30 75 71 71
Sodium hydroxide 10 NR NR 50 60 66 25 30 NR 80
Sat. NR NR NR 80 104 25 NR
Sodium hypochlorite 14 NR NR 60 55 75 NR
Sulphuric acid 50 80 60 80 100 104 93 100 70 65 85
75 NR NR 25 40 25 25 30 60 65 65
Tartaric acid, aq. Sat. 55 50 75 95 104 93 100 80 120 80
Toluene 100 25 NR NR NR NR NR 30 30 25
Trichloroacetic
acid 25 NR 30 50 60 90 25
50 NR NR 30 50 104 93 30 40 90 25
Turpentine 100 30 25 25 30 40
White spirit 100 35 25 25 30 50
Xylene 100 40 NR NR 25 25 25 30 50 38 NR
a Intermittent contact.
b Concentration by weight in water where less than 100%.
aq. = aqueous; NR = not recommended; Sat. = saturated.
All laminates were made with a resin-rich finish in contact with the reagent.
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156 FRP TECHNOLOGY
The weak link in the polyester molecule is the ester group and it is this
that needs protecting from chemical attack. This can be accomplished by
increasing the degree of cross-linking of the resin and by hindering attack
by placing bulky groups around the ester links.
Intermediate levels of chemical resistance can be obtained with isoph-
thalic polyester resins. These will vary somewhat in performance depend-
ing on their precise formulation.
A higher level of chemical resistance can be obtained by replacing the
propylene glycol with neopentyl glycol to give an isophthalicjNPG resin.
Chemical resistance can be further increased by using bisphenol A
derivatives or by using HET acid to make the resin.
Most suppliers have built up considerable data over the years on the
resistance of their resins to particular environments 3 and are in the best
position to advise on specific requirements. Some selected data are given in
Table 9.4 to serve as an indication of the types of chemicals which can be
resisted by fully cured polyester resins. Typical examples of the use of
chemically resistant polyester resins in chemical plant are shown in
Figs. 9.5 and 9.6.
Fig. 9.5. A scrubber unit moulded in GRP using Crystic 600 polyester resin-a
chemical resistant grade. (Courtesy of Scott Bader Co. Ltd.)
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POLYESTER RESINS 157
Fig. 9.6. GRP gas main for sulphuric acid plant. Moulded by Viking Industrial
Plastics Ply, Australia, with Crystic polyester resin. (Courtesy of Scott
Bader Co. Ltd.)
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158 FRP TECHNOLOGY
Fig. 9.7. GRP panels for car park moulded with Crystic 345 fire retardant resin by
Durapipe and Lambert Sales Ltd. Internal surfaces coated with Crystic Fireguard
resin. (Courtesy of Scott Bader Co. Ltd.)
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POLYESTER RESINS 159
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160 FRP TECHNOLOGY
styrene emission from a laminate has been the addition of film forming
materials, essentially incompatible with the resin. Such resins are fre-
quently referred to as 'Environmental Resins'.
Wax additives have been used for many years to prevent air inhibition of
exposed surfaces. Such additives also reduce styrene emission. However,
where wax containing polyester resins are used with multi-stage laminating
processes there is a risk of subsequent delamination, particularly under
impact conditions.
Other additives S (undisclosed) have been developed which do not suffer
this disadvantage. These have proved to be more effective than paraffin wax
but only with thixotropic resins. If the thixotroping agent is removed,
styrene emission remains at the unmodified level. The effectiveness of such
additives is illustrated in Table 9.5.
With all environmental resins, styrene emission remains at the same level
as with normal resins while the laminate is being worked since the resin
surface is continually being changed. It is only once the laminate has been
put on one side that the film forming additive can exert its effect. As with all
hand or spray lay-up processes adequate ventilation must be provided.
9.3.6 Low shrink/low profile polyester resins
Some 12 years or so ago the first low shrink/low profile unsaturated
polyester resins became commercially available. Since that time, whilst
some major advances have been made, their acceptance has been notice-
ably slower than at first expected.
With normal unsaturated polyester resins containing about 35% of
styrene, shrinkage of about 8% usually occurs during cure. With large flat
mouldings this high shrinkage results in sink marks and a generally poor
quality finish, unacceptable for many applications.
Table 9.5 Effect of environmental additive on styrene emission
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POLVESTER RFSINS 161
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162 FRP TECHNOLOGY
Flexible resins
Flexible resins are those which in the cured state are soft and rubbery.
They are prepared by replacing part or all of the saturated acid with a
dibasic aliphatic acid such as adipic or sebacic acid. In so doing, the
chemical resistance of the cured resin is generally reduced and water
absorption increased.
Their main applications are in increasing the flexibility and impact
resistance of the more rigid laminating systems and in casting and
encapsulating systems.
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POLYESTER RESINS 163
Fig. 9.8. Road tanker cab mouldedfrom Crystic SMC by Bifort Engineering Ltd.
Tools by J. J. Harvey Ltd. (Courtesy of Scott Bader Co. Ltd.)
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164 FRP TECHNOLOGY
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POLYES1ER RESINS 165
For fast production rates, a high reactivity, low viscosity resin, with fast
air release is needed. Various resins are available which meet all of these
requirements.
Several production techniques may be used depending on the type and
number of buttons required.
Fancy buttons, in single or double relief, may be cast in a mould with a
small opening to permit introduction of the resin system. Moulds can be
made from silicone rubber, flexible PVC or polyethylene.
Where buttons are to be machined to produce the relief pattern, sheets of
resin are made by centrifugal casting and the blanks punched out while the
resin is still flexible, before full cure, generally between 30 min and 2 h after
casting. Various different buttons are shown in Fig. 9.9.
Clear colourless resins are also used for encapsulation. Here, the resin
must exhibit rapid air release for bubble-free castings. Low viscosity resins
are used, preferably with some degree of flexibility to withstand impact.
The resin should also be resilient, crack resistant and have moderate to low
shrinkage during cure, with low exotherm. Where filled systems are used,
the colour of the resin is unimportant and brown or straw coloured resins
may be used. For some applications good electrical properties are also
required.
Where decorative castings are to be produced, such as paper weights, the
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166 FRP TECHNOLOGY
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POLYFSTER RFSINS 167
resin system to disperse exothermic heat and reduce shrinkage during cure.
Electrical components may be embedded using metal or plastic moulds,
or potted using metal or plastic containers which remain part of the finished
component. In this latter case, thin walled metal or polystyrene containers
may be used. With polystyrene, excellent adhesion to the polyester resin is
obtained and if a thin-walled container is used it follows the shrinkage of
the resin on curing. Vacuum encapSUlation is often used to ensure complete
penetration of the resin into the component and bubble-free castings.
Casting resins are also used for making synthetic marble. Here, chunks
of marble are encapsulated in polyester resin. When cured the blocks are
sawn and polished and used in a similar way to whole marble slabs. By so
doing, marble waste can be fully utilised. Resins used for this application
must have good adhesion to marble, good impact resistance, good elasticity
to permit sawing, minimum shrinkage and good polishability. They must
also be heat resistant and resistant to most foodstuffs, since slabs cut from
blocks are frequently used as table tops. Low exotherm systems must be
used to prevent shrinkage stresses from occurring, since a typical block
would be 3·05 m long by 1·25 m wide and 0·83 m deep. Marble flour and
pigment paste may be added to the resin system prior to casting. The cast
blocks are usually stored for at least 1 week after cure before being sawn
into slabs and polished.
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168 FRP TECHNOLOGY
Mitex foam can be filled with lightweight fillers and glass reinforcements
such as chopped strand mat and continuous filament mat. It can be used to
produce lightweight sandwich panels and to provide thermal and sound
insulation. The cured foam has a low coefficient of expansion, good
weathering resistance and is self-extinguishing. Mechanical properties
depend on density and filler and reinforcement levels.
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POLYESTER RESINS 169
REFERENCES
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Table 9.6 Commercial polyester resins
,£
----- ';: ';S '"" -s
.~ '" ~ ---
~
..,
. ~ >::: '- >::: ~ ~
'-- c >::: c
..,~ G !::
'"
0 -s
..,'"
<:I
II<:I'""
Supplier -~v ">::: '- '"",'"" ~
~ " '" 0 '" .., r...~
Trade name 8N h ~~ >::: '" '--
" Q c
'~~ "'-5.."
Product code Type
"'" ..s::
~ ::~ V3~ CI:l ::t:: ~~ ~ ~~ Remarks
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flexible than 431
450 )-0-1-3 34 55 2 (0-3) Chemical resistant
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1·07 1·6a 41 7 110 70 2-4 Chemical resistant
W35 neopentyl glycol
1·06 1·4a 43 115 60 2·5 Chemical resistant
W37 isophtha lic/NPG
1·09 3·5 a 38 7 115 75 4·0 15 Chemical resistant
W41 bisphenol A
1·03 0·6a 50 7 120 60 2·5 IS Chemical resistant
W45 bisphenol A
1·17 1·1" 30 8 55 60 4·8 24 Flame retardan t
F24 chloroparaffin/
isophthalic
1·35 2·8 a 25 5 80 40 I· 3 12 Self-extinguishing,
F 30 HET acid
clear
1·30 0·7a 29 6 55 40 1·7 18 Self-extinguishing,
F 30 S HET acid
light stabilised
1·18 2·5a 29 7 80 60 1·8 14 Flame retardan t
F 35 chloroparaffin
1·12 1·la 34 6 RT 8 80 Putties, mortars
E 70 flexible
1·13 ).0- 26 6 RT 10 30 88 Flexibiliser
E 81 flexible
Table 9.6 (Continued)
~
., ~
::::
0: """"' "S -~
~~
~
.2,. '- ~
~
'-
~
::: <:) s:
'" u
""...''""
~ '"
-~ -<:>
-~u " '~" '-
<::-..
Supplier ., D -\(
""
$" f... ~~
-;; ~
t...~
<.J
'"'"
Trade name 8~ ...'" ~ -5'- ~ "''-
Q
Product code Type '" ~~
(1),- (I) Remarks
~ ~~ "'" ::t: ~~ ~ ~~
Leguval (contd)
E 90 flexible 1-09 1-2" 30 6-7 RT 10 50 Improved water resis-
tance over E 81
E 91 flexible 1-09 0-25" 33 6 RT 100 50 Sealing compounds
K 14 1-10 I-I" 35 100 Putties
-.J K27 1-13 3-0- 30 8 75 50 2-0 16 Putties
tv
K41 bisphenol A 1-09 3-5" 38 7 115 75 4-0 15 Chemical resistant
K65 tetrahydro- 1-12 0·85" 33 7 RT 8 65 37 Putties, sealing
phthalic compounds
K 70 flexible 1·12 I-I" 34 6 RT 8 80 85 Putties, floors
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LP 15 low profile 1-05 2-3" 50 110 Hot press moulding
BP Chemicals Ltd
Cello bond
A253/67 orthophthalic 1-07 0-19 45 92 Methyl methacrylate,
light stable
A259/204 orthophthalic 1-07 0-28 41 Vacuum impregnation
of castings
A259/214 flexible 1·13 0-82 24 Stoppers
A2593 flexible 1-13 0-16 36 Flexibiliser
1·26 T 38 72 BS 476 pt 7 class I,
A261/65 fire retardan t,
opaque
orthopht halic BS 476 pt 7 class I,
fire retardan t 1-60 0·9 22 80
A261/383 opaque
T 46 120 Fire retardan t, chem-
A261/1973 RET acid 1·12
ical resistant
= Retron 1973
0·33 41 73 General purpose
A262/249 orthophthalic 1·11
38 100 Filament winding,
A262/288 orthophthalic 1·11 0·39
hot press moulding
0·35 40 78 General purpose
A262/400B orthopht halic 1·10
0·36 36·5 63 General purpose, low
A262/420BLE orthophthalic 1·12
styrene emission
0·66 38 Stoppers
A262/424 orthophthalic 1·10
0·58 38 72 General purpose
A2622 orthophthalic I·ll
T 42 78 General purpose
A265/500B orthophthalic 1·09
0·9 41 100 White pigmented,
...,..... A265/51 IB/NI56 orthophthalic 1·12
acrylic baths
T 39·5 64 Low styrene emission,
A265/520BLE orthophthalic 1·10
general purpose
T 40 75 General purpose
orthophthalic 1·12
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A2656 130 Good chemical and
A266 I special 1·\2 0·53 37
heat resistance
T 39 65 BS 476 pt 7 class 2,
A271/77B orthophthalic 1·14
clear
T 28 94 BS 476 pt 7 class 2,
A271/84B fire retardan t 1·37
translucent
45 72 Methyl methacrylate,
A2712 orthophthalic 1·12 0·18
light stabilised
20 Gelcoat, BS 476 pt 7
A272/1 special, fire 1·54 T
class I
retardan t Gelcoat, BS 476 pt 7
orthophthalic 1-47 T 20 56
A272/3A class 2, opaque
Table 9.6 (Continued)
0
.,
---- ;: ";5 .~
';:: ~ ---- i>IJ ----
~ '"
~ ~ 0: '- ~
0:
I: '- <:l 0: El
i>IJ <..J G !::
'"
., .~ .::l
0
<..J <:1-----
.2\..l '"i>IJ<:I '-
Supplier ., 0 ..:.: .... ~
:s.
<..J
'0:" .5 f... ~~
.,Q.,
Trade name 8~ "
'~:6 ~<:l
"''-
'" . ~
Product code Type ~ ~B ~~ ~ ::r:: ~~ 1<5 ~ ~ Remarks
Cellobond (contd.)
A273j302A isophthalic 1·12 T 39 105 Weather, water
resistant
A273j380A isophthalic '·06 T 50 80 Flexible spray geicoat
A273j381A isophthalic I· I3 T 32 80 Flexible brushing
~ geicoat
A273j281AjN129 orthophthalic 1·32 T 32 68 Spray gelcoat, con-
tainers
A273j365AjN180 orthophthalic '·32 T 30 42 Roller geicoat, con-
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tainers
A2784 isophthalic 1·09 0·99 42 118 Marine, etc.
A2785CV isophthalic 1·09 T 43 118 Thixotropic version
of A2784
A283j270 isophthalic 1·11 0·56 36 80 Chemical resistant,
hot press moulding
A284j34 special 1·13 0·7 37 134 Non-shrink DMC
A360j82A orthophthalic 1·10 T 42 76 General purpose
A360j151 orthophthalic 1·15 T 32 Amine accelerated
for stoppers
A360j212B orthophthalic 1·09 T 45 64 Spray lay-up
A360j212C orthophthalic 1·09 T 45 64 Long gel time version
of A360j212B
A360j215C orthophthalic 1·10 0·36 40 74 Long pot-life resin
A370/111B orthophthalic 1·06 T 45 58 Fast cure, general
purpose
A3700A orthophthalic 1·11 T 40 58 Containers
A7ll/24 isophthalic 1·18 0·6 44 130 Low shrink for DMC
A7ll/26 isophthalic 1·\0 1·8 34 97 High reactivity
for SMC
A7ll/31 special 1·09 1·79 43 80 High reactivity for
SMCjDMC
A711/34 isophthalic 1·09 0·55 41 125 Non-shrink for DMC
[email protected]
836 E 1·10 0·4T 42 9 59 48 10 Low reactivity,
general purpose
837 E 1·11 0·4T 42 9 59 48 10 High reactivity,
general purpose
840 E 1·11 0·4T 42 9 59 48 10 Medium reactivity,
general purpose
844 bisphenol AI 1·04 0·75T 48 9 125 56 24 Chemical resistant
hydrog.
bisphenol A
849 reduced flam- 1·17 0·33 T 39 11 72 36 15 BS 476 pt 7 class 2
mability
Table 9.6 (Continued)
~
~
.:
-<: S
t>
.;;: '" 0;,
<l ~ ~ 1::: ~ ~
... C 1::: C
be v :::" .S ..t:)
''"""
.2v " '"~ '- '" '"
<::s~
Supplier 'S, 1::: ..\( 10..~
,,~
" ~~ f..., ~~
",Cl.,
Trade name ~
"... ~
""< " ... Q
"'" ..:::
Product code Type ~ s=~ ~~ V)
" :t: ~~ ~ ~ ~ Remarks
Beetle (contd.)
854 reduced 1·17 0·33 T 39 11 72 36 15 BS 476 pt 7 class 2
flammability
855 reduced 1·54 0·55 T 23 4 60 10 12 BS 476 pt 7 class 1
flammability
-..J 856 reduced 1·15 0·33 T 39 10 81 38 19 Clear, UV stabilised
0-
flammability
8564 reduced 1·16 T 36 II 70 37 21 BS 476 pt 7 class 2,
flammability translucent
859 orthophthalic 1·11 0·31 42 10 112 48 18 Resin injection
[email protected]
862 isophthalic 1·09 0-43 40 8 73 76 23 Stoppers, etc.
864 E 1·11 0·4 T 42 9 59 48 10 Fast cure, general
purpose
865 E 1·09 0·2T 47 9 60 45 9 Medium-fast cure,
general purpose
867 E 1·12 0-4 T 42 9 59 48 15 White pigmented,
similar to 840 E
868 methyl meth- 1·10 0·25 44 7 85 45 21 Light stabilised
acrylate
870 HET acid 1·13 0·35 T 44 7 115 44 16 Reduced flammabi-
lity = Hetron 1973
872 1·11 0·2 T 44 9 92 50 19 Acrylic baths
873 isophthalic 1·07 T 49 7 95 62 18 High quality resin
874 I·ll T 38 9 102 54 20 Chemical resistant,
mould making
876 E 1·12 T 40 9 82 48 15 Marine and tropical
use
878 E 1·12 T 40 9 82 48 15 Pre-accelerated
version of 876 E
8797 1·15 2·5 <0·5 Pigment dispersing
resin
8110 wax modified 1·11 0·54 39 8 62 46 14 Contains paraffin
wax
8116 1·11 0·54 39 8 62 46 14 Casting resin
8123 1·15 3-3 28 8 65 61 16 Hot press moulding
8128 1·12 0'88 35 8 95 56 22 Moulding compounds
8134 flexible 1·12 0·35 33 Flexibiliser,
castings
[email protected]
etc.
804 1·12 0·6-0·7 Low exotherm,
marble casting
8211 1-08 0·38 T 65 1·8 (0,2) High production rate
8213 1·09 0·4-0·5 T 62 1·7 (0'2) Rapid cure, hand/spray
8214 1·09 0·4-0·5 T 62 1·7 (0,2) Rapid cure, hand/spray
8215 1·08 0'07-0·1 62 1·8 (0'2) High production,
high filler
8216 1·08 0·2-0·25 Filled mouldings
8217 1·08 0·06-0·1 Filled mouldings
8218 1·08 0·15-0·22 Filled mouldings
8219 1·08 0·1-0·15 Filled mouldings
Table 9.6 (Continued)
.:
---.., t; -S .S:
.2 ~ --- ~---
. ~ ~ ~ '-- ~
~ '-
..:
c.... . ..:
I>C U '"
::; .S: ]
'" 0
.... ·£u '- <::---
Supplier .., 0 ..: ....~
<:>...,
'" ~~
.:; 1:1.,
... ~
Trade name
$....
5 h
""", " Q
~ "''-
'~~ .. <:>
Product code Type '" v;~ t:;j I>C Remarks
~ ~~ ~ ::t: ~~ ~ E
8220 1· \0 OA-0·5 T 65 1·8 (0·2) Low exotherm, large
mouldings
8221 1·\0 0·4-0·5 T 65 1-8 (0,2) Low exotherm, long
trim time
8224 1·08 0·43 T 65 1·8 (0,2) Winter use, fast cure
....,
00 8243 J.08 0·43 T 65 1·8 (0,2) Low exotherm, short
trim time
8245 1·08 0043 T 65 1·8 (0,2) Low exotherm, small
mouldings
[email protected]
8249 J.08 0·39 T 65 1·8 (0,2) Low exotherm, large
mouldings
8255 J.09 OA-0-5 T 62 1·7 (0,2) Fast cure, short
trim time
8256 J.09 0·4-0·5 T 62 1·7 (0,2) Fast cure, short
trim time
8263 1.09 0-4-0·5 T 62 1·7 (0,2) Fast cure, hand/spray
8285 I·!O 0-4-0-5 T 65 1.8 (0'2) Low exotherm, long 'green' time
8286 1· \0 OA-0·5 T 65 1·8 (0,2) Low exotherm, long 'green' time
8314 flexible 1,140-35-0·4 6·9 80 (0,7) Encapsulation, stoppers
8318 flexible 1·14 004-0045 Encapsulation, stoppers
8336 flexible 1·15 o· 35-0'45 6·9 80 (0'7) Adhesives
8400 1·14 0·5 T 84 69 3·0 (0,24) Slow gel, fast cure, moulds
8411 1·08 0·4-0·5 T 65 1·8 (0,2) Fast demould
8446 1·03 0·4-0·5 Good chemical resistance
8450 isophthalic 1·09 0-4-0'5 T 115 69 2·0 Chemical resistant
8490 isophthalic 1·11 0·9 115 69 2·0 Corrosion resistant, pultrusion
8525 fire retardant 1-3 0·6-0·7 T 100 38 (0,18) General purpose
8530 1-08 0-4-0·5 T 65 1·8 (0'2) Low exotherm, hand/spray
8540 1·08 0·4-0·5 T 65 1·8 (0'2) Low exotherm, large mouldings
8575 fire retardant 1·3 0·6-0·7 T 100 38 (0,18) Medium gel and cure
8593 isophthalic 1·17 2·8 83 75 4·0 (0,24) Craze and impact resistant
8704 0·1-0·16 Transformers
8725 1·05 0·05-0·1 Water emulsions
8801 1·14 1·1 Marble casting
8804 1·12 Marble casting
8808 1·14 Marble casting
.... 8809 l·ll Casting, fast demould
'" 88ll 1·12 0·08 Casting, fast demould
8831 1·13 1·4 Casting, fast demould
8881 1·14 1·2 Low exotherm, casting
8882 1·14 1·2 Low exotherm, marble casting
[email protected]
8884 1·12 0·6-0·7 Low exotherm, marble casting
8885 1·12 0·6-0·7 Low exotherm, marble casting
8911 1·14 2·8 71 68 1·8 (0'2) Matched metal moulding
8942 1·14 2·2 90 67 1·8 (0,22) Matched metal moulding
8953 1·17 2'6-3·0 83 75 4·0 (0,24) Hot press moulding
8960 flexible 1·05 0·8-1·1 9-4 65 (0-4) Flexibilising resin
8974 1·17 2'6-3'0 90 82 2·9 (0,24) Matched metal moulding, BMC
~
~
.:
:; ~ ·9
.~ '" -::
. ~ ~ ~ ~
~ :::: ~
c ~ ::::
~ '-> G ·9 ]
0 <::s~
'->
Supplier
---.~u '~" '"
:s, '" 0
::::
'" -'< --- ~~ ... ~
Trade name c.., .5 h ",1:1., "'---
"'" '"
~~ ... c:::
~c
Product code Type ~ "'"
~~ V3~ ~ ::t:: ~~ iii ~r Remarks
Synolac (contd.)
6321 isophthalic GeIcoat, spray version of 6320
6322 35-55 37 White, light stabilised geIcoat
6323 12-25 44 Spray version of 6322
6325 NPG 40-55 33 GeIcoat, brush application
co 6327 35-55 GeIcoat, tooling grade
0
- 6329 T 58 Flexible topcoat
6340 silica filled 0'6-0·8 31 Contact moulding
6344 0'6-0·8 32 74 Contact moulding
[email protected]
6344-002 0·23-0·28 40 74 General purpose, fast cure
6344-060 T Paste for stoppers
6344-211 0-45 35 74 Pre-accelerated version of 6344
6344-302 0·25 40 74 Injection moulding
6345 0·5-0·9 33 77 Contact moulding,
sheet grade
6345-211 0·45 36 77 Pre-accelerated 6345
6345-213 0·2 45 77 Low exotherm, long
gel time
6345-214 0·28 39 77 White pigmented 6345
6345-217 0·45 34 77 Low exotherm, long
gel time
0·23-0·2 8 37 74 Injection moulding
6354-00 2 fire retardan t
0·3-0,35 32 72 BS 476 pt 7 class 2,
6356 fire retardan t
filled
0'6-0·7 35 97 High HDT
6370 orthopht halic
J.3-1·7 31 100 Chemical resistant
6375 White, acrylic baths
6382 orthopht halic 0-45 37 97
0·45 40 97 Improved version of
6383
6382
0·45 40 97 Unpigme nted 6383
6384
0·7-1·0 40 85 Chemical resistant,
6390 pipes, etc.
1·0-1·2 29 120 Chemical resistant
6392 fire retardan t
0·75 40 100 Semi-rigid, pipes,
6393 isophthalic
tanks
0·6-0·9 40 95 Tanks, containers
6394 isophthalic
0·7-0·9 40 100 Chemical resistant
00 6395 isophthalic
1-4-1,9 48 Zero shrink, hot press
6401 low profile
moulding
1'0-1'5 49 Hot press moulding
6403 low profile
1·1-1·8 35 Hot press moulding
6404
[email protected]
0·5-0·6 34 BS 476 pt 7 class 2,
6410 fire retardan t
unfilled
0·35-0-45 20 72 Filled, fire retardan t
6416 fire retardan t
0·45 25 72 Filled, BS 476 pt 7
6417 fire retardan t class 1
10-20 34 Ge1coat
6420 fire retardan t
0·7 57 Spray gelcoat for
6421 acrylic sheet
40 47 Brush version of 6421
6422 For use in low profile
Synocryl 4008 powder
systems
Table 9.6 (Continued)
,£
;: ";'5 ·9
~ --- ~
---
~ '- ~
.s. ~---'" ~
'-
>: c
c .... >:
~ '""'
G
0
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;;; ·9 i~
Supplier ~v '- ~
.~ 0 ~~ .... ~
$'""' '>:" .....5~ !-. .;;; Q.;,
Trade name ~ ~'-
'""' "N "
'~~ .... ..Sl
Product code Type ~ ~~ C;S~ c55 § ~~ r..) ~eo Remarks
[email protected]
40-1096 isophthalic 1·10 0·18-0·25 40 90 65 2-4 19 Pipes and tanks
40-1097 special 0·96 0·9-1-1 37 Contains diallyl
phthalate
40-2012 orthophthalic 1·14 0·75-0·85 32 8 35 Flexibilising resin
40-2417 orthophthalic 1·2 204-2·9 29 75 56 1·3 30 Hot press moulding
40-2756 orthophthalic 1·18 T 33 60 45 1·8 35 Fire retardant, BS 476
pt 7 class 2
40-2769 fire retardant 1·55 T 27 75 12 18 Filled, BS 476 pt 7
class 1
40-2989 isophthalic 1·08 T 48 110 65 204 20 Resilient, corrosion resistant
40-3250 orthophthalic 1·11 0·13-0·16 33 80 Flexible jointing resin
40-3252 orthophthalic I· I2 0·12-0-15 34 80 Flexible jointing resin
40-6003 orthophthalic H5 1-4-1'6 30 72 85 5·5 22 SMC,DMC
40-6006 isophthalic 1·09 0·95-1·05 42 110 45 2·5 30 High reactivity, SMC, DMC
40-6020 orthophthalic 1·11 0·92-1·07 33 115 40 1·1 25 High reactivity, SMC, DMC
40-6021 orthophthalic 1·11 0·92-1·07 33 115 40 1·1 25 Rigid, high reactivity, DMC
40-6207 orthophthalic 1·52 4·8-7·7 14 6 Filled, resilient cast-
ing resin
40-6502 orthophthalic 1·46 1·5-2·1 21 10 80 Flexible, filled cast-
ing resin
40-6749 Ge1coat
40-6754 orthophthalic 1·53 T 25 45 49 H 32 Fire retardant gelcoat
40-6764 isophthalic 1·15 T 35 53 63 4·5 20 Resilient, brush gelcoat
40-6878 orthophthalic 1·2 0'17-0·26 40 65 65 1-8 18 Hand lay-up, containers
40-6879 orthophthalic 1·14 T 38 70 65 1·8 20 Hand/spray lay-up,
containers
40-6990 orthophthalic, 1·10 T 40 100 30 1· 3 25 High reactivity, sanitary
00 clear ware
w
- 40-6993 orthophthalic, 1·10 T 40 100 30 I· 3 25 High reactivity, sanitary
white ware
40-7488 1·12 0'92-1'07 34 150 27 0·9 40 Use with low profile
additive for SMC, DMC
[email protected]
40-8200 bisphenol 1·04 2·6 7·5 130 43 SMC, DMC, matched metal
moulding
.:
-S ·S
~
.S,. ---"" --- ---
~ .::: ~ '- ~
t:
~ '- C
" t:
. <> ... G r ·s
Supplier <> .21..1
..., 0
~ ~ ""
..!(
...t: ~
$ c.,.., ... ~~
f.... ~ '-
.S 'r;;
i...... -"
Trade name ...<> <>", ... Q
~
Product code Type ~~ ~~
"J,,- ~ ::::; ..s
t.:i Remarks
~ ~~ ~r
Hetron (contd.)
92 fire retardant 1·33 2·2 29 Press moulding, pultrusion
92AT fire retardant 1·29 0·5 36 Chemical resistant
92FR fire retardant 1·29 0·5 33 Chemical resistant
00 92FS fire retardant I· 3 0·11 38 Chemical resistant
"" 197 fire retardant 1·2 2·0 31·5 Chemical resistant,
press moulding
197-3 fire retardant 1·14 0·5T 42 Chemical resistant, fila-
ment winding
[email protected]
197P fire retardant 1·14 0'5T 42 Chemical resistant, fila-
ment winding
197L fire retardant 1·17 0·55 38 Chemical resistant, fila-
ment winding
197AT fire retardant 1·25 0·5 37·5 Chemical resistant, fila-
ment winding
197A fire retardant 1·15 0·5 T 45 High impact, chemical
resistant
197-8515 1·15 0·28 40 High impact, filament
winding
700 bisphenol AI 1·03 0·5 50 Chemical resistant
fumarate
700C bisphenol AI 1·03 0·5 50 Chemical resistant
fumarate
28091 brominated 1·5 0·7 28·5 Fire retardant,
(37% Br) SMC,DMC
[email protected]
UP 462 chlorinated 1·24 0·35 35 86 11·6 0·3 13 Fire retardant, chemical
resistant
UP 468 fire retardant 1·45 0·54 28 58 20 1·0 7 BS 476 pt 7 class 2,
filled
UP 745 terephthalicl \·06 0·8" 44 7 145 50 2·3 Chemical resistant
NPG
UP 746 isophthalicl 1·06 1·6 " 45 8 60 2·5 Chemical resistant
NPG
Honeywill-Atlas Ltd
Atlac 382 E propoxylated
bisphenol 1·16 solid 0 Chemical resistant,
solid resin
Table 9.6 (Continued)
.:
"' ,0 ·9
.~
,. '" .,
~
"' -S
"<
"'
.'-
~ ::: '- ~
ci' -! ::: c
c !: :::
~ "~ G
0
" ·9 '"
Supplier .Sv '- '" ~"'
"::: -"t
$'" ~ 0 " ~~ ,~
Trade name ·5 h ~Q.; ~ " '-
'"" "'~ "~:6 .. ~ -9
Product code Type ~ ~~ C;S~ ~ ::r: ~~ [.:,l ~ ~ Remarks
Atlac (contd.)
382-05A bisphenol 1·03 0·4-0·55 50 140 70 2·5 Solution of 382
A/fumarate in styrene
00 387 flexible 1·03 32-45 0 For blending with 382
0-
480 terephthalic Chemical resistant, general
purpose resin
490-05 terephthalic 1·10 0·6 40 125 49 1·8 30 Chemical resistant, general
purpose resin
[email protected]
711-05A fire retardant 1·23 0-45-0'6 120 Chemical resistant
4010 flexible blend 1·02 0·24-0'34 50 96 68 4·0 Blend of 382/387-40/10
[email protected]
310 flexible 1·17 1·0 27 7·1 50 25 20 Flexibilising resin
320 flexible 1·13 0·95 25 7·3 12 25 Flexibilising resin
330 flexible 1·13 0·25 30 6·5 4 80 Flexibilising resin
400 special 1·11 4·5 35 5·1 105 80 2·5 Hand lay-up, gelcoats
X2814 experimental 1·08 1·0 40 7·3 145 50 1·5 Hand Jay-up, gelcoats,
chemical resistant
510 1·07 J·O 38 8 115 80 2·5 Hand Jay-up, press
moulding
511 J.07 1·0 38 8 115 80 2·5 SMC, DMC
530 1·10 1·0 40 7·6 130 65 2·2 Hand Jay-up, press
moulding
710 1·13 0·4 33 6·6 10 45 Amine accelerated,
putties
Table 9.6 (Continued)
Vestopal (contd.)
730 1·13 1·0 34 8 105 85 3·5 Amine accelerated, putties
810 1·13 0·4 33 6·6 10 45 Non-accelerated, putties
8Il 1·12 0·4 35 6·7 10 45 N on-accelerated, putties, etc.
00 830 1·13 1·0 34 8 105 85 3·5 Non-accelerated, putties, etc.
00
- Test methods DIN 2 4 11 6 7 7
[email protected]
5560 C 8007 orthophthalic 1·10 0·22 T 45 76 43-4 2·5 14 General purpose
5560 C 8008 orthophthalic 1·12 0·5 T 40 70 54·5 2·8 15 General purpose
5560 C 8009 orthophthalic 1·10 0·22 T 45 76 43-4 2·5 14 General purpose
5560C 8016 orthophthalic 1·12 0'5 T 40 70 54·5 2-8 15 General purpose
5561 C 8813 fire retardant 1·18 0·3 T 39 70 34·6 12 BS 476 pt 7 class 2,
clear
5561 X 0009 fire retardant J.32 0·3 T 32 74 37·3 12 BS 476 pt 7 class 2,
opaque
5566C 8003 isophthalic 1·10 0·26 44 III 23 Hand/spray lay-up,
injection
5566 C 8095 flexible, iso- 1·10 0·32 45 83 78·8 4·0 23 Hand/spray lay-up,
phthalic injection
5567 C 8000 orthophthalic 1·10 0·26 T 45 74 42·7 2·5 14 Hand/spray lay-up
5567 X 0004 orthophthalic 1·12 0·30 42 91 22 White, bath manufacture
5567 C 8026 orthophthalic 1·10 0·27 40 72 51·7 2·0 16 Resin injection
5567 C 8060 orthophthalic 1·10 0·27 T 43 70 48·0 18 Hand/spray lay-up,
fast cure
5567 C 8106 isophthalic Clear, resin injection
5568 Z 0001 fire retardant l-41 0-45 30 69 21·5 9·5 Filled, BS 476
pt 7 class I
5618 C 8005 isophthalic Brush gelcoat, clear
5618XOOO5 isophthalic Brush gelcoat, white
5618 X 0007 isophthalic Brush gelcoat, white,
fire retardant
5619 C 8005 isophthalic Spray gelcoat, clear
5619 X 0005 isophthalic Spray ge1coat, white
oc
'-&)
- Test methods 4 5 6 7 9
[email protected]
71 1·09 0·65 40 9 101 56 3·3 16 Chemical resistant grade
83 flexible 1·14 0·35 28 8 37 14 27 51 Flexible resin
213 FM low shrinkage 1·07 0·4 3 98 23 1·7 47 Low shrink, encapsulation
249 1·10 0·35 37 8·5 99 70 3·0 20 Fuel tank grade
292 orthophtha1ic 1·10 0·35 37 9 89 60 2·0 18 General purpose
294 T 1·10 0·35 37 8·5 98 69 3-0 21 Food industry grade
297 1·18 5·0 20 7 50 63 4·9 25 Hot press moulding
453 self-extin- 1·25 0-4 30 8 94 67 3-8 22 Fire retardant
guishing
502 1·11 0·25 38 9 60 34 H 16 High clarity for
roofing sheets
533 1·10 0·2 38 8·5 69 62 3·0 18 Casting resin
574 orthophthalic 1·11 0·25 38 8 68 56 2·0 13 General purpose
Table 9.6 (Continued)
.:
;: ~ .s=
.S ---'" -:: ~
---
;. ~ '-
~ s::: ~ ~ ~
~ '- c .... s::: c
be G ;:;" .s=
"~ 0 i~
Supplier .2\") ""s::: '-
... ~
$" '" 0 ~~
Trade name c'" ""'.s...." f.... ",Q., ~ ~'-
Type
" "'" "~~ § ~
Product code ~ ~';j ci;~ ~ ~~ ~ ~ ~ Remarks
Norsadyne (contd.)
601 1·10 0·14 38 8·5 80 64 4-4 23 Translucent, building grade
904 1·11 0·35 38 For SMC
~
- Test methods 6
[email protected]
D09BS 1·12 0·85-0·95 35 8·0 80 44 1·5 Casting, encapsulation
D 13 T orthophthalic 1·15 T 28 55 2·4 Ge1coat
DIS 1·14 2·0-2·2 30 7·5 77 55 2-4 Hot press moulding
D18RC 1·12 0·85-0·95 33 8·2 80 52 2·2 Coatings
D 20 1·12 0·6-0·65 36 8·2 84 52 2·2 Cold press moulding
D 26 1·10 0·22-0·25 42 8·2 90 50 1·9 Hand/spray lay-up, injection
D 35 R 1·07 0·06-0·08 50 10 95 58 2·1 Polyester concrete
D 320R 1·12 0·67-0·75 36 7·3 69 59 2·7 Continuous sheet pro-
cessing
D 325 1·11 0-4-0-45 38 7-3 70 50 1·8 Vacuum casting
D 328 SN 1·10 0·2-0·25 43 7·6 70 50 1·8 Sandwich panels
D 416 R2 1·13 1·2-1·3 34 8·0 72 45 1·3 Buttons
D 420 R 1·12 0·6-0·65 36 8·2 84 57 2-4 Contact moulding
D 426 1·10 0·22-0·25 44 8·4 86 58 2·3 Hand/spray, injection
D 426T 1·10 0·65-0· 75 40 8A 86 58 2·3 Hand/spray lay-up
D 428 T 1·09 0·3-0·38 42 8·4 86 58 2·3 For tropical use
D 430 TN 1·100·37-0·43T42 8·4 90 56 2·2 Long pot-life, general
purpose
D 1524 N 1·12 0,3-0·35 39 8·5 62 60 2·8 Good impact strength
D 1207 MRL methyl meth- 1·12 0·27-0·29 40 9·4 66 65 3·2 Continuous sheet
acrylate production
D 2522 RU 1·10 0·65-0·7 36 8·4 73 63 3·8 Continuous sheet
production
D 2530 TS 1·08 0·4-0·5 T 45 8-5 78 69 3·8 Fast production rate
D 2730 VU 1·09 0·14-0·17 45 9-2 74 57 2-2 Continuous sheet
production
D 2807 F 1·17 4-8-5'2 24 5-4 47 45 3·0 Hot press moulding
D 3232 isophthalic 1·07 OA-0'45 46 8·4 96 75 3·3 Corrosion resis-
::0 tant, SMC
- D 3319 1·14 2·0-2·2 34 8-0 60 79 4·8 SMC
D 3325 S 1·!2 O· 55-0·65 40 8·2 70 60 3·0 Containers
D 3422 VU H2 0-65-0-7 39 8- I 54 54 2-2 Continuous sheet
production
[email protected]
C 60-150 0 Pigment dispersing resin
C5 1·19 <30 0 Pigment dispersing resin
C 113 TIL isophthalic I- 14 5·0-6·0 T 28 8·3 60 45 9·1 Clear gelcoat
C 1I5 T isophthalic 1-14 17·5-22 T 34 8·3 60 45 9·1 Gelcoat and addition
to other resins
C ll8 isophthalic 1-14 0'6-0,65 34 8·3 60 45 9-1 Ge1coat, cold press
moulding
C 215 T3 orthophthalic 1-15 4-0-5-0 T 30 5- I 60 49 H Clear gelcoat
C 420 1-13 1-2-1'3 35 57 68 4-5 Buttons, coatings
CIF 5100 self-extin- 1·66 1·4-1·6 26 Cold press moulding,
guishing etc.
Table 9.6 (Continued)
~
.:
;;: ~ .:=:
~ "" -S
';: ~ ~ ~
---~ ~
~ I:: C
'-- c\..l I::
~ b/) G ~ .:=: oC)
""<:1---
I.> .2u '<:I" ~
Supplier .., 0 I::
'" """'~ Io...~
$ f...
Trade name I.> 8~ "'.5..." ~~ "''--
'" "
'~~ ~c
Product code Type ~ :::~ ~~ t5 § ~~ 1:<l ~ E" Remarks
Ukapon (contd.)
CIF 75185 self-extin- 1·49 0·9 -1·0 24 91 Filled, contains no
guishing chlorine
::0
N
CIF 76176 self-extin- I· 38 0·32-0·37 36 60 Filled, contains no
guishing chlorine
F210 flexible 1·18 104-1·6 25 6·7 IS 30 Flexi bilising resin
F 335 flexible 1·02 0·6-0·65 50 9·5 4·7 140 Flexibilising, casting
F 418 J flexible 1·12 0·6-0·65 34 8·8 18·5 18 Putties
[email protected]
F 531 S flexible 1·16 0·2-0·25 36 6·3 10 90 Pipe jointing
IF 220 R chlorinated diol 1·20 0·4-0·45 36 8-4 101 51 3·2 Self-extinguishing
IF 520 chlorinated diol 1·24 0,6-0·65 34 7·) 75 55 3·0 Self-extinguishing
IF 1126 self-extin- 1·14 0'11-0·13 50 8·8 52 48 4·8 Contains no chlorine
guishing
IF 1217 S 1·27 0·25-0·3 50 7-3 42 5·4 U sed in CIF 5100
IF 1325 fire resistant 1·22 1,2-104 40 8·1 130 65 2·9 SMC
T 120 SI 1·10 1·05-1·15 40 8·5 125 41 1·5 Heat resistant, SMC
T 215 MRL methyl meth- 1·16 0·22-0·25 41 7·5 85 56 2·3 Transparent sheets, etc.
acrylate
T 215 MARL methyl meth- 1·10 0·14-0·17 43 7·5 87 55 2·2 Transparent roof lights
acrylate
T 216 1·13 1·2-1·3 32 7·6 106 50 1·9 Cold press moulding
T 260WDC 1·08 0·11-0·15 39t t Without styrene
for SMC
T 723 J 1·09 0·6-0·65 38 9·5 81 45 1·4 Putties
T 620 1·12 1·4-1'6 32 7·3 79 64 3·5 Cold press moulding,
winding
T 623 1·10 0·6-0·65 35 8·1 86 70 3-8 Transparent, injec-
tion moulding
T 624 PS J.09 0·27-0·32 40 8·2 90 70 3-8 Centrifugal moulding
T 928 1·\0 0·85-1·0 42 8·6 140 25 1·0 Low shrink with
75131 and 75132,
low profile with 76118
Ukadiol 220 S chlorinated diol 1·22 0·6-0·65 40 6·8 100 55 2-4 Self-extinguishing
~
t.H Test methods ISO 6 8 8
[email protected]
zero shrink SMC/DMC
P-543 low profile 0·98 1·2 67 Acrylic polymer/
additive styrene syrup
P-681 low profile 0·98 1·32 70 Acrylic polymer/
additive styrene syrup
P-701 low profile Acrylic polymer/
additive styrene syrup
P-713 low profile 0·98 I· 5 70 Thermoplastic polymer/
additive styrene syrup
Table 9.6 (Continued)
~
---- ;;; -S .9
.~ '" ~ ---- ~
----
~ ~ ~ "-- ~
I::
"-- <::> I::
'"::!
b< ~o, .9 ]
.~\.,) '~" o:s----
Supplier o, 0
"I::
'" ~ "'----
:s-" <::>.,., ""~
Trade name ·5
t.... ~~ ~ "'''--
"
'" '-'"" "
'""----
c.~
...
..0: ~
Product code Type ~ ~~ CIl~ CIl ~ ~~ t<l ~ ~ Remarks
[email protected]
HET acid stabilised
Gelcoat 46PA isophthalic 1·40 T 65 35 1·1 17 Light stabilised, low
fire hazard
Gelcoat 47PA HET acid 1·48 T 65 35 1·0 18 Light stabilised, low
fire hazard
GeJcoat 65PA isophthalic 1·11 T 36 75 70 2·5 17 Resilient, marine
applications
GeJcoat 68PA isophthalic 1·10 T 65 65 3·0 17 Spray application
GeJcoat 69PA isophthalicj
NPG 1·10 T 90 65 2·5 15 Chemical and water
resistant
Fireguard 75PA HET acid 1·35 T 53 Intumescent coating
II3PA orthophthalic 1·10 T 62 65 2·0 16 Low styrene emission,
general purpose
189LV orthophthalic 1·15 0·36 38 60 70 4·0 13 Tough, long 'green' stage
189MV orthophthalic 1·l7 0·9 33 56 70 4·0 13 Tough, long 'green' stage
191LV orthophthalic 1·11 0·35 36 66 60 2·0 19 Clear, light stabilised
193HR orthophthalic 1·11 0·18 40 64 65 2·3 22 Methyl methacrylate,
light stabilised
196 orthophthalic 1·12 0·9 33 72 69 2·3 16 Resilient, general purpose
198 orthophthalic 1·11 0·65 36 110 60 2·1 25 Chemical resistant
199 isophthalic 1·10 0·6 38 130 62 2·5 25 Good temperature and
chemical resistance
272 isophthalic 1·10 0·35 41 75 75 3·5 16 High performance,
winding, etc.
302 HET acid 1·33 1·05 27 60 55 1·9 12 BS 476 pt 7 class 2
306 HET acid 1·18 0·35 31 52 48 4·0 30 Light stabilised, fire
retardant
323PA orthophthalic 1·20 0·8 33 70 43 1·4 13 BS 476 pt 7 class 2,
:c
v. opaque
328PA orthophthalic 1-39 T 60 35 I· 3 26 Opaque, low fire
hazard, class 2
345PA orthophthalic/ 1-45 T 72 30 0·6 12 BS 476 pt 7 class 1,
HET acid opaque
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346PA HET acid 1-48 T 64 35 0·5 12 BS 476 pt 7 class 1,
opaque
385PA isophthalic/ 1·15 T 70 55 2·9 30 BS 476 pt 7 class 2,
HET acid clear
386 HET acid 1·33 0·2 50 46 1·5 12 BS 476 pt 7 class 1,
light stable
389PA orthophthalic 1·l7 T 60 50 2·0 20 BS 476 pt 7 class 2,
clear
390 isophthalic 1·14 0·95 52 68 6·0 20 Tough, flexible, gelcoats
392 isophthalic/ 1·07 0·8 90 70 3·0 14 Laminates on uPVC
NPG
Table 9.6 (Continued)
s::'
.::. 0: "S ;;-.: ·9
.;:
--'"
~ ~ --
~ be ----
'-- ~
~ '--
s:: <::>
<::> s::
be <J G
.....s:: .Q
'"
<J
, ~ ·9
Supplier .~<;,.)
., 0
~ '--
:s <::>",
"'< .. -- ~~
<J .5 ~ 'E;~ ~'--
...s::
Trade name .. l:!'" ""---- ... ~
~
<::>
Product code Type ~ s:~ ~~ ~ ::t:: ~~ t<i ~ ~ Remarks
Crystic (con/d.)
405PA orthophthalic 1·12 T 69 65 2·0 18 Marine use
406PA orthophthalic \·10 T 62 65 2·0 16 Low exotherm, fast
mould release
~
- 471PA orthophthalic 1·1\ T 72 69 2·0 17 Spray, short mould
release
474PA orthophthalic 1·10 T 110 60 2·1 25 Thixotropic version
of 198
491PA isophthalic 1·1\ T 40 75 75 2-9 19 High performance, chem-
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ical resistant
504 orthophthalic 1·1\ 0·35 67 65 1·8 18 Cold press moulding
505 orthophthalic 1·19 0·52 62 60 1·4 12 Low fire hazard,
cold press
506 orthophthalic 1·1\ 0·35 75 69 2·0 17 Resin injection, cold
press, clear
586 fatty acids 1·14 0·31 45 Flexibilising, putties
600PA bisphenol 1-04 0·75 47 120 70 4·0 17 Chemical resistant
625MV isophthalic 1·13 0·8 94 65 2·2 18 High performance
17449 DCPD modified 1·10 0·38 115 60 2·0 27 Heat resistant
[email protected]
595 isophthalic 1·12 0·7-0·9 40 H 95 64 1· 3 Rigid, chemical resis-
tant
711 flexible 1·05 0·8-1·1 28 5·1 9-4 65 Mortars, etc.
822 HET acid 1·28 1·8-2·2 25 7·0 82 98 2·8 Self-extinguishing,
hot press
823LS HET acid 1·27 0·6 26 5·8 46 24 10 Light stabilised,
sheets
892 HET acid 1·34 1·6-2·2 29 6·1 90 34 1-4 Fire retardant, chem-
ical resistant
922 T 6·0 Thixotropic paste,
8% Aerosil
940 isophthalic T 7·0 95 Ge1coat based on
594LS
Table 9.6 (Continued)
i
o,
""" ~ .S::
C- ~ ~ """
.;: ~ ~
~ I:: ~ ~ e.
C
'-- c .. I:: o,
G ~
.:::'o," .S
0
t .S\.) '-- <::I"'
Supplier ., 0
$" c.,.,
.."I:: t-. "'--- t...~
~'--
.. .....5""<::I
Trade name ... ~~ ~c
.." ~~ ~
Product code Type ~ "'"
~~ VJt... ~ ::t; ~~ ~ ~ E' Remarks
Synolite (contd.)
943 orthophthalic 1-14 T 6·5 94 49 1-3 High reactivity
version of 375
945 orthophthalic T 6-3 45 Gelcoat based on
~ 544LS/711
00
[email protected]
34-308A isophthalic 2-2-3-2 115 66 2-2 (0-09) Gelcoat, tooling,
marine, etc_
54-01A isophthalic 2-5-3-5 79 69 3·4 (0-28) White version of
34-02A
259A flexible 2-0-3-0 53 38 3-5 (0-17) Gelcoat
633A fire retardant 1-5-2-5 50 38 3-0 (0-06) White gelcoat
644A 1-5-2-5 67 49 2-0 (0-06) Gelcoat also as low
viscosity grade
DralamLSE 25-01A 0-3-0-4" 70 45 2-0 (0-13) Low styrene emission,
GP resin
LSE 27-0IA 0-3-0-5 140 59 2-5 (0-06) Low styrene emission,
chemical resistant
LSE 28-02A fire retardant 0-35-0-45" 58 29 I-I (0,17) BS 476 pt 7 class 2, clear
33-01A T Thixotropic paste,
adhesives
33-072A 0·15-0·25 70 38 1-4 (0·13) Hand/spray lay-up
33-402NA 0·5-0·6 106 42 3·2 (0·09) Filament winding
80-1403 orthophthalic 2·0-2-6 106 29 2·0 (0·13) Hot press moulding
80-1405 isophthalic 2·2-3·0 82 73 3·0 (0·13) Hot press moulding
83-1571 low profile 1·5-2·0 Low shrink, SMC
90-1001 0·6-0·9 Pigment grinding resin
228A 0·15-0·3 70 59 1·5 (0·1) General purpose
466/6A Thixotropic bonding paste
500A 0·2-0·4 130 35 2·0 (0·07) Chemical resistant
BH 703F 0·6-0·8 94 (0·1) Low colour casting resin
1346 0·1-0·14 78 50 1·1 (0·08) Translucent sheets
1347 fire retardant 0·1-0·14 50 37 1·2 (0·23) Translucent sheets
1355A fire retardant 0·35-0·45 82 29 1·1 (0·13) White, BS 476 pt 7
class 2
~
- 1368A 0·3-0·5 140 60 2·5 (0·06) Chemical resistant
1385 fire retardant 0·25-0·35 78 50 1·7 (0·1) Resin injection
2073A 0·3-0·5" 90 Acrylic bath reinforce-
ment
4620 0-4-0·6" 115 56 2·0 (0·16) Chemical resistant
[email protected]
5320 bisphenol 0·3-0·6 115 60 3·0 (0·1) High chemical resistance
8005 0·2-0·3 92 52 1·5 (0·08) Resin injection
8048S 0·2-0·35 70 59 1·5 (0·1) Spray lay-up, fast cure
8151 flexible 0·35-0-45 (0·55) Flexibilising resin
8227A 0·4-0·5 73 48 1·7 (0·11) Surface coating resin
8726AHT 0·15-0·3 70 59 1·5 (0·1) Hand/spray lay-up
8748A 0·3-0·5 70 59 1·5 (0·1) Hand/spray lay-up
8800A 0·5-0·8 92 31 0·9 (0·07) Cold press moulding
Test methods 6 8 8 9
~
~ --"" ~ -;:: ,0
.;; ~ ~-- ~
'Sl"
~ '-- ~ ~
'-- ~ S;
~ "" ~ v ';; "Sl ~~
.2v " <::
Supplier ., 0 ~ ~
:s." ~~ 10..~
Trade name .5 f.... .,Q" ~ ,,'--
"" ~~ """~~ ... Q
Product code Type ~ ~~ V3~ C'l
"" ::t:: ~~ "
~ ~ ~ Remarks
Norpol (contd.)
42-00 orthophthalic 1·12 1·2-1·7a 34 6 80 64 1·5 General purpose
42-04 1·12 1·2-1·7a 34 6 80 64 1·5 Tropical grade
N
8 43-01 orthophthalic 1·11 0·6-0·7a 35 5 65 54 1·6 Light stabilised,
sheets
44-20 1·10 0·9-1·1 Ta 43 6 68 1·4 Fast cure, spray
44-30 1·10 0·9-1·1 T" 43 6 68 ~ 104 Slow cure, spray
44-70 orthophthalic 0·9-1·1 Ta 43 6 54 104 Fast cure, hand/spray
[email protected]
1·10 68
44M-75 1·10 0·85-1·1 T" 42 6 65 50 1·6 Low styrene emission
44-80 orthophthalic 1·10 0·9-1·2 Ta 42 6 65 50 J.6 Low exotherm
44M-85 )·)0 0·8-),) Ta 42 6 65 50 ),6 Low styrene emission
45-50 orthophthalic 1·10 0·5-0·6" 34 3 Light stabilised, clear,
casting
48-00 1·13 )·2-],7" 34 7 84 68 H Chemical resistant
68-00 isophthalic 1·10 0·8-]·D" 37 ]30 50 I· 5 SMC,DMC
72-00 isophthalic 1·13 1·2-1'7" 34 7 83 70 3·0 Oil tanks, pipes, etc.
72-70 isophthalic 1·11 1·0-1·3 T" 7 88 69 2·8 Oil tanks, pipes, etc.
73-00 flexible, isophthalic 1·13 1·2-1·7" 34 7 52 66 6·0 FlexibiIiser, high impact resistance
80-20 chlorinated paraffin 1·21 0·7-0·9 T" 37 6 72 59 1·6 Opaque, self-extinguishing
90-00 bisphenol Chemical resistant
GA acrylic/ 1·2 13-16 T" 35 6 83 54 2·2 Gelcoat, hand
isophthalic application
GA acrylic/ 1·2 9-12 T" 40 6 83 54 2·2
- Gelcoat, spray
isophthalic application
GI isophthalic 1·2 13-16 Ta 35 6 74 49 2·6 Gelcoat, hand
application
GI isophthalic 1·2 9-12 Ta 40 6 74 49 2·6 Gelcoat, spray
application
GM 925 1·2 11-13T" 35 6 102 40 1·6 Gelcoat, hand, tooling
GM 925 1·2 9-12 T" 40 6 102 40 1·6 Gelcoat, spray, tooling
GM 930 1·2 11-13Ta 35 6 76 60 3·3 Flexible gelcoat, hand,
tooling
GM 930 1·2 9-12 T" 40 6 76 60 3·3 Flexible gelcoat,
spray, tooling
N
:= Test methods ISO 6 8 8
[email protected]
9 TSE AC LSE self-extin- 1·31 0-4-0·5 T 32 65 BS 476 pt 7 class 2
guishing
B9TA bisphenol 1·05 0·4-0·5 T 50 135 Manufactured from
Atlac 382
19 T LSE isophthalic 1·10 0·4-0·5 T 45 110 Chemical resistant
15 T 1·12 1·2-l-6T 31 65 Thixotropic, general
purpose
129 T GAC isophthalic 1·14 2·0-2·5 T 34 65 Resilient gelcoat
I 29 T GAC white isophthalic 1·14 2·0-2·5 T 34 65 Resilient gelcoat
230 AC 1·13 0,45-0,55 35 72 Pre-accelerated
version of 312/35
312/35 LSE 1·12 0·5-0·6 35 72 General purpose
1188 1·13 0·3-0·35 37 125 High HDT
Table 9.6 (Continued)
~ ,,'
~
~ ,0 9
'" ~ "Sb()
.;:
=- ~
~ ~ ~
c
1:'b() "c b() V
"..
;;;'" ~
."---"
" '"<:! 0 9 '"
<:!~
Supplier .2v "'~ ... ~
:$
" '" f.., ~
Trade name ~ .5 ~~ "'---
~~ Q
"'.'"" ..
"""...,
Product code Type
"'" "'~ "c Remarks
~ ~~ ~ :t:: ~~ i'il ~~
::::"
Polymaster (contd.)
1209 AC 1-12 0-2-0-25 35 50 Colourless casting
resin
1592 flexible 1-17 0-6-0-8 28 Amine accelerated
N 1704
0 1-24 T 32 Amine accelerated
N
bonding paste
1775 AC 1-22 T 32 Resilient bonding paste
1959 1-!7 0-1-0-14 0 For colour pastes
2003 fire retardant 1·28 0-35-0-38 29 65 BS 476 pt 7 class I,
[email protected]
clear
2110 1·12 0-1-0-15 40 90 Resin injection
2123 self-extin- 1-16 0-1-0-15 30 75 BS 476 pt 7 class 2,
guishing resin injection
2136 light stabilised 1-13 0-17-0-18 33 65 Translucent sheet
2197 TAC LSE self-extin- 1-48 0-5-0-6 T 31 70 Opaque, BS 476 pt 7
guishing class I
2345 AC methyl I-ll 0,14-0-16 40 50 Translucent sheet
methacrylate
2580 1-16 1-0-1-2 28 Amine accelerated for
site use
2685 TAC LSE self-extin- 1·200·25-0·3T 33 55 Clear, BS 476
guishing pt 7 class 2
I 2722 TAC LSE isophthalic 1·16 0-4-0·5 T 42 115 General purpose
2774 self-extin- 1·18 0·24-0·28 30 Clear, BS 476
guishing pt 7 class 2
2774 AC self-extin- 1·20 0·14-0·16 40 53 Clear, BS 476.
guishing pt 7 class 2
12798 T/GAC isophthalic 1·14 1-0-1·2 T 40 65 Gelcoat
2946 TAC LSE isophthalic 1·11 0·3 T 37 70 Laminating resin
2946 TAC LSE isophthalic 1·11 0·3 T 37 70 White laminating resin
white
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Styrene content 5 = BS 2782 Method 107B; II = DIN 16945.
Shrinkage 12 = DIN 16946.
HDT 6 = ASTM D 648-72 = ISO/R 75 = BS 2782 Method 121 A & B = DIN 53461.
Tensile strength 7 = ASTM D 638-77a = DIN 53455;
and elongation 8 = BS 2782 Method 320 A-F (301 A, 302 D) = ISO/R 527.
Water absorption 9 = BS 2782 Method 502 G = ISO/R 62 = DIN 53475.
10 = ASTM D 570-77.
Chapter 10
10.1 INTRODUCTION
204
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UNSA TURA TED POLYESTER RESINS 205
Catalysts and accelerators should never be mixed together since this will
result in violent decomposition of the peroxide with the risk of fire and
explosion.
Although the wide range of catalysts available gives considerable scope
in selecting a system with the desired pot-life, occasions can arise when it is
desired to lengthen the pot-life without altering gel and cure times so that
demoulding is not affected. This can be accomplished by adding an
inhibitor to the system. This is in addition to the inhibitor already present in
the resin. Some inhibitors increase pot-life, gel time and cure time whilst
others just extend gel time-such an effect is shown in Fig. 10.1.
In order to achieve the optimum cured properties from the resin system,
the catalyst and accelerator must be chosen with care and the correct
amount used. Suppliers generally recommend particular catalyst!
accelerator combinations for use with each of their resins, together with rec-
ommended proportions. These systems have been arrived at by experimen-
tation and when used as recommended will give cured resins with optimum
properties-mechanical, chemical, etc. Often more than one catalyst/accel-
200
2
160
u
0
3
~
III
L. 120
.....It!
::I
L.
III
0-
S 80
III
I-
40
20
0 10 20 30 40 50 60
Time, minutes
Fig. 10.1. Effect of inhibitor on gel time and cure rate. Formulations: 1, resin
(Vestopal150) 100, MEK peroxide 2, cobalt accelerator (1% Co) 0·3; 2, resin
(Vestopal150) 100, MEKperoxide 2, cobalt accelerator (1% Co) 0·3, inhibitor (1%
solution) 1; 3, resin (Vestopal150) 100, MEKperoxide 1, cobalt accelerator (1%
Co) 0·14. (Courtesy of Huls (UK) Ltd.)
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206 FRP TECHNOLOGY
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UNSATURA TED POLYESTER RESINS 207
Peak exotherm
150
o
u 100
~
~
:::l
+->
E 50
QJ Gel time
0-
S
~ 25
10 20 30 40 50 60
Time, minutes
Fig. 10.2. A typical exotherm curve.
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208 FRP TECHNOLOGY
an active oxygen content of 3·2%. Various methods are used for determin-
ing active oxygen content. 1
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UNSA TURA TED POLYESTER RESINS 209
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210 FRP TECHNOLOGY
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UNSA TURA TED POLYESTER RESINS 211
2.4-Dichlorobenzoyl peroxide
Molecular weight 380
Active oxygen content 4·28%
Critical temperature 60°C
Maximum storage temperature 25°C
Half-life: Temperature COc) 50 60 70 80
Time (h) 17·8 8·2 1·4 0·5
2,4-Dichlorobenzoyl peroxide is used with an amine accelerator either
alone or in combination with benzoyl peroxide to obtain gelation of
polyester resins down to O°C, providing that a post cure above 15°C is given
to ensure full cure. It has a low peak exotherm when used below 70°C and
can be used to produce fairly large crack-free castings. It finds use in
contact moulding, hot press moulding and low temperature curing systems.
Dilauroyl peroxide
Molecular weight 404
Active oxygen content 4·0%
Critical temperature 65°C
Maximum storage temperature 25°C
Half-life: Temperature COc) 50 62 70 80 100
Time (h) 60 10 3 I 0·1
Dilauroyl peroxide is used in heat cured systeIlls over the temperature
range 60-80°C. It is effective some 10-15°C below the temperature needed
to obtain full cure with benzoyl peroxide. It does not affect the yellowing of
polyester resins. It is a powder which is directly soluble in the resin.
Diacetyl peroxide
Molecular weight 118
Active oxygen content 13·6%
Critical temperature 75°C
Maximum storage temperature 25°C
Half-life: Temperature COc) 50 70 100
Time (h) 190 7·3 0·2
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212 FRP TECHNOLOGY
Diacetyl peroxide is only suitable for use in heat cured systems and finds
application in SMC and DMC. No yellowing of cured systems is observed
on ageing.
This is perhaps the most common class of peroxides used with polyester
resins. Two commonly encountered ketone peroxides are methyl ethyl
ketone (MEK) peroxide and cyclohexanone peroxide. These are used for
cold curing polyester resins in the presence of a cobalt accelerator. Whilst
they are described as peroxides they are in fact mixed peroxides containing
a number of different products. Cyclohcxanone peroxide is also used at
lS0°C to prevent staining of metal moulds.
Other peroxides included in this class are acetylacetone peroxide, methyl
isobutyl ketone peroxide and various ketone peroxide mixtures. The
typical chemical structure for the pure ketone peroxide is shown on the left
above whilst the hydroperoxide structure is shown on the right.
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UNSA TURA TED POLYESTER RESINS 213
Cyclohexanone peroxide
Molecular weight 228
Active oxygen content 13-1%
Critical temperature 88°C
Melting point 7SoC
Maximum storage temperature 2SoC
Half-life: Temperature eC) 70 80 90 100 120
Time (h) 140 34 9 7·7 0·9
Cyclohexanone peroxide is available as a pure powder, a SO% paste in a
phthalate plasticiser and in solvent solution. Like MEK peroxide it is a
mixture of different compounds. I t is used with a cobalt accelerator over the
temperature range 0- 2SoC but, if used below ISoC, a post cure above this
temperature is necessary to achieve full cure. Tertiary amine accelerators
can also be used but polyesters cured in this way have a tendency to yellow
with age. It is often used in body stoppers with a mixed tertiary
amine/cobalt accelerator. It can also be used without an accelerator to cure
polyester resins at temperatures above 160°C.
Very long pot-life systems can be obtained by using a manganese
accelerator. Another accelerator sometimes used is vanadium octoate.
Cyclohexanone peroxide offers several advantages over MEK peroxide.
It generally gives a lower peak exotherm, is less sensitive to cure
temperature and has a lower tendency to yellow in transparent sheeting. It
is also preferred when a low stress cure is desired.
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214 FRP TECHNOLOGY
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UNSA TURA TED POLYFSTER RFSINS 215
Accele-
rator Kick-off Cure Peak Pot-
1% Co temp. time exotherm life
Catalyst (% wt) (0C) (min) (0C) (min)
Ketone mixtures
Various mixed ketone peroxides are available based on unspecified
ketones. These have generally been formulated for specific applications.
10.3.3 Hydroperoxides
General formula: R3 - C - 0 - 0 - H
Only two hydroperoxides are found in common use, namely, t-butyl
hydroperoxide and cumene hydroperoxide. Both can be used with cobalt
or vanadium accelerators.
t-Butyl hydroperoxide
Molecular weight 90
Active oxygen content 17·7%
Critical temperature 88°C
Maximum storage temperature 25°C
Half-life: Temperature eC) 100 120 130 150
Time (h) 170 12 3·2 0·4
This was one of the earliest hydroperoxides in use but is not so widely
used today due to its lower stability compared with MEK peroxide or
cyclohexanone peroxide. It can be used with a vanadium accelerator for
surface coating and dip coating applications. It has an inhibiting effect on
MEK peroxide/cobalt systems and lowers peak exotherm. It can be used
alone for elevated temperature cure.
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216 FRP TECHNOLOGY
Cumene hydroperoxide
Molecular weight 152
Active oxygen content 10·5%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature caC) 115 130 150
Time (h) 472 113 10
Cumene hydroperoxide can be used in high temperature cured dip
moulding compounds or combined with benzoyl peroxide for intermediate
cure temperatures. For example, with a blend of these two peroxides used
to cure a polyester resin at 70°C, the benzoyl peroxide starts to cure the
resin and when the temperature reaches 100°C the cumene hydroperoxide
takes over.
Cobalt and vanadium accelerators can be used with cumene hydro-
peroxide to give systems with long working times and good final cure.
Such systems find application with air drying topcoat resins.
Dicumyl peroxide
Molecular weight 270
Active oxygen content 5·9%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature (0C) 100 120 135 150
Time (h) 100 6·8 1·0 0·2
Dicumyl peroxide is generally used in potting compounds and sheet and
dough moulding compounds. It has an exceptionally long pot-life coupled
with good elevated temperature cure. It cannot be accelerated.
Di-t-butyl peroxide
Molecular weight 146
Active oxygen content 10·9%
Critical temperature 100°C
Maximum storage temperature 25°C
Half-life: Temperature caC) 100 120 150
Time (h) 210 20 0·8
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UNSATURATED POLYESTER RESINS 217
Di-t-butyl peroxide is used for hot cured systems where a long catalysed
pot-life is needed. Pot-life is not influenced by pigments. As supplied, di-t-
butyl peroxide is a highly volatile liquid; this limits its storage life and
hence its use.
10.3.5 Peroxyesters
General formula: R3-C-O-O-C-R
II
o
Several different types ofperoxyesters are found in use, mostly for hot press
moulding and sheet and dough moulding compounds. They can be used
over a wide range of processing temperatures from about 70°C to above
IS0°C.
t-Butyl peroxybenzoate
Molecular weight 194
Active oxygen content 8·2%
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218 FRP TECHNOLOGY
t-Butyl peroxydiethylacetate
Molecular weight 188
Active oxygen content 8·5%
Critical temperature 65°C
Maximum storage temperature 10°C-refrigerated
Half-life: Temperature eC) 50 70 90 100
Time (h) 330 19 1·7 0-46
This peroxide catalyst finds use in SMC, DMC and hot press moulding
compounds.
t-Butyl peroxyester
This peroxide catalyst is used for filament winding, hot press moulding
and continuous sheet manufacture over the temperature range 60-1 00°c.
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UNSATURATED POLYESTER RFSINS 219
Di-t-butyl diperoxyphthalate
Molecular weight 310
Active oxygen content 10·3%
Critical temperature 9SoC
Maximum storage temperature 2SoC
Half-life: Temperature (0C) 100 120 ISO
Time (h) 21 1·2 0·01
This peroxide catalyst gives systems with a long pot-life. It is used for hot
press moulding at temperatures above IS0°C.
t-Butyl peroxypivalate
Molecular weight 174
Active oxygen content 9·2%
Critical temperature SO°C
Maximum storage temperature O°C-refrigerated
Half-life: Temperature (0C) SO 70 90
Time (h) 23 1·9 0·16
t-Butyl peroxypivalate is used for hot press moulding in the temperature
range 90-110°C where it gives a short cure cycle. It can also be used for
continuous sheet production. If accelerated with a cobalt or vanadium
accelerator it can be used in the temperature range SO-70°C. It gives less
yellowing than benzoyl peroxide. The major disadvantage is that it requires
refrigerated storage.
2,5-Dimethylhexane-2,5-diperoxybenzoate
Molecular weight 386
Active oxygen content 8·3%
Critical temperature
Maximum storage temperature 2SoC
Half-life: Temperature caC) 100 118 ISS
Time (h) 10 1 0·017
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220 FRP TECHNOLOGY
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UNSATURATED POLYESTER RESINS 221
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222 FRP TECHNOLOGY
Cobalt accelerators
These are based on such materials as cobalt siccatolate, naphthenate or
octoate. Solutions are available with cobalt concentrations ranging from
O' 5 to 10%. The more concentrated solutions are either diluted before use or
added directly to large batches of resin to reduce the amount of diluent or
plasticiser added. The typical level of cobalt used with a normal polyester
resin is between O' 5 and 2% of a solution containing I % of cobalt. Cobalt
accelerated resins tend to be pale pink in colour.
Manganese accelerators
Manganese salts are occasionally used as accelerators for polyester resin
systems. They give long gel times at ambient temperature when used to
accelerate ketone peroxides (Table 10.2).
Vanadium accelerators
Vanadium accelerators are used to accelerate ketone peroxide catalysed
polyester resins for low temperature cure or peroxyester and perketal
catalysed systems at elevated temperatures. They give faster hardening
Table 10.2 The effect of cobalt and manganese accelerators on gel time of a general
purpose polyester resin
5(/'/0 Cyclohexanone
peroxide paste, 50% MEK peroxide,
2"/0 addition 2"/0 addition
Temperature eC) 20 40 50 20 40 50
Accelerator
Cobalt salt (l % Co) 22 13 9 18 13 8
Manganese salt (l % Mn) 316 55 25 495 88 41
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UNSA TURA TED POLYESTER RESINS 223
NN-Dimethylaniline
This is normally referred to as dimethylaniline. It gives normal gel times
and quick cure when used to accelerate diacyl peroxide catalysed systems.
It can also be used as a co-accelerator with cobalt accelerated ketone
peroxide catalysed systems to reduce gel times. In this respect it is of
particular use in cold press moulding and resin injection systems.
N N- Diethylaniline
This is normally referred to as diethylaniline. It gives long gel times
coupled with fast cure at room temperature when used as an accelerator in
benzoyl peroxide catalysed resin systems.
Table 10.3 Effect of different tertiary amines on gel time of a general purpose
polyester resin
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224 FRP TECHNOLOGY
Table 10.4 Effect of mixed accelerator on gel time of a general purpose polyester
resin system
General purpose polyester resin 100 100 100 100 100 100
Cyclohexanone peroxide (50%) 2 2 2 2
MEK peroxide (50%) 1 1
Cobalt naphthenate (1 % Co) 1 1·5 1· 5
Dimethylaniline (10%) 0·1 0·75
Dimethyl-p-toluidine
---- .-~~-----~-.
NN-Dimethyl-p-toluidine
Dimethyl-p-toluidine gives short gel and cure times in conjunction with
benzoyl peroxide catalysed resin systems. It is used where short moulding
cycles are needed with ambient temperature cure.
10.5 INHIBITORS
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UNSA TURA TED POLYESTER RESINS 225
Two inhibitors which are used to prolong pot-life are t-butyl catechol
and di-t-butyl-p-cresol. Some of the commercially available inhibitors are
listed in Table 10.7.
REFERENCES
1. Chalkley, N. J. and Whalley, C. (1978) Proc. Anal. Div. Chern. Soc., 15,
December, 327.
2. Simmonds, 1. (1974) Reinforced Plastics, February, 41.
[email protected]
Table 10.5 Commercial peroxide catalysts tv
tv
0'1
Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code
Benzoyl peroxide
Akzo Chemie UK Ltd
Lucidol Soft powder + 25% water 75 4·9 A
Lucidol B-50 Paste in phthalate plasticiser 50 J3 D 1, 2, 4, 6, 7, 8, 10
Lucidol B-25 Paste in phthalate plasticiser 25 1·7 D 1, 2, 4, 5, 6, 7, 8, 9, 10
Lucidol M-60 Paste in phthalate plasticiser 60 3·9 D 1,2,4,6, 7, 8, 10 >rj
~
Lucidol C-50 Paste in phosphate plasticiser 50 J3 D 1,2 '"C
Lucidol S-50 Paste in silicone fluid 50 3·3 D ..,
ttl
("')
Lucidol G-20 White powder in calcium sulphate 20 1·3 C 10, 12 :I:
Lucidol 50 PO White powder 50 3·3 C 5 Z
0
Lucidol40 Pourable emulsion 40 2·65 D 1, 2, 5, 6, 7, 8, 9 t"'
Lucipal E White powder BP/amine complex 16 1·1 C 10,11 8-<
[email protected]
Interox Chemicals Ltd
Interox BP 70P Paste 70 4·6 3
Interox BP 60P Phthalate paste 60 3·9 4 1,2,6
Interox BP 50P Phthalate paste 50 3·3 4 1,2,6
Interox BP 50 FT Soluble powder 50 J3 4 1, 2, 4, 5, 6, 11
Interox BP 60 P CL Paste in Cerechlor 60 3·9 4 4,5,6, 11
Luperox GmbH
Luperco ANS-50 Phthalate paste 50 3·3 1,2, 3, 6, 8, 12
Luperco BP Phthalate paste 55 3-6 1,4,6, 10
Luperco ANS-50-AT Phthalate paste 50 3·3 10
Luperox FL Plasticiser suspension 36 2-4 2,3,6
Luperco ANS-60 Phthalate paste 60 4·2 3, 6, 7, 12
Scott Bader Co. Ltd
Catalyst powder B Paste 50 3·3 6
2,4-Dichlorobenzoyl peroxide
Akzo Chemie UK Ltd
Peradox SD White powder + 50% water 50 2·0 A
lnterox Chemicals Ltd
Interox DCLBP 50PSi Paste in silicone oil 50 2·1 4
c::
Dilauroyl peroxide Z
U'.>
Akzo Chemie UK Ltd ..,>
Laurydol Granular 98 3-94 B 12 c::
Laurydol B-40 Phthalate paste 40 1·6 D 4, 12 ~
@
lnterox Chemicals Ltd 0
Interox LP Powder 95 4·0 4
0-=
t""
Diacetyl peroxide -<
Akzo Chemie UK Ltd
rn
@
Trigonox RM-25 Solution in dimethyl phthalate 25 H E 7 ~
[email protected]
Di-n-octanoyl peroxide (caprylyl peroxide) ~Z
Akzo Chemie UK Ltd U'.>
MEK peroxide
Akzo Chemie UK Ltd
Butanox LPT Solution in phthalate plasticiser 8·4 G 3,9, L
Butanox M-50 Solution in phthalate plasticiser 9·0 G 1,2,4, 8, 11, 12, 13, H
Butanox AM-50 Solution in phthalate plasticiser 10·75 G 1,2,4, 13, VH
Butanox B-50 Solution in phthalate plasticiser 9·0 13,H N
G N
I, 2, 4, 8, 11, 12, 13, VH -..J
Butanox PC Solution in phthalate plasticiser 7·9 G
Table 10.5 (Continued)
IV
IV
00
Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code
[email protected]
Luperox GmbH
Luperox DDM-S Phthalate solution 50 8·4 1,2, 3, 8, 9, 11, L
Luperox GZ-N Phthalate solution 50 9·0 1,2,3,4, H
Luperox S-55 Phthalate solution 50 9·3 1,2,4, VH
Luperox Delta-K Phthalate solution 50 11·0 4, VH
Luperox GH Plasticiser solution 50 10·4 I, 2, 3, 4, 11, H
Luperox DNF 10·6 I, 2, 8,9, H
British Industrial Plastics Ltd
Catalyst 347 Medium reactivity
Freeman Chemicals Ltd
Stypol Catalyst 24 High reactivity
Scott Bader Co. Ltd
Catalyst L High reactivity
Catalyst M Medium reactivity
Catalyst 0 Low reactivity
Synthetic Resins Ltd
Catalyst Quickset Extra Solution 50
Cyclohexanone peroxide
Akzo Chemie UK Ltd e
Cyclonox White powder 95 12·3 B 13 z
rJ>
Cyclonox E White powder 95 6·9 B 13 >
..,
Cyclonox M -60 Phthalate paste 60 7·8 D 1,2,4, 10, II, 12, 13 e
Cyclonox B-50 Phthalate paste available 50 6·5 D 1, 2, 4, 10, II, 12, 13 ~
pigmented til
0
Cyclonox C-50 Phosphate paste 50 6·5 D I, 2 '1:1
Cyclonox B-25 Phthalate paste 25 3·2 D 10 0
t"'
Cyclonox LE-50 Liquid 50 5·3 G 11,13 -<ttl
Cyclonox LTM-50 Liquid 6·3 G I, 2, 4, 11, 13 rJ>
50
Cyclonox LTM til~
[email protected]
20EA Liquid 20 2·5 H 10
Interox Chemicals Ltd
~
52rJ>
Interox CHP 50PFO Phosphate paste 50 6·5 4 I, 2
Interox CHP NAI Phosphate solution 50 6·0 4 1, 2
Interox CHP 50PT Thixotropic paste 50 4 10
Interox CHP 50PT Black thixotropic paste 50 4 10
Interox CHP 37PT Grey thixotropic paste 37 4 10
Luperox GmbH
Luperco CH90 Powder + 10% water 90 11·7 13
Luperco JDB-50-T Paste in dibutyl phthalate 50 6·5 1, 10 N
N
Luperco CH-S Plasticiser solution 50 5·4 1,2,3,4,6,10,13 \0
N
Table 10.5 (Continued) w
0
Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code
[email protected]
Methyl isobutyl ketone peroxide
Akzo Chemie UK Ltd
Trigonox HM Liquid 10·1 G 3,4,9, 12
Interox Chemicals Ltd
Interox MIBK Solution 60 10·0 3 3,9
Ketone mixtures
Akzo Chemie UK Ltd
Trigonox 40 Liquid 4·0 G 1,2, 5, 11, 12
Trigonox 48 Liquid 9·5 G water filled polyesters
Trigonox XOM-2 Phthalate solution G 4
Luperox GmbH
Luperox Delta-M Plasticiser solution 45 7-4 1,2,3,4
Luperox 43-M Liquid 8·7 3,4
t-Butyl hydroperoxide
Akzo Chemie UK Ltd
Trigonox A-75 Solution in di-t-butyl peroxide 75 13-2 F 13
Interox Chemicals Ltd c:
Interox TBHP 70 Aqueous solution 70 12-4 3 ztil
...,;I>
Luperox GmbH c:)1;1
Luperox H 70 X Aqueous solution 70 12·4 13 ;I>
;;l
Cumene hydroperoxide 0
'tI
Akzo Chemie UK Ltd 0
t"'
Trigonox K -80 Mixed solvent solution 80 7·9 F 5, 14, 15 ><:
!}l
Luperox GmbH ;;l
Luperox CU80 Solution in cumene 80 8·4 15 )1;1
[email protected]
Dicumyl peroxide ~
Akzo Chemie UK Ltd Z
til
Peradox SB Crystalline solid 95 5·6 B 6,7
Peradox BC-40 Powder + calcium carbonate 40 2·4 B
Luperox GmbH
Luperco 500-R Crystalline solid 99 5·9 6,7
Luperco 540 Powder + silicate 40 2·4 6,7
Luperco 540G Powder + silicate + calcium 40 2·4
carbonate N
w
Table 10.5 (Continued)
N
t;J
Active N
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code
Oi-t-butyl peroxide
Akzo Chemie UK Ltd
Trigonox B Liquid 95 10·6 F 7
Interox Chemicals Ltd
Interox OTBP Liquid 95 10·6 4
'f1
Luperox GmBH :xl
"C
Luperox Oi Liquid 97 10·6 6,7
;j
("')
t-Butyl cumyl peroxide :t
Akzo Chemie UK Ltd z
0
Trigonox T Liquid 95 7·3 E 6,7 t'"
8><:
[email protected]
2,5-Dimethyl-2,5-bis(t-butylperoxy)hexane
Luperox GmbH
Luperox 101 Liquid 90 9·9 6,7
Mixed peroxides
Akzo Chemie UK Ltd
Trigonox KSK Liquid 5·7 G 6, 7
Trigonox KSM Liquid 6·2 G 6,7
t-Butyl peroxybenzoate
Akzo Chemie UK Ltd
Trigonox C Liquid 97 7·9 F
Trigonox CM-50 Solution in dimethyl phthalate 50 4·1 E 6, 7, 13
Interox Chemicals Ltd
Interox TBPB Liquid 95 7·8 3
Interox TBPB 50Ff Phthalate solution 50 4·1 3
Luperox GmbH
Luperox P Liquid 98 8·1 6,7
t-Butyl peroxydiethylacetate
Akzo Chemie UK Ltd
Trigonox 27 Liquid 95 8·1 E 3,6,7
e
Z
CIl
t-Butyl peroxyester
Luperox GmbH ...,>
Luperox DPIO Liquid in plasticiser 80 6·6 3,4,6 e
:=
>
...,
tTl
t-Butyl peroxyisononanoate
Akzo Chemie UK Ltd '"0
"
0
Trigonox 42 Liquid 94 6·5 F 3,6 r
><:
Trigonox 42PR Liquid 94 5·9 F 3,6 tTl
CIl
[email protected]
Interox TPBIN Liquid 95 6·6 4 3,6 :=
Luperox GmbH
rn
Luperox 270 Liquid 98 6·8 6,7
Z
CIl
t-Butyl peroctoate
Akzo Chemie UK Ltd
Trigonox 21 Liquid 95 7·0 F 4,13
Interox Chemicals Ltd
Interox TBPEH Liquid 95 7·0 3
N
Luperox GmbH w
w
Luperox 26-R Liquid 98 7·25 6,7
N
......
Table 10.5 (Continued) .j::..
--~
Active
Peroxide oxygen
Supplier Assay content Hazard
Product code Form (%) (%) code Application code
Di-t-butyl diperoxyphthalate
Akzo Chemie UK Ltd
Trigonox EM-50 Phthalate solution 50 5·2 E 6
'rj
t-Butyl peroxypivalate :=
Akzo Chemie UK Ltd ."
o-!
Trigonox 25/75 Liquid 75 6·9 F 6 ttl
n
Interox Chemicals Ltd ::t::
Z
Interox TBPPI 75 AL Hydrocarbon solution 75 6·9 3 0
t"'
2,5-Dimethylhexane-2,5-diperoxybenzoate
8><:
[email protected]
Interox Chemicals Ltd
Interox DHPB Powder 95 7·5 3 6
Mixed peroxyesters
Akzo Chemie UK Ltd
Trigonox 33 Liquid G 6,7
Trigonox 37 Liquid G 6,7
2,2-Bis (t-butylperoxy) butane
Interox Chemicals Ltd
Interox BU 50 WO Phthalate solution 50 6·8 4 6,7
Luperox GmbH
Luperox 220 Solution in dibutyl phthalate 50 6·8 6,7
1,1-Bis(t-butylperoxy)cydohexane
Interox Chemicals Ltd
Interox CH 50 Phthalate solution 50 6·2 4 6,7 e
Z
Luperox GmbH V>
:>
Luperox 331-50 Solution in dibutyl phthalate 50 6·1 6,7 >-l
e~
:>
1,I-Bis(t-butylperoxy)-3,3,5-trimethylcydohexane >-l
ttl
Akzo Chemie UK Ltd 0
Trigonox 29/40 Solid + calcium carbonate 40 4·2 C '"d
0
Trigonox 29B-50 Liquid 50 5·3 E 6,7, 13 t""'
-<
ttl
Interox Chemicals Ltd V>
>-l
Interox TMCH 50FT Phthalate solution 50 5·2 4 6,7 ttl
~
[email protected]
~
Luperox GmbH ttl
V>
Luperox 231-50 Solution in dibutyl phthalate 50 5·28 6,7 Z
Luperco 231 XL/G Powder 40 4·23 V>
Ketal peroxides
Luperox GmbH
Luperox 43-M Plasticiser solution 50 8·6 3,4
Luperox 233-50 Solution in dibutyl phthalate 50 5·47 7
Luperco 233 XL/G Powder 40 4·37 7
N
Luperco 233 XLP Paste 25 2·74 7 w
Vl
tv
.....
0\
[email protected]
HAZARD CLASSIFICATIONS
Akzo Chemie UK Ltd
A Powders, when in a dry state are explosive on ignition, friction or percussion, but are normally stored and transported
in a damped-with-water condition to keep them relatively safe.
B Powders, transported and used in the dry state, flammable - will burn furiously on ignition-but not explosive.
C Powders, diluted with inert extenders, are relatively safe.
D Pastes, with plasticisers, very flammable.
E Liquids, in plasticiser solution, flammable-flash point over 43°e.
F Liquids, flammable-flash point over 100e. c
G Liquids, in plasticiser solution, flammable-flash point over 80°e.
z
~
G/LH Low hazard ketone peroxides.
H Liquids, flammable-flash point below 100e. ~
~
Interox Chemicals Ltd ~
I The material is sensitive to friction or mechanical shock. (3
2 The material can be detonated by an explosive priming charge or it decomposes with explosive violence when heated t""
unconfined, as when involved in a fierce external fire. -<
tTl
en
3 Though not detonatable nor explosive when heated unconfined, the material may decompose violently. The rate and ;:;l
magnitude of the heat released may be sufficient to propagate decomposition through the mass. Included in Hazard ::c
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Rating 3 are also materials which have a relatively short half-life at normal air temperature and therefore require
refrigerated storage. ~
4 The material is thermally stable and does not support propagating decomposition, but it is readily flammable and burns
Z
en
fiercely when ignited.
5 The material is flammable only with difficulty and/or burns only slowly when ignited.
6 The material is non-flammable.
tv
w
-..l
238 FRP TECHNOLOGY
Accelerator
Supplier
Product code Description
Cobalt accelerators
Akzo Chemie UK Ltd
NL 48 S O· 5% Cobalt solution in styrene,
flash point 31°C
NL49 S 1·0% Cobalt solution in styrene,
flash point 31 DC
NL 51 S 6'0% Cobalt solution in styrene,
flash point 31 cC
NL51P 6·0% Cobalt solution in dioctyl phthalate,
flash point 150°C
NL 53 A \0% Cobalt solution in white spirit,
flash point 43°C
All as cobalt siccatol
Luperox GmbH
Accelerator CS I % Cobalt solution in styrene, as octoate
Accelerator CW 1% Cobalt solution in dioctyl phthalate, as
octoate
Accelerator C6 6% Cobalt solution in xylene, as octoate
Accelerator CIO 10% Cobalt solution in xylene, as octoate
Freeman Chemicals Ltd
Stypol accelerator 16 6% Cobalt as naphthenate
Scott Bader Co. Ltd
Accelerator E 0·4% Cobalt solution in styrene, as octoate
Accelerator G 1·0% Cobalt solution in styrene, as octoate
Accelerator R 6·0% Cobalt solution in styrene, as octoate
Synthetic Resins Ltd
Accelerator SC 0'6% Cobalt solution, as naphthenate
Accelerator C 6·0% Cobalt solution, as naphthenate
Manganese accelerators
Akzo Chemie UK Ltd
Manganese siccatol 10% Solution
Vanadium accelerators
Luperox GmbH
Accelerator VX 0·5% Vanadium solution
Dimethylaniline
Akzo Chemie UK Ltd
NL 63/100 100% NN-Dimethylaniline
[email protected]
UNSATURATED POLYESTER RESINS 239
Accelerator
Supplier
Product code Description
Dimethylaniline (contd.)
Luperox GmbH
Accelerator AS 10% Amine solution in styrene
Accelerator A W 10% Amine solution in dioctyl phthalate
Diethylaniline
Akzo Chemie UK Ltd
NL 64/100 100% NN-Diethylaniline
Luperox GmbH
Accelerator AE 10% Solution in styrene
Dimethyl-p-toluidine
Akzo Chemie UK Ltd
NL 65/100 100% NN-Dimethyl-p-toluidine
Luperox GmbH
Accelerator DW 10% Amine solution in dioctyl phthalate.
Supplier
Product code Description
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Chapter 11
EPOXIDE RESINS
11.1 INTRODUCTION
240
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EPOXIDE RESINS 241
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242 FRP TECHNOLOGY
/'"
° ~I~
CH 3
2 CH2---CH~H2CI + HO~T~'-'H
CH 3
Epichlorohydrin Bisphenol A
~
/0", r ?H /0", l
CH2---CH~H2+R~H2~H~H2±R-CH2~H---CH2
Diglycidyl ether of bisphenol A
n = 0, 1, 2, 3, etc.
n = 0 represents the pure diglycidyl ether of bisphenol A.
[email protected]
EPOXIDE RESINS 243
1 2 3 4 5 6
Fig. 11.1. A typical thin layer chromatogram showing epoxide resins of different
molecular weights. 1, Epikote828, EMM 182-194; 2, Epikote834, EMM 225-280;
3, Epikote 1001,EMM 450-500;4, Epikote 1004, EMM 850-900; 5, Araldite 7065,
EMM 455-500; 6, Araldite XD761, EMM 2500-4000. Chromatogram developed
twice in chloroform, silica gel G plate, visualised with chromic acid spray and
heated to 100°C.
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244 FRP TECHNOLOGY
1000
800
600
400 "\.\.
\r\.
1\",
200
100
80
60
40 "-
\. '""'\
'" "
20
10
8
:II 4
6
, '-.:
'R
> ""-. '-
"
'~ 2
A/F "-
:> 1 ~
o 10 20 30 40 50 60 70 80 90 100
Temperature ·C
[email protected]
EPOXIDE RESINS 245
remain virtually the same. One disadvantage, however, is the higher cost of
making a bisphenol F resin due to the lower conversion efficiency of the
process.
HO-o-CH2-o-0H
Bisphenol F
C-O--{:H 2 --{:H--CH 2
oII "0' /
Whilst numerous resins of this type can be made from all types of di-
acids, few are in commercial production. A resin such as the one shown
above offers considerable advantages over the bisphenol A based resins in
terms of viscosity, outdoor weathering and tracking resistance. Such resins
are used for high voltage electrical insulators and heat cured laminates. In
general, resins of this type are used with anhydride curing agents, to give
systems with viscosities and reactivities ideally suited to vacuum impreg-
nation, laminating and casting applications. These resins cannot generally
be used with normal ambient temperature curing agents due to lack of
adequate cure.
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246 FRP TECHNOLOGY
/""
o o
CH 2--CH-CH 2 CH 2
/""
-CH----CH 2
~ /
N-R-N
/ 2
CH 2--CH-CH "" CH2-CH----CH2
~/
o ""/
0
Such resins can be made from most diamines and may be liquids or
solids. One such resin is the tetraglycidyl amine of 4,4' -diamino-
diphenylmethane. Other resins may be based on secondary amines such as
hydantoin, where a diglycidyl amine resin results.
Few resins of this type are commercially available. Those which are
available are mostly cured with anhydrides to give products with good high
temperature strength retention and good resistance to nuclear radiation.
These systems are used for wet lay-up laminating and filament winding.
J: r J: 1
Gt-rH,UtcH,-6
OH
[email protected]
EPOXIDE RESINS 247
Normally the curing agents used with epoxy novolac resins for prepregs
are aromatic diamines and boron trifluoride complexes. Anhydrides are
used for wet lay-up (heat cured) and filament winding processes.
/~o
CHz---CH--CHz-O -p-I:Q-
Br
'I '\
-
CH
C
I
'I '\
-
Br
/~
0
O-CHz-CR--CH z
Br CH 3 Br
These resins are used to confer flame retardancy to composites. They are
mostly used in the manufacture offire retardant printed circuit boards, for
example to NEMA Grade FR4 specification, 3 where cure is effected with
dicyandiamide.
o
/~
~R-0-CH2-CH--CHz
0'0
or the tetraglycidyl ether of tetraphenylene ethane.
Some of these other resins have been developed under various govern-
ment and military contracts specifically to provide high performance
composites for aerospace applications. One resin which proved to be of
considerable interest for use in carbon fibre composites was
bis(epoxycyclopentyl) ether. Unfortunately, due to production difficulties,
this resin is no longer available. Other resins are, however, now available
which fulfil a similar role.
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248 FRP TECHNOLOGY
11.3 DILUENTS
Diluents are added to epoxide resins primarily to lower viscosity and thus
improve handling characteristics. They also modify the cured properties of
the resin. In general terms, the higher the proportion of diluent added to the
resin the lower the viscosity and the lower the mechanical properties and
chemical resistance of the cured system. The level at which properties start
to drop dramatically varies from one diluent to another. Most cause little
concern up to between 10 and 15% addition.
Diluents can be divided into two classes: (a) the reactive diluents such as
the monoglycidyl ethers and (b) the non-reactive diluents. The reactive
diluents are the most widely used, since they form an integral part of the
cured structure and cannot be leached out.
Most resin manufacturers supply a range of diluted resins designed to
meet specific end-user needs. These cover a wide range of viscosities, with
diluent concentrations generally within the range 0- 20%. Many of these
resins have been specifically formulated for end uses other than laminating.
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EPOXIDE RESINS 249
EMMo!
Molecular resin +
weight 15%
Diluent ( EMM) diluent" Comments
usually occur. Once a resin has crystallised it can be returned to the liquid
state by warming to above 50°C, followed by thorough stirring to ensure
uniform diluent distribution.
Each of the different diluents behaves quite differently in its viscosity
reducing effect and also in its effect on mechanical properties. Fig. 11.3
shows the effect of some of the common diluents on the viscosity of a typical
liquid DGEBA resin. Clearly, the actual viscosity resulting from the
addition of a particular level of diluent to a resin must depend on the
viscosity of the base resin before dilution.
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250 FRP TECHNOLOGY
10
9
8
7
6
5
1
0·9
0-8
01
~
0·6
0
"- 0·5
>= 0·4
..
..
0
v
0·3
>
0-2
5 10 15 20
Diluent, %
Fig. 11.3. The effect of various reactive diluents on the viscosity of a standard
DGEBA resin.
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EPOXIDE RESINS 251
Table 11.2 Effect of diluent on gel time and tensile strength of DGEBA resin cured
with TETA
p-t-Butylphenyl glycidyl 15 50 91
ether 20 53 94
Epoxide 7 15 86 38 66
Epoxide 8 15 86 38 63
All systems cured with TETA (13 phr) for 1- 5 days at 20°C + 2 h at 120°C.
[email protected]
252 FRP TECHNOLOGY
10
~,
~
9
8 ~
~
"'" I'...
" '"
7 .~.
", ~
~
,
5
4
~
3
~
""" ~
2
~ ~
DBP
1
~""
" ,,"'-....
~
0·9
0 0'8
0-
0'7
>.. 0·6 "'-'"~ Benzvl alcoh 01
0'5
~
0
:;( Furfuryl ale ohol
> 0·4
0·3
(}2
5 10 15 20
Diluent, %
Fig. 11.4. The effect of non-reactive diluents on the viscosity of a standard DGEBA
resin.
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EPOXIDE RESINS 253
Tensile
strength Elongation
Diluent (%) (MPa) (%)
None 0 77 6·8
Benzyl alcohol 20 46 3·5
Furfuryl alcohol 20 35 5·4
Dibutyl phthalate 20 54 5·5
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254 FRP TECHNOLOGY
For most wet lay-up heat cured systems the resin chosen will be the
standard liquid DGEBA resin EMM 183-195. For prepreg preparation
either the same liquid resin or a solid resin with an EMM 400- 500 will be
used.
For special applications, such as where a fire retardant system is
required, then a brominated resin or brominated diluent will be used.
Where high temperature performance is needed, either a polyfunctional
resin or an epoxy novolac used with an appropriate curing agent will give
better performance than the standard resin. For outdoor weathering or
improved tracking resistance the glycidyl ester resins offer superior
performance.
When it comes to site applied laminates, resin viscosity is important and
it is here that the diluted resins are used. Various blends of resin and diluent
are available commercially, covering a fairly broad viscosity range. As
a general rule, the lower the viscosity, the higher the diluent level and the
lower the cured properties. Thus, wherever possible, a low level of diluent
is preferable. Choice is generally restricted to viscosity/handling characteri-
stics-some diluents being less pleasant to handle than others.
Many of the grades of diluted resins available have been developed for
applications other than laminating, often for their ability to take high filler
loadings. In these cases, the filler often compensates for a reduction in
mechanical properties of the cured system.
With all resins, cured properties are very dependant on the curing agent
used, particularly as far as chemical resistance is concerned, but also with
respect to other properties. ,Thus for any particular application, system
properties must be considered, rather than just resin properties alone.
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EPOXlDE RESINS 255
REFERENCES
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N
VI
0-.
Table 11.4 Commercial epoxide resins
Berger (Reichhold Albert Chemie A G) Other high molecular weight resins also available
Beckopox EP 128 190-210 0·5-1·0 1·12 100% reactive modified resin for laminating and casting
EP 130 185-200 0·5-0·9 1·13 100% reactive modified resin for laminating and casting
EP 133 230-250 1·2-1·6 1·14 Plasticised resin for casting, cable jointing, etc.
EP 134 230-250 2·1-3·1 1·14 Plasticised resin for coatings and flooring 'tj
EP 135 185-200 5·0-8·5 1·15 100% reactive resin for laminating and casting ~
'Ii
EP 139 180-190 6·0-10·0 1·16 Unmodified general purpose resin
EP 140 185-195 1·16 Unmodified resin for tooling and laminating ;l
10-15 (")
EP 144 230-280 0·5-1·0" 1·17 Unmodified resin for coatings and adhesives :I:
Z
EP 151 400-500 25-35 1·08 Internally plasticised resin, 100% reactive 0
t"'
EP 200 245-265 75 1-40 100% reactive self extinguishing resin for laminating
EP 300 370-440 Solid 1·18 Solid resin for casting and laminating 8-<
[email protected]
Borden (UK) Ltd Other products also available
Epophen EL-5 185-200 10-16 1·16 Medium-high viscosity DGEBA resin for laminating, etc.
EL-1O 200-220 220-40 1·2 Unmodified DGEBA resin
EL-17 185-200 10-16 1·2 Medium viscosity DGEBA resin
EL-18 190-205 2.0-2.5 1·15 DGEBA resin containing reactive diluent
EL-23 190-205 1.0-1.3 1.2 DGEBA resin containing reactive diluent
EL-24 190-205 0.6-0.9 1·2 DGEBA resin containing reactive diluent
EL-25 185-200 6-9 1·2 Unmodified DGEBA resin
EL-26 190-205 0.7-1.l 1·14 DGEBA resin containing reactive diluent
Boston Chemical Co. Ltd
ER 1 185-200 11-15 1·16 Unmodified DGEBA resin
ER2 195-207 1·2-1·8 1·14 DGEBA resin containing reactive diluent
ER 3 212-232 3·3-5·0 1·16 Flexible resin
[email protected]
GY279 200-212 1·2-2·2 1·12 Low viscosity resin containing reactive diluent
GY 280 233-278 1·18 Semi-solid DGEBA resin
GY 292 217-238 5-10 1·16 Medium viscosity modified resin
CT 200 370-435 1·18 Solid DGEBA resin
CY 219 194-200 10-15 1·18 Medium-high viscosity DGEBA resin for laminating, etc.
LY 558 175-182 Semi-solid epoxy novolac resin
LY 560 172 1·5-3·0 1·15 Liquid DGEBA resin for laminating
LT 579 182-200 Solid polyfunctional resin for laminating
MY 720 128-137 1·19 Viscous polyfunctional epoxide resin for laminating
MY 750 188-198 10-16 1·18 Medium viscosity DGEBA resin
MY 753 227-238 1·6-2,4 1·18 Plasticised liquid DGEBA resin tv
VI
-.)
Table 11.4 (Continued) N
VI
00
Supplier Epoxy Viscosity
Trade name molar at 25°C Specific
Product code mass (Pa s) gravity Comments
Araldite (contd.)
MY 778 188-200 0'6-1'0 1·18 Liquid DGEBA resin containing reactive diluent
7065 455-500 Solid 1·19 Solid DGEBA resin for prepregs
8011 455-500 Solid Solid brominated resin, 21% Br, for laminating
8047 222-244 Semi-solid brominated resin, 18-22% Br, for laminating
LZ 1620 GB 454-500 Solid brominated resin, 80% solids in MEK, 19-23% Br
XD 927 140-150 1-0-1,5 1·17 Low viscosity laminating resin "!j
:=
o-g
XD 928 Gelcoat for XD 927
XD 955 172-185 4,5-6,5 1·17 DGEBA/F blended resin t;l
XD 761 2500-4000 1·19 Supplied as 50% solution of high molecular weight DGEBA t"l
resin for coating applications (TLC Fig. 11.1)
:=
~
t""
Crodo Resins Ltd Other types of resin also aviailable 8-<
Plastokyd SC 480 295-310 0'1-0'15< Silicone modified epoxy for laminating, etc.; 25% silicone
[email protected]
Dow Chemical Co. (UK) Ltd Other resins also available
D.E.R.321 182-192 0'5-0'7 1·14 DGEBA resin containing CGE
D.E.R.324 195-213 0·5-0·7 1·10 DGEBA resin containing C 12 -C 14 glycidyl ether
D.E.R.330 182-189 7-10 1·16 Undiluted DGEBA resin
D.E.R.331 186-192 11-14 1·16 Undiluted DGEBA resin
D.E.R.332 172-176 4-6 1·16 High purity DGEBA resin
D.E.R. 334 176-186 0'5-0'7 1·13 DGEBA resin containing nBGE; withdrawn in Europe
D.E.R.337 230-250 0·4-0·8 d 1·16 High viscosity DGEBA resin
D.E.N.431 172-179 1·1-1·7' 1·21 Epoxy novo lac
D.E.N.438 176-181 20-50' 1·22 Epoxy novo lac
D.E.N.439 191-210 ]·22 Semi-solid epoxy novolac
D.E.R.511 445-520 1·40 Solid brominated resin containing 18-20% bromine
D.E.R.542 350-400 1·79 Semi-solid brominated resin containing 44-48% bromine
D.E.R.599 308 0·25 max. 1·77 Dibromophenyl glycidyl ether
D.E.R. 661 475-575 1·16 Solid DGEBA resin for prepregs
D.E.R.662 575-700 1·19 Solid DGEBA resin
D.E.R.671 475-550 1·19 Solid DGEBA resin
D.E.R. 732 305-335 0·05-0·1 1-06 Flexible polyglycol diepoxide
D.E.R.736 175-205 0·03-0·06 1·14 Flexible polyglycol diepoxide
XD 5567·01 170-183 5-7 1·19 Blended bisphenol A/F resin
XD 7475 175-187 0·8-1·0 1·19 Blended bisphenol A/F resin containing nBGE
[email protected]
EL 303 185-200 12,5-15 1·17 Medium-high viscosity DGEBA resin
EL 304 192-206 15-25 1·17 High viscosity DGEBA resin
EL 305 182-196 9-13 1·17 Medium viscosity DGEBA resin
EL 306 175-189 6-7·8 1·19 Medium viscosity DGEBA/F blended resin
EL 307 225-280 1·18 Semi-solid DGEBA resin
EV 401 179-196 0,5-0·9 1·13 Low viscosity resin containing a reactive diluent
EV 402 182-188 0·56-0·25 1·14 Low viscosity resin containing a reactive diluent
EV 403 189-200 4·5-6·0 1·16 Medium-low viscosity resin containing a reactive diluent
EV404 189-200 3·0-4'0 1·16 Medium-low viscosity resin containing a reactive diluent
EV 405 196-204 11-13 1·16 High viscosity resin containing a reactive diluent
Medium-low viscosity resin containing a reactive diluent N
EV406 158-173 2'6-3·0 1·16 VI
Low viscosity resin containing a reactive diluent \0
EV 407 141-153 0·7-0·85 1·16
Table 11.4 (Continued) IV
0-
0
Supplier Epoxy Viscosity
Trade name molar at 25°C Specific
Product code mass (Pa s) gravity Comments
Grilonit (contd.)
EY 408 120-127 0,18-0,22 1·14 Low viscosity resin containing a reactive diluent
EY 409 175-188 1·2-1·6 1·15 Medium-low viscosity resin containing a reactive diluent
EP SOl 220-240 2·0-2'6 1·15 DGEBA resin containing a plasticiser
EP 502 227-244 1·1-1·5 1·14 DGEBA resin containing a plasticiser
EF 601 196-212 4·5-5·0 1·16 100% reactive flexibilised resin
EF602 213-232 1-3-1·6 1·15 100% reactive flexibilised resin ;il
EF603 227-250 0·4-0·5 1·14 100% reactive flexibilised resin '"Cl
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708 185-200 12-19 1·17 Medium viscosity DGEBA resin
710 178-196 9·0-13 1·17 Medium viscosity DGEBA resin
716 182-190 7·0-10 1·16 Medium viscosity DGEBA resin
720 182-192 6,5-9,0 1·17 Medium viscosity DGEBA resin
730 182-189 7·0-10 1·16 Medium viscosity DGEBA resin
761 217-233 1·2-1·6 1·14 Low viscosity modified DGEBA resin
780 178-196 0·7-1·1 1·11 Low viscosity modified DGEBA .resin
7000 365-420 1·2 Solid DGEBA resin
7001 445-500 1·19 Solid DGEBA resin
7002 590-715 1·19 Solid DGEBA resin
7003 700-875 1·19 Solid DGEBA resin
Shell Chemicals UK Ltd Other resins also available
Epikote 191 145-165 0-32-0-4 1-22 Low viscosity diglycidyl ester resin
210 240-270 1-20 Semi-solid modified resin for prepregs
213 190-210 0-7-1-1 1-15 Low viscosity DGEBA resin containing reactive diluent
214 190-210 10-15 1-16 Medium viscosity DGEBA resin, low crystallisation grade
215 200-220 0-8-1-2 1-10 OdourJess, low viscosity DGEBA resin, low surface tension
216 190-210 5-0-6-0 1-15 Medium viscosity DGEBA resin containing reactive diluent
220-B-80 400-440 1-09 80% solution of solid DGEBA resin in MEK for prepregs
DX235 175-185 6-5-9-5 ]-17 Medium viscosity DGEBA/F blended resin
DX285-B-80 640-750 ]-5-2-5 Brominated resin, 80% solids in MEK, 40% bromine
solution
808 188-198 6-5-9-5 ]-16 Medium viscosity DGEBA resin ttl
815 180-200 0-7-1-1 1-14 Low viscosity DGEBA resin containing nBGE C3
~
816 195-215 1-5-2-1 1-l3 Low viscosity DGEBA resin containing reactive diluent ....
I:)
817 210-240 2-0-2-5 1-15 Low viscosity plasticised DGEBA resin ttl
827 180-190 8-0-10 1-16 Medium viscosity unmodified DGEBA resin
828 182-194 10-15 1-16 Medium-high viscosity unmodified DGEBA resin ~
834 225-280 0-4-0-79 1-18 High viscosity unmodified DGEBA resin Z
til
[email protected]
836 290-335 1-19 Semi-solid unmodified DGEBA resin
1001 450-500 1-19 Solid unmodified DGEBA resin, also available in solution
1002 575-700 1-19 Solid DGEBA resin
1004 850-940 1-19 Solid DGEBA resin
1045-A-80 450-500 1-22 80% solution in acetone of brominated resin for prepregs
[email protected]
• 70% in butyl diglycol.
b 40% solids in butyl carbitol.
c 70% in xyloljoxitol acetate_
d 70% in Dowanol DB glycol ether_
eat 52°e.
f at 120°C_
g 70% solution in butyl dioxitol.
Chapter 12
12.1 INTRODUCTION
263
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264 FRP TECHNOLOGY
Adduct Adduct
Blend S blend SE blend TE
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CURING AGENTS FOR EPOXIDE RESINS 265
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266 FRP TECHNOLOGY
o R
OH R
/ \ / I /
R-CH-CH + HN R-CH-CH-N
\
R " R
The primary aliphatic amines react with DGEBA resins at room
temperature to give products with excellent properties, but only react
slowly with non-glycidyl ether resins. Those amines which are com-
mercially available are generally polyamines and may contain both
primary and secondary amine groups. The ones commonly encountered
either alone, or partially adducted to improve handling characteristics,
include ethylenediamine, diethylenetriamine (DT A), triethylenetetramine
(TETA), dimethylaminopropylamine and trimethylhexamethylenedi-
amine (TMD). These may be blended with polyamides for adhesive
applications to improve flexibility.
The alicyclic amines may contain primary, secondary and tertiary amine
groups and may also require an accelerator to ensure full cure at room
temperature. Examples of these materials are N-aminoethylpiperazine
(AEP) and isophoronediamine (IPD). Salicylic acid and phenol are
frequently used as accelerators for these materials.
The aromatic amines are generally used alone for heat cured systems or
in solution, with an accelerator, for room temperature cure. They are
widely used for laminating applications and give cured products with
excellent mechanical, electrical and chemical resistance up to fairly high
temperatures. Typical examples of aromatic arnines in common use are
4,4' -diaminodiphenylmethane, m-phenylenediarnine and diarninodiphenyl-
sulphone. All three are solids and so need to be dissolved in the resin prior
to gelation.
A list of commonly used amines, together with some properties, is given
in Tables 12.2 and 12.3.
Care should be taken when handling all amine curing agents and in
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CURING AGENTS FOR EPOXIDE RESINS 267
particular the aliphatic and alicyclic amines, which can cause skin
dermatitis. All normal precautions should be taken to avoid skin contact
and inhalation of vapours.
Each of the amines will now be discussed briefly in turn.
Ethylenediamine (EDA)
EDA is a mobile, fuming liquid which is used to cure liquid DGEBA
resins at room temperature. It is unpleasant to handle and so is mostly
adducted with resin and used for coating applications, frequently in
solution.
Trimethylhexamethylenediamine (TM D)
TMD is a colourless, low viscosity, aliphatic branched chain diamine
consisting of a blend of two isomers. It can be used to cure liquid DGEBA
resins alone or more generally as an activator for IPD. TMD is often
partially adducted with resin and the viscosity of the adduct reduced with
benzyl alcohol. Salicylic acid can be used as accelerator for room
temperature cure. It is mostly used for coating and flooring applications.
Diethylenetriamine (DTA)
DT A is a mobile, almost colourless, fuming liquid used to cure liquid
DGEBA resins at room temperature. It can be used for tooling and
laminating applications and is often blended with polyamides for adhesive
applications. It is not as unpleasant to handle as EDA. Cure under high
humidity conditions causes surface bloom.
Handling can be improved by reacting DT A with ethylene oxide to give
2-hydroxyethyldiethylenetriamine.
2-Hydroxyethyldiethylenetriamine (T)
This is often referred to as Amine T. It is an almost colourless low
viscosity liquid used to cure liquid DGEBA resins at room temperature. It
is more pleasant to handle than DTA but can still give rise to bloom on
cured surfaces under high humidity conditions. It is used for casting,
adhesive and wet lay-up laminating-often with diluted resins.
Dipropylenetriamine (DPTA)
DPTA is a colourless to pale yellow mobile liquid used with liquid
DGEBA resins for coating and casting applications. If used immediately
after mixing, the surface is prone to bloom. It can be adducted with resin to
reduce this tendency.
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268 FRP TECHNOLOGY
Number of
Mol. Equiv. active Calc.
Curing agent Form wt wt/NH hydrogens phr·
Ethylenediamine EDA 60 15 4 8
Trimethylhexamethylene-
diamine TMD L 158 39·6 4 20
Diethylenetriamine DTA L 103 20·6 5 II
Dipropylenetriamine DPTA L 131 26 5 14
Triethylenetetramine TETA L 146 24·3 6 13
Tetraethylenepentamine TEPA L 189 27 7 I
Dimethylaminopropylamine DMAPA L 102 51 2 7
Diethylaminopropylamine DEAPA L 130 65 2 7
2-Hydroxyethyl DTA T L 147 37 4 20
rn- Xylylenediamine rnXDA L 136 34 4 18
N-Aminoethylpiperazine AEP L 128 42·6 3 22
Isophorone diamine IPD L 170 42·6 4 22
Cyclohexylpropylenediamine CHPDA L 156 52 3 27
3,3' -Dimethyl-4,4' -diamino-
dicyclohexylmethane DMACM L 238 60 4 32
Diaminodiphenylmethane DDM S 198 49·5 4 27
rn-Phenylenediamine MPD S 108 27 4 14·5
Diaminodiphenylsulphone DDS S 256 64 4 33
Triethylenetetramine (TETA)
TET A is a mobile pale yellow liquid used to cure liquid DGEBA resins at
room temperature. It is used for casting, tooling and wet lay-up laminating
applications, often with diluted resins. HDT of the cured system can be
increased by giving an elevated temperature post cure. Cured properties are
similar to those obtained with DT A. Cure under high humidity conditions
can result in bloom on the surface.
Tetraethylenepentamine (TEPA)
TEPA is a liquid aliphatic polyamine with reactivity and cured
properties similar to those of TET A. It is mostly used for coating
applications from solution.
Diethylaminopropylamine (DEAPA)
DEAPA is an aliphatic amine containing a tertiary amine group which
acts as a catalytic curing agent at room temperature. For this reason it is
used at only 4-8 phr rather than the level expected from calculation based
on two active hydrogens. It is often used in adhesive formulations.
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CURING AGENTS FOR EPOXIDE RESINS 269
Dimethylaminopropylamine (DMAPA)
DMAPA is a similar curing agent to DEAPA and is used for similar
applications.
m-Xylylenediamine (mXDA)
mXDA is a colourless low viscosity liquid amine which gives excellent
cured properties with DGEBA resins after heat cure, but which requires the
addition of an accelerator and diluent to complete cure at room tempera-
ture. It is mostly adducted with a resin or glycidyl diluent to overcome
problems of amine bloom. The adducts are used for coating and wet lay-up
laminating applications and cure well at room temperature.
N-Aminoethylpiperazine (AEP)
AEP is a mobile liquid giving cured systems with excellent impact
resistance after full cure. Whilst cure will take place at room temperature, a
post cure of 2 h at 100°C is necessary to develop full properties, particularly
impact resistance. It gives a short pot-life and high exotherm with liquid
DGEBA resins. It is often used in formulated amine curing agents.
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Table 12.3 Some properties of amine cured epoxide resin systems
Cast resin properties"
Volume
Tensile Tensile Elongation Flexural Permittivity Loss resistivity
Curing strength modulus at break strength at 23°C tangent (lOglO
agent HDT(°C) (MPa) (GPa) (%) (MPa) at 1 kHz at 1 kHz ohm em) Typical cure schedule
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eHPDA 95 65 2·7 90 4·1 0·016 16 1 h/80oe + 4 h/150oe
DMAeM 152 76 2·6 102 4·1 0·013 16 1 h/80oe + 4 h/150oe
DDM 155 80 2·8 5·2 117 4·1 0·006 15 1 h/l00°C + 4 h/150oe
MPD 155 82 II 6·5 4·2 0·018 16 1 h/lOOoe + I h/200°C
DDS 193 78 3·1 6·0 4·0 0.(J.t7 2 h/l30°C + 2 h/200°C
XD 927 55-120 90 3·1 6·0 100 16 h/25°C + 5 h/80°C
Cyclohexylpropylenediamine
This is a colourless low viscosity cyclo-aliphatic polyamine used for
casting and laminating applications. Heat cure is required to achieve
optimum properties, although when used with an accelerator, co-curing
agent or diluent, cure will take place at room temperature. It can be used
with liquid DGEBA resins and gelled at room temperature. It is
intermediate in reactivity between the aliphatic and aromatic amines.
Typical accelerators for room temperature cure are salicylic acid, phenol
and triphenyl phosphite.
4,4'-Diaminodiphenylmethane (DDM)
DDM is also known as methylenedianiline (MDA), although this latter
name is mostly used in the USA. DDM is an off-white solid at room
temperature and is supplied either as a powder or flake. Normal mixing
procedure is to melt the DDM at about 100°C and add to the resin, also at
100°C. Once the resin and curing agent have been thoroughly mixed the
blend can be cooled to about 50°C to prolong pot-life. At 50°C with a liquid
DGEBA resin, pot-life is about 2 h.
DDM can be used for wet lay-up laminating, casting or prepreg
preparation. For prepreg preparation both the resin and curing agent are
dissolved in solvent-either methyl ethyl ketone or acetone.
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272 FRP TECHNOLOGY
m-Phenylenediamine (MPD)
MPD is a colourless crystalline solid at room temperature which rapidly
darkens on exposure to light. It can either be added as a powder to resin at
80°C and dissolved with stirring or both resin and MPD can be heated to
about 65°C and thoroughly mixed. In either case irritating fumes are given
off. Once mixed the blend should be cooled to room temperature to prolong
pot-life. Skin and clothes turn brown on contact with MPD. These stains
resemble those obtained from walnut shells and are very difficult to remove.
Although MPD can be used both for wet lay-up and prepreg manufac-
ture, it finds limited use due to its unpleasant handling characteristics.
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Table 12.4 Properties of different resins cured with DDS
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DDS 100/40 550 65% at 1900e 5,1-5,3 0,009-0,011
Brominated resine /
DDS/BF 3 400 100/28/2 540 5·0-5·4 0·025-0'045
ing is to warm the resin to about 130-140°C and add the DDS slowly with
stirring until it is all dissolved (about 20 min). Pot-life at 130°C is about I h.
If an accelerator is to be used the blend should be cooled to below 100°C
before adding it.
DDS is used more as a curing agent in prepreg systems than for wet lay-
up. Here the resin and DDS are both dissolved in a ketone solvent such as
acetone or MEK. Prepreg without an accelerator would normally be dried
for about 20 min at 150°C, while if an accelerator is present, drying time
would be about 15 min at 115°C. During this drying period partial reaction
occurs between the resin and curing agent.
Laminates prepared from a liquid DGEBA resin cured with DDS show
good strength retention up to about 150°C (Table 12.4). DDS can also be
used to cure resins other than those based on bisphenol A. Some properties
of such systems are given in Table 12.4.
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CURING AGENTS FOR EPOXIDE RESINS 275
Crystallisation HDT"
Anhydride blend e
temperature C) phr eC)
HHPA/NMA (60/40) -20 85 112
HET/NMA (40/60) + 15 95 112
HET/HHPA (40/60) + 10 85 128
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276 FRP TECHNOLOGY
Mol. m.p.
Anhydride curing agent Form wI. ("C) phrc
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CURING AGENTS FOR EPOXIDE RESINS 277
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Table 12.7 Some properties of anhydride cured epoxide resin systems
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HET 186 82 3·2 2·6 3-3 0·006 568 26 382 27/73
HHPA l30 85 2·7 7·0 3·2 0·009 625 26 400 40/60
TMA 189 21 2·5 0·9 4·0 0·007
PDMA 290 22 z.s 4·0 0'002 502 23 40/60
DDSA 78 50 2·4 3·5 z.s 0·006 516 25 40/60
Liquid DGEBA resina /NMA/DY 063 100/85/1 190 304-3'6 0·003-0·005 480 52% at l30°C 38/62
Epoxy novolacb/NMA/DY 063 100/85/1 250 3,7-3,9 0·003-0·005 450 65% at 190°C 40/60
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High functionality resinc/NMA 100/140 260 3,7-3·9 0·005-0'01 520 67% at 190°C 40/60
Table 12.9 Effect of cure schedule on properties of NMA cured DGEBA resin
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CURING AGENTS FOR EPOXIDE RESINS 281
dissolved. For this reason it is often used in blends with other anhydrides
such as maleic anhydride or phthalic anhydride, the maleic
anhydride/PDMA blend showing superior heat resistance.
With mixed anhydrides the resin should be heated to about 70°C prior to
addition of the anhydride, followed by continuous stirring and warming to
120°C. Once all the anhydride has dissolved, the mix should be cooled to
90°C to prolong pot-life. Some properties of mixed anhydride systems are
given in Table 12.10.
PDMA is often used in solvent solution for making prepregs. Solubility
of PDMA in various solvents is shown in Table 12.11.
Acetone 20 7
56 9
Dimethyl sulphoxide 20 20
120 95
Dimethyl formamide 20 16
140 100
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282 FRP TECHNOLOGY
The polyamides used to cure epoxide resins are all reactive compounds with
free amine groups. They may be amidopolyamines, aminopolyamides or
imidazolines. They are mostly used in coating systems and to a lesser extent
in adhesive formulations. They are rarely used for laminating.
Manufacturing procedure depends on the type of polyamide to be
produced. In general they are derived from polyamines reacted with mono-
or di-basic carboxylic acids. The carboxylic acids used are mostly those
tK54 from Anchor Chemical Co. or DMP-30 from Rohm & Haas.
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CURING AGENTS FOR EPOXIDE RESINS 283
obtained from fats and oils such as soya, tall oil, castor oil, etc. A typical
dicarboxylic acid used is the dimer acid prepared from linoleic acid by a
Diels-Alder reaction. Imidazolines are prepared by the high temperature
reaction of a polyamine with a carboxylic acid to cause ring closure.
Numerous polyamide curing agents are commercially available, includ-
ing water dispersible ones, ranging from low viscosity liquids to semi-
solids. Most can be used over a wide range of mixing proportions. For
example Versamid 125-a typical aminopolyamide-can be used in
proportions from 50 to 100 phr with a liquid DGEBA resin; however,
cured properties vary considerably over this range.
Some suppliers of polyamide curing agents are listed below:
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N
00
.j::.
Table 12.13 Properties and cure schedules for various epoxide resin curing agents
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·With liquid DGEBA resin EMM 190.
bWith solid DGEBA resin EMM 500.
CWithout accelerator.
dListed at the end of this chapter.
S = solid; L = liquid; phr = parts per hundred resin.
Table 12.14 Properties of various cured epoxide resin systems
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t!l
K 61 B 12 80 76 4·7 516
tv
00
VI
286 FRP TECHNOLOGY
Dicyandiamide (Dicy)
Dicyandiamide is a solid curing agent used with solid DGEBA resins for
the preparation of prepregs from solution. It is only sparingly soluble in
solvents and so the ones which have to be used are 2-methoxyethanol,
acetone/water (3/2) or dimethylformamide, the former being preferred.
Prepreg has a shelf-life of up to 6 months at room temperature and is
generally used for the preparation of printed circuit boards (NEMA Grade
G.IO). Although cure takes place fairly rapidly in the temperature range
150-170°C, accelerators are sometimes used to reduce cure time or cure
temperature. A typical accelerator would be BDMA used at 0·1-0·4 phr,
with a typical cure schedule of }h at 165°C.
2-Ethyl-4-methylimidazole
2-Ethyl-4-methylimidazole is a liquid which can be used either as sole
curing agent at 4-8 phr or as an accelerator for anhydride cured systems. It
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CURING AGENTS FOR EPOXIDE RESINS 287
acts as a catalytic curing agent with liquid DGEBA resins. It can be used in
casting and laminating formulations and is particularly suitable for
filament winding applications. Laminates show some 70% flexural strength
retention at 70°C after a cure of 2 h at 60°C.
N-n- Butylimidazole
This is a liquid curing agent which can be used to cure liquid DGEBA
resins. It gives long pot-life systems with relatively low temperature cure
(60°C). It is used in casting and laminating systems.
Other imidazoles
Various other substituted imidazoles and their salts are available, many
of which are used as curing agents for epoxide resins. Some of these salts
can be used in prepreg formulations since they require heat to initiate the
curing reaction, by dissociation of the salt into its component parts. They
can provide excellent cured properties with short, low temperature cure
schedules.
K61 B
This is the tris-2-ethylhexoate salt of K54 and is available from Anchor
Chemical Co. It is used for wet lay-up laminating and casting applications.
It gives a 4-6 h pot-life at 25°C with liquid DGEBA resins.
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Table 12.15 Properties of some epoxide resin systems used for hand lay-up laminating
Resin Epikote 816 Epikote 816 Epikote 816 Epikote 816 Epikote 816 Araldite XD 927
Curing agent DX 150 DX 151 Ancamine TLS Ancamine TLS Epikure J14 Araldite XD 927
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eure schedule 7 days/20oe 7 days/20oe 7 days/20oe 7 days/20oe 7 days/23°e 7 days/20oe
+ 1 day/50oe + 1 day/50oe + 1 day/50oe + 1 day/50oe
Tensile' strength (MPa) 96 100 98 98 80
Flexural strength at
break (MPa) 112 112 112 128 120" 415
Flexural modulus (GPa) 4·13 4·28 4·14 3-61 4·13 17
Glass content (%) 33 33 33 33 25 60
"Two layers of chopped strand mat (450 g/m 2 ) plus surface tissue.
bWoven glass cloth laminate, 12 ply.
C Increases to 170 MPa after 3 weeks cure at 23°e.
CURING AGENTS FOR EPOXIDE RESINS 289
used to provide a system with a fixed pot-life of say 2 h, over a very wide
range of ambient temperatures from about 5°C up to about 50°C. Some
properties of these systems are given in Table 12.15.
The reinforcement generally used is chopped strand mat-preferably
one recommended for use with epoxide resins. Most binders used on
chopped strand mats are insoluble in epoxide resin systems and so fibre
pattern remains the same as in the mat as supplied (Fig. 12.1).
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290 FRP TECHNOLOGY
12.7.3 Electricallaminates
These cover a wide range of applications including printed circuit board
laminates, filament wound switch links or tie bars, stator restraining rings
and woven or knitted glass reinforced radomes. Many different systems
may be used to meet the various requirements of these different appli-
cations. Properties of some of the systems used are given in Tables 12.3 and
12.7; other systems are mentioned below.
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Table 12.16 Typical properties of systems conforming to NEMA specifications
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novolac/DDS/BF 3400
FR-5 440-540 0-02-0-1 1-8-2-2 5-0-5-4 0-025-0-045 Brominated resin/
DDS/BF 3 400
450-550 0-05-0-14 1-8-2-2 5-0-5-4 0-021-0-045 Brominated resin/epoxy
novolac/DDS/BF 3400
292 FRP TECHNOLOGY
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CURING AGENTS FOR EPOXIDE RESINS 293
Unidirectional
Composite propertieS' E-glass
·Carbon fibre Type II, 60% fibre volume, properties measured at 20°C.
blnterlaminar shear strength.
c 70% glass by weight.
d65% glass by weight.
REFERENCES
1. Lee, H. & Neville, K. (1967) Handbook of Epoxy Resins, McGraw-Hill Book
Company, New York.
2. NEMA Publication No. LI.I-1971. National Electrical Manufacturers
Association, Washington, DC, USA.
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294 FRP TECHNOLOGY
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Chapter 13
13.1 INTRODUCTION
Apart from polyester and epoxide resins, several other resins are used for
laminating applications and in moulding compounds. These include vinyl
ester resins, furane resins, Friedel-Crafts polymers, polyimide resins,
silicone resins, phenolics, and melamine- and urea-formaldehyde resins.
Of these, only the furane, vinyl ester and Friedel-Crafts resins will be
discussed in detail, although some comments will be made about the other
resins.
Vinyl ester and furane resins can be considered to be complementary to
polyester and epoxide resins, since they can be processed in similar ways
and extend the range of uses to which FRP composites can be applied. The
other types of resin extend the range of press moulded composites which
can be made. Each of the other resins mentioned requires processing at
elevated temperature and under pressure.
295
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296 FRP TECHNOLOGY
resistant tile grouts and cements, as hard wearing coatings on mould tools
and as binders for foundry cores. With the continual demand for GRP
systems with improved chemical resistance for the manufacture of chemical
plant, they are an obvious candidate for laminating applications.
Unfortunately furane resins require acidic catalysts such as p-
toluenesulphonic acid, phosphoric acid or hydrochloric acid generators.
Such systems tend to be difficult to handle for laminating applications. One
of the problems has been to find a catalyst which will give an adequate
working pot-life, coupled with relatively slow increase in viscosity of the
catalysed resin. This is necessary to ensure adequate wetting out of the glass
reinforcement. Another problem has been brittleness of the gelcoat-which
severely limits gelcoat thickness.
These problems have been overcome by the Quaker Oats Company with
their 'Quacorr' 1001 resin and catalyst 2001. Indeed a number of very large
vessels have been successfully constructed from this resin system by the
hand lay-up technique. 1,2
Also available are two flame retardant, low smoke emission resins,
'Quacorr' 1500FR and 'Quacorr' l200FR, both used with catalyst 2001.
All of these systems can be successfully used and cured at room
temperature. The proportion of catalyst used is fairly critical and should
generally be within the range 3-4%.
Another supplier of a furane resin system for laminating applications is
Borden (UK) Ltd, who supply resin P 910 with catalyst P 911. They also
supply a furane resin for coating applications.
Whilst furane resins can be processed by normal hand lay-up and
filament winding techniques, they are somewhat different in handling
characteristics and smell from polyester resins. Contact with the skin or
clothing causes brown or black discolouration. Like polyester resins they
must be used in well ventilated areas. Threshold Limit Values for furfuryl
alcohol and furfural are compared with those for other materials in
Table 13.1.
Recently, spray equipment has been introduced by Venus Products for
th~ spray lay-up of furane resin systems and is available from CT (London)
Ltd, from whom details may be obtained.
Why use furane resins? When fully cured they provide probably the best
chemical resistance of any thermosetting resin in non-oxidising conditions.
For example, laminates immersed at room temperature for 1 year in methyl
ethyl ketone or perchlorethylene show greater than 99% flexural strength
retention, while after 6 months at 65°C in glacial acetic acid flexural
strength retention is still some 79%. Polyester and epoxide resins disinte-
grate under these conditions. Maximum continuous service temperature is
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OTHER RESIN SYSTEMS 297
Boiling point
TLV(ppm)a ("C)
a Taken from the Health & Safety Executive Guidance Note EHI5j76.
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298 FRP TECHNOLOGY
used these must be hard waxes (Carnauba wax) since soft waxes inhibit
cure. Also, waxes stick to the laminate surface and so the mould must be
rewaxed each time it is used. PVA and silicones are attacked by the resin
and Cellophane is embrittled, so none of these should be used as release
agents.
If a furane resin laminate is to be used as a lining for a steel or concrete
Table 13.2 Typical properties of forane resin laminates
Garrick Chemical & Equipment Co. Ltd- UK Agent for Ashland Chemicals
Hetron 800 250 1·2 15 Laminating resin
Catalyst 801 L Used at 4 phr
Hetron 800FR 450 1· 2 15 Fire retardant
laminating resin
Catalyst 801 L Used at 5 phr
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OTHER RESIN SYSTEMS 299
vessel then great care has to be taken in the design of the system and
application of the resin, since the acid catalyst will attack the substrate and
cause lack of bond. To overcome this the substrate must first be thoroughly
sealed with a suitable primer, such as an amine cured epoxy resin system.
This coating must be checked to ensure that it is pinhole free and all amine
must be washed off the surface until it is neutral. The laminate can then be
applied. The difference in coefficient of expansion between the laminate
and the substrate must be considered during the design of the lining, to
prevent delamination in service.
Some typical laminate properties are given in Table 13.2 and com-
mercially available materials in Table 13.3.
1=
structure is shown below.
CH 2 =CH-C-
oII c4c OH
I
H 2 -CH-CH 2 -R n
OH
I 0
II
H 2 -CH-CH 2 -O-C-CH=CH 2
0-
CH 3
R=-0-o-~
-
~.~
I~ CH 3
Although based on bisphenol A, the structure is different from that of a
conventional bisphenol polyester, which has ester groups and double
bonds in the repeat unit. Vinyl ester resins contain a reduced number of
ester links-two per molecule-and a reduced number of double
bonds-again two per molecule, situated at either end of the molecular
chain. The main backbone is the bisphenol A epoxy structure. Thus in the
cured resin there are fewer ester linkages and hence improved chemical
resistance, whilst the terminal double bonds result in a tougher, more
resilient resin structure. Styrene emission and flash point are similar to
those of polyester resins and so similar handling precautions are necessary.
Vinyl ester resins can also be made from brominated resins to give fire
retardant grades.
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300 FRP TECHNOLOGY
Styrene Viscosity
Supplier content Specific at 25°C HDT
Product code (%) gravity (mPa s) ("C)
Garrick Chemical & Equipment Co. Ltd- UK Agent for Ashland Chemicals
Hetron 901 45 1·05 500
Honeywill-Atlas Ltd
Atlac 580-05 47 350-500 118
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OTHER RESIN SYSTEMS 301
As with polyester resins air inhibition can occur, which can be overcome
by the addition of a small proportion of paraffin wax to the final coat of
resin. This addition will, of course, prevent or impair adhesion of any
further layers of resin without thorough surface preparation.
The main uses of vinyl ester resins are in the manufacture of chemical
plant, pipes, storage tanks, etc., where high chemical resistance is required.
Some typical properties of vinyl ester resins are shown in Table 13.4 and
some commercially available materials are given in Table 13.5.
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302 FRP TECHNOLOOY
OH
6 + CH,-O-CH,--Q-CH,-O-CH,
lhea!.
SoCI.
rr IHl OH
(3t-CH,-cr=H,-Q±cH,--Q-cH,-t6
compounds. With laminates the reinforcement is impregnated with the
resin and pre-cured for about 10 min at 130-165°C, followed by pressing at
165-175°C under a pressure of 3.5- 7 MPa. A post cure at between 175
and 250°C is necessary to develop full high temperature properties.
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Table 13.7 Commercial phenol-aralkyl resins
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Xylok 337 resin 60 MEK 1·04 Epoxy cured. Mixing ratio 1:1. For
Xylok hardener 90 MEK 1·13 1,0-3,0 laminating applications up to
2ODoe
n
"Powder density.
b Abel closed cup.
ASTM
test Silicone
Property Units method resin
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OTHER RESIN SYSTEMS 305
Melamine-- Urea-
Polyimide Phenolic formaldehyde formaldehyde Polyester Epoxide
resin resin resin resin resin resin
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306 FRP TECHNOLOGY
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OTHER RESIN SYSTEMS 307
REFERENCES
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Chapter 14
REINFORCEMENTS
14.1 INTRODUCTION
308
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Table 14.1 Typical properties of reinforcing fibres and some materials with which they compete
Ultimate Specific
tensile Tensile tensile Specific
Specific sirength modulus strength modulus
Fibre gravity (GPa) (GPa) (GPa) (GPa)
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Asbestos 2·5 0·7-104 135-170 0·28-0,56 54-68
Cotton 1·6 0'3-0'7 0·19-0·44
Sisal 1· 3 0·8 0·61
Aluminium (bulk) 2·8 0·5 75 0·18 27
Steel 7·8 1·0 200 0·13 26
Titanium DTD 5173 4·5 0·96 110 0·21 25
Boron 2·62 H 344 1-30 130
Beryllium (bulk) 1·82 1·03 310 0·57 170
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0
\0
310 FRP TECHNOLOGY
have all been prepared and evaluated. Frequently the effect being sought is
only a slight increase in the rigidity of a glass reinforced system and this can
readily be achieved by the addition of a small proportion of carbon fibre
into the system. A variety of different hybrids can be prepared, each of
which may be of use in a particular situation. Clearly, therefore,
considerable design scope exists.
Another fibre used as a reinforcement in resin systems is asbestos. This
provides composites with greater stiffness than can be obtained with glass
reinforcements alone. Asbestos reinforced composites also have improved
water and chemical resistance. Thus a layer of asbestos reinforced resin
may be used to provide a chemically resistant liner to a GRP vessel.
Various other fibres are used in dough moulding compounds where cost
is of prime importance. These include cotton, sisal and cellulose (wood,
paper).
A comparison of the properties of some of the different fibres in use is
shown in Table 14.1.
For convenience this chapter has been divided into the following
sections:
Surfacing tissues
Glass fibre reinforcements
Carbon fibre reinforcements
Aramid fibre reinforcements
Other fibre reinforcements
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REINFORCEMENTS 311
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312 FRP TECHNOLOGY
Composition (%)
A C E R S
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REINFORCEMENTS 313
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314 FRP TECHNOLOGY
Fig. 14.2. A typical roving cheese. (Courtesy of K & C Mouldings (England) Ltd.)
Spray lay-up
Here the roving should chop easily 7 and exhibit good fibre integrity with
excellent wet out, minimum air entrapment and low static build up. The
strands are usually medium hard with a fibre diameter of about 10 !lm.
Normally a full 40 tex strand is used. Similar rovings are used for the
preparation of preforms.
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REINFORCEMENTS 315
integrity for good flow characteristics during moulding. They are also
designed to give some breakage during moulding to reduce surface
waviness and to produce minimum fibre visibility in the finished moulding.
Fibre diameter varies from 10 to 14 Jlm and full strand construction is used.
Weaving
Rovings intended for weaving need to be similar to those used for
filament winding, that is soft or very soft. They also need to be highly
ribbonised to prevent the strands from separating during weaving. The
resultant woven rovings must exhibit good wet out. Fibre diameter varies
from 10 to 14 Jlm.
Classification offibres
Fibres have been classified, wherever possible, according to the BSjISO
code- for example EC 10 40 2400. Here EC indicates E-glass continuous;
10 indicates the nominal filament diameter in 11m (microns); 40 indicates
the weight per 1000 m (tex); 2400 indicates the roving yield or total weight
per 1000 m.
Table 14. J 1 lists the commercially available rovings classified as far as
possible by the BSjISO code.
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Table 14.3 CommerciaUy available chopped strands
w
Supplier 0'1
-
Product code Size BS/ISO code Fibre length (mm) Applications
Fibreglass Ltd
FGCS 1401 EC 13 38 3, 6, 12, 25 DMC-epoxy, polyester
FGCS 1617 EC 13 38 3, 6, 21, 25, 50 DMC, preforms
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Vetrotex (UK) Ltd
K35 Silane EC 10 80 6, 13, 25, 50 DMC-polyester
K52 Silane EC 10 80 3 DMC-epoxy, polyester
Silane EC 14 150 6, 13,25 DMC-epoxy, polyester
P343 Silane EC 10 160 6, 13 Epoxy, phenolics
Silane EC 14 300 6, 13 Epoxy, phenolics
PS24 Silane EC 10 160 6, 13 Plaster, paper
VB/OI Silane EC 10 40 3,6 Epoxy, phenolic, melamine
MDS Silane EC 10 40 6, 13 DMC, plaster
P3 Silane EC 10 40 3,6, 13,25, 50 DMC
P5 Silane EC 10 40 3, 13 Epoxy, phenolic
REINFORCEMENTS 317
Supplier
Product code Finish Length Applications
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318 FRP TECHNOLOGY
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REINFORCEMENTS 319
Supplier Weight
Product code Binder (gjm 2 ) Applications
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320 FRP TECHNOLOGY
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REINFORCEMENTS 321
number of different weaves, the variety being greater for yarn based fabrics.
Examples of these are given below.
Plain weave
Here each warp and weft thread passes over one thread and under the
next (Figs 14.4 and 14.5). These fabrics often have good resistance to
distortion and give reproducible laminate thicknesses. Plain weave is also
known as taffeta. Materials are available made from yarn and rovings.
Twill weave
With twill weave the number of warp ends and weft picks which pass
over each other can be varied. In a 2 x 1 twill, weft yarns pass over one and
under two warp ends, while in a 2 x 2 twill the weft yarns pass over two and
under two warp ends (Fig. 14.6). This produces a regular diagonal pattern
on the cloth. Twill weave cloth has good drapability and somewhat
improved laminate strength. It can be made either from rovings or yarns.
Twill weave is also known as serge.
Satin weave
Here the number of warp ends and weft picks which pass over each other
before interlacing is greater than with twill weave and the interlacing is
always with one crossing thread (Fig. 14.7). In consequence one side of the
fabric consists mostly of warp threads, the other weft threads. Satin weave
cloth has excellent drapability and imparts high tensile and flexural
properties to a laminate. This weave is used both with rovings and yarns.
Leno weave
In this type of weave the warp yarns are twisted between each weft yarn.
This imparts stability to very open fabrics and stops slip. This weave is only
used with yarn.
Unidirectional weave
Here the warp threads are held together by fine weft threads so that the
fabric is mostly unidirectional in structure (Fig. 14.9). With this type of
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322 FRP TECHNOLOGY
i :m:m:
:!: :::: II
:!j
~:!'
:i; :!;
m
Wi: I:::
:i ::i [:,'
Fig. 14.6. Twill weave roving. Type Fig. 14.7. Satin weave cloth. Type 284 ;
271; weight 750 g/m2. weight 865 g/m 2.
Fig. 14.8. Mock leno weave cloth. Fig. 14.9. Unidirectional roving. Type
Type 138; weight 288 g/m2. 280; weight 610 g/m2.
(All materials illustrated are supplied by Marglass Ltd, whose codes are given.)
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REINFORCEMENTS 323
Although carbon fibres have been known for very many years,l it was not
until around 1964 that the first high strength, high modulus carbon fibres
were produced. These first fibres were produced at the Royal Aircraft
Establishment, Farnborough, the process being covered by British Patent
1 110791. Prior to this the only carbon fibres available were oflow strength
and generally unsuitable for use as reinforcing fibres.
In the 1880s Thomas Edison used carbon fibre as the filament material in
incandescent lamps. This was later to be replaced by tungsten filaments. It
was not until the late 1950s that interest in carbon fibre as a reinforcing
material arose. This was mainly due to the need for high strength, light
weight, thermally stable materials for the aerospace industry, much of
which could be met by the use of carbon fibre. Developments therefore
went ahead to try to produce continuous high strength fibres.
In the USA, developments centred around the use of cellulose fibre as a
precursor (US Patents 3 454 362 and 3 503 708) whilst in the UK
polyacrylonitrile fibre was used (British Patent 1 110791). Other pre-
cursors examined were lignin and pitch, both in Japan.
Today high strength, high modulus carbon fibres are available in large
quantities prepared both from cellulose and polyacrylonitrile precursors,
whilst somewhat lower strength fibres are available based on a special
hydrocarbon pitch. In all processes the carbon fibres are produced by
controlled oxidation and carbonisation of the precursor fibre at tempera-
tures of up to about 2600°C. This results in a high strength fibre. By
subsequently increasing the temperature to about 3000°C the high strength
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324 FRP TECHNOLOGY
Carbon
content Carbonisation yield
Precursor material (% wt) (% wt)
Cellulose fibre 45 10-15
Polyacrylonitrile 68 40
Lignin ~70 50
Hydrocarbon pitch 95 85-90
carbon fibre can be converted into a high modulus graphite fibre. Both
forms are commercially available today.
Considering the various processes available for manufacturing carbon
fibres, the conversion of polyacrylonitrile fibre to carbon fibre is somewhat
more efficient than that using cellulose fibre, due to the higher carbon
content of the precursor. In Table 14.6 are shown the carbon contents and
yields of the various starting materials. Properties of fibres resulting from
these various precursors are given in Table 14.7.
When considered in terms of composite properties, carbon fibre
reinforced resins offer more to the designer than any other material in
current use, in terms both of strength and rigidity. The materials which
approach closest to CFRP are boron composites, beryllium and titanium.
Composites are usually prepared by some form of pressure moulding
technique and have a typical fibre volume of about 60%, although hand lay-
up carbon fibre composites can be prepared with lower fibre contents. Test
results are mostly quoted at 60% fibre volume, if necessary after a simple
arithmetical adjustment.
Carbon fibres are generally surface treated to improve the bonding of the
resin matrix to the fibres. They are also frequently sized with a resin to aid
handling and to prevent damage during processing.
Like glass fibres, carbon fibres can be obtained in a number of different
forms, from continuous filament tows (this is equivalent to roving in glass
terms) to chopped fibre mat. Composites with the highest strength and
modulus result from the use of unidirectional reinforcement. Examples of
three types of carbon fibre reinforcements are shown in Figs. 14.10-14.12.
Carbon fibre is manufactured as continuous filament twist-free tow,
consisting of 5000, 6000, or 10 000 individual filaments, depending on
manufacturer. These tows are then used for the manufacture of other
materials. Apart from pure carbon fibre products several hybrid products
are available, consisting of alternate tows of glass and carbon fibres.
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Table 14.7 Properties of some carbon fibres
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Polyacrylonitrile Graphite Graphil HM 8 1·87 2·4 330
W
N
Ul
326 FRP TECHNOLOGY
Fig. 14.10. Carbon fibre aligned sheet. Continuous carbon fibre warp with fine
carbon fibre weft.
Fig. 14.11. Unidirectional woven carbon fibre tape. Unidirectional carbon fibre
warp, fine glass fibre weft.
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REINFORCEMENTS 327
Carbon fibre, unlike any other reinforcing fibre, has a negative coefficient
of thermal expansion along the fibre axis but a positive transverse
coefficient of thermal expansion. This means that any resin system
reinforced with carbon fibres must be capable of absorbing this strain. This
is particularly true where 90° cross-plied composites are made.
One of the first resin systems reinforced with carbon fibre was an epoxy
novolac resin cured with a boron trifluoride complex. The unreinforced
cast resin has a strain of between 1 and 1· 5% at break, which is only of the
same order as the strain set up within the matrix when the composite is
cooled from processing temperature to ambient temperature. Thus some of
the early cross-plied composites made with this resin system failed almost
immediately. Today, where such a resin system is needed to give high
temperature performance, fibre orientation is restricted to a maximum
angle of 30°.
Most resin systems developed for use with carbon fibre reinforcement
have a strain at break of between 4 and 6% to accommodate adequately the
differences in coefficients of thermal expansion between resin and fibre.
Thus cross-plied composites can be made for service over the temperature
range - 40°C to above 100°C. The actual upper temperature limit depends
on the matrix used and may be as high as 200°C in certain circumstances.
Some of the commercially available materials are listed in Table 14.14
(pp. 347-8).
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328 FRP TECHNOLOGY
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REINFORCEMENTS 329
Supplier
Products
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330 FRP TECHNOLOGY
14.6.3 Nylon
Nylon fabrics may be used as reinforcements for epoxide resin systems to
give flexible laminates with high impact, abrasion and chemical resistance.
They are mostly combined with glass fibre reinforcements for specialised
applications and are rarely used alone.
14.6.5 Cotton
Cotton fibres provide a cheap fibrous reinforcement for use in dough
moulding compounds-mostly phenolic resin based. They are rarely used
in polyester or epoxide resin compositions, although printed fabrics can be
used to provide a decorative finish for such applications as walling panels.
Here the printing ink must be insoluble in the resin and not discoloured by
the catalyst.
14.6.6 Sisal
Sisal is another cheap fibrous material which is used in phenolic based
dough moulding compounds but rarely with polyester or epoxide resin
systems.
14.6.7 Asbestos
Asbestos is frequently used with phenolic resins in dough moulding
compounds to provide rigid, hard wearing, temperature resistant com-
posites. Such composites are used as friction brake pads on vehicles and a
variety of different machines; they have many other applications. Asbestos
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REINFORCEMENTS 331
can also be employed with epoxide and polyester resin systems to provide
composites with increased rigidity over glass and improved water and
chemical resistance.
Asbestos is available in a number of different forms, although chrysotile
asbestos-a hydrated magnesium silicate-is the most commonly used as a
reinforcement. It is available as paper, cloth, mats and ropes, all of which
find widespread use as reinforcements in phenolic resins but far less use in
epoxide and polyester resin systems. With legislation pending on the
restriction of the use of all forms of asbestos, it is debatable how much
longer asbestos will be used as a reinforcing material, except perhaps/where
no alternative can be found.
14.6.8 Paper
A variety of printed papers, such as wall paper, may be used to provide
decorative finishes to polyester mOUldings. Where such printed papers are
used they must obviously be able to be thoroughly wetted by the resin
system, and the printed colours must not run or change in contact with the
resin or catalyst. They find uses in decorative wall panels, coffee table tops
and other similar applications. Printed papers are also used widely to
provide the decorative finish to melamine based laminates.
14.6.9 Jute
Work is being carried out in India on the use of jute fibres as a
reinforcement for polyester resins 10 since this is a cheap readily available
fibre. Jute can be used as woven cloth or in yarn form for filament winding.
A variety of objects including houses, grain silos and fishing boats have
been evaluated.
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332 FRP TECHNOLOGY
REFERENCES
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Table 14.10 Surfacing tissues
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FPL 498 Pl5 C-glass Polystyrene 30 General, polyester, epoxy
FPL 498 P23 C-glass Polystyrene 50 General, polyester, epoxy
FPL498 C64 C-glass Polystyrene 27 0·25 General, polyester, epoxy
Overlay F 499 C-glass Polystyrene 44 General, polyester, epoxy
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N 34 Polyester None 0·23 General, continuous filament
N 44 Polyester None 0·24 0·24 Heavy duty applications,
continuous filament
N75 Polyester None 0·30 0·30 Electrical, continuous filament
Drape veil Polyester None 0·40 Hand lay-up, continuous filament
Printing service available for
printing designs on veils
REINFORCEMENTS 335
Product code
Supplier Type Finish BSjlSO code Applications
Fibreglass Ltd
Muhi:spray Chrome EC 10 40 2400 Spray lay-up
EC 10 80 2400
EC 10804800
Supn:spray Silane EC 1040 2400 Spray lay-up, SMC,
EC 10404800 sheet
Supr.<:preg Medium Silane EC 10 160 2400 SMC, DMC
hard EC 14802400
Supr~spray CC Silane EC 1040 2400 Centrifugal
casting
XRE 25 Silane 2400 Pultrusion
4800
Supr.<:wind Silane EC 13 2100 Filament winding,
EC 13 2400 pultrusion
EC 13 4700
Equ~rove Silane EC 13 600 Equitension for
EC 14 750 filament winding,
EC 17 1200 weaving
EC 21 1800
EC 17 2400
Supr~ave Silane EC 10 2400 Weaving
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336 FRP TECHNOLOGY
Silenka UK Ltd
051 Silane 300 Winding, pultrusion,
600 weaving
900
1200
2400
4800
058 Silane EC 10 1200 Weaving
EC 10 2400
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REINFORCEMENTS 337
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338 FRP TECHNOLOGY
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REINFORCEMENTS 339
HP Fabmat
800
{ISO CSM/crimp free
300 woven roving.
450 Hand lay-up,
press, winding,
pultrusion
Total
Fibreglass Ltd
Equc:mat Liquid Silane EC 1227 38 300 Hand lay-up, fast
450 wet out
600
Supr~mat Liquid Silane EC 1227 38 225 Hand lay-up. Fast
51 300 wet out. Suitable
51 450 for epoxies
EC 1351 51 600
51 750
51 900
Supr~mat Polyester powder Silane EC 1240 51 225 Hand lay-up, SMC
PB 51 300 Translucent
mouldings
51 450 Suitable for
epoxies
51 600
Supr~mat Polyvinyl acetate Silane EC 1227 51 450 SMC
SMC
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340 FRP TECHNOLOGY
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REINFORCEMENTS 341
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342 FRP TECHNOLOGY
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REINFORCEMENTS 343
Fibreglass Ltd
Fibreglass Ltd supply Fabmat and Linrovmat made by F.G. Industries. For
details see under chopped strand mat (Table 14.12).
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344 FRP TECHNOLOGY
Marglass Ltd
Woven ravings
269 Plain 270 0·3 47 43 Silane finish
263 Plain 339 0·33 61 55 Silane finish
280 Unidirec- 610 0·61 26 24 Silane finish
tional
271 Twill 750 0·58 32 32
316 Plain 610 0·59 16 12
364 Twill 646 0·61 31 24 Volan finish
266 Plain 848 0·69 20 16 Silane finish
Woven fabrics
7T Plain 186 0·15 142 126
IIOJ Mock lena 366 0·41 146 102
IllS 2/2 twill 329 0·28 118 118
113J Plain 176 0·18 59 67
116S 8 end satin 302 0·20 220 213
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REINFORCEMENTS 345
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346 FRP TECHNOLOGY
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REINFORCEMENTS 347
Courtaulds Ltd
Courtaulds 'GrafiI' carbon fibre, manufactured from polyacrylonitrile precursor,
is available in several different forms as follows:
Ultimate tensile Young's
Specific strength modulus
Fibre type gravity (GPa) (GPa)
Grafil A High strain 1·82 2·55 185-215
Grafil XA Super A, high performance 1·82 3·2 230
Grafil HT High tensile strength 1·76 3·27 220-250
Grafil HMHigh modulus 1·87 3·39 310-345
Grafil 0 Oxidised acrylic 1-35
Continuous filament tow
Generally supplied with o· 5% epoxy resin in lengths of 200- 2000 m. Each tow
contains 10000 filaments of approx. 8,um diameter.
A vailable sized with 2- 3% of either Shell Chemicals 'Epikote' 834 epoxide resin
or Scott Bader 'Crystic' 189 MV (polyester resin) or available unsized.
E = epoxy size S = surface treated
Grafil E/A-S; Grafil E/XA-S; Grafil E/HT-S; Grafil E/HM-S.
Short staple fibre
Available in all fibre types in lengths of 3 mm and 6 mm.
Unidirectional woven fabrics
Two types are available:
75/G Unidirectional Grafil continuous tow (warp) secured with a weft of 330
decitex glass or polyester yarn.
75/GE Unidirectional Grafil continuous tow alternated with 1200 tex E-glass
(warp) secured with a weft of 330 decitex glass or polyester yarn.
Grafil high modulus continuous ribbon
This consists of two, three, or five 10 000 filament tows of high modulus carbon
fibre in a knitted glass fibre tape 16 mm wide.
GrafilO
Grafil 0 is a new product recently introduced. It consists of an oxidised acrylic
fibre suitable for processing on normal textile machinery and is available as tow,
tops, yarn, woven or knitted fabrics. It can be used for making carbon/carbon
composites.
Hyfil Ltd
HYFIL-Torayca carbon fibre, manufactured from polyacrylonitrile precursor, is
available in only one fibre type.
Continuous fibre sheet
This consists of continuous collimated tows of 6000 filaments held together with
less than 0·5% of fine weft material, also carbon fibre.
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348 FRP TECHNOLOGY
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Chapter 15
15.1 INTRODUCTION
With hot press moulding, injection and transfer moulding processes, the
most convenient procedure is to use a pre-formed moulding compound to
which all necessary ingredients have been added. This eliminates mixing
errors and enables faster production rates to be achieved.
Moulding compounds can be divided into three broad categories:
(i) Dough or Bulk Moulding Compounds (DMC, BMC).
These compounds consist of a resin system containing chopped
fibre reinforcement and a filler. Pigments may be added if required.
The resin system may be polyester, epoxide, phenolic,
melamine-formaldehyde, urea-formaldehyde or one of several
others.
(ii) Sheet Moulding Compounds (SMC).
These are invariably polyester resin based and consist of chopped
strand mat or chopped rovings impregnated with a filled resin
system, to which pigments and other additives have been added. As
its name implies it is supplied in sheet form.
(iii) Prepreg.
Prepreg is used to describe a reinforcement which has been
pre-impregnated with a resin system prior to use. Generally fillers are
absent from such a system. Whilst the term mostly refers to
reinforcement impregnated with an epoxide resin system, other
resin systems are encountered, such as certain types of polyester
resin and polyimide resins.
All three types of material require heat to soften and consolidate the resin
system and to effect cure. Products are available which can be processed by
349
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350 FRP TECHNOLOGY
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DOUGH AND SHEET MOULDING COMPOUNDS AND PREPREGS 351
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352 FRP TECHNOLOGY
[email protected]
Ci
§
:z:
>
zCi
a -POlyethYlene film
Polyethylene
~..,
film 3:
8
t""
Ci
a Z
C'l
SMC wind-up
[email protected]
~
Ci
oI 'tj
~
~
@
w
VI
W
354 FRP TECHNOLOGY
Parts by weight
Polyester resin 100
t-Butyl peroxybenzoate (95%) 2-3
Zinc stearate (release agent) 3-4
Magnesium oxide (thickening agent) 2-3
Pigment dispersion 5-8
Filler 140-180
Thermoplastic additive 5-20
CSM or chopped rovings 50--100
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DOUGH AND SHEET MOULDING COMPOUNDS AND PREPREGS 355
15.4 PREPREGS
Fig. 15.2. A typical printed circuit board viewed/rom the component side.
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356 FRP TECHNOLOGY
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DOUGH AND SHEET MOULDING COMPOUNDS AND PREPREGS 357
Reinforcement
Nip rollers
~~~~--ReSin bath
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358 FRP TECHNOLOGY
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Table IS.1 Some commercial dough and bulk moulding compounds
Mould Tensile Flexural Flexural
Product Reinforce- Specific shrinkage strength strength modulus Water
code ment gravity (%) (MPa) (MPa) (GPa) absorption Comments
[email protected]
Ciba-Geigy Plastics and Additives Company (%)b
Araldite
NU 471 1·95 0·6-0,8 80 0·03 Epoxy based mineral filled, CjT
NU 475 Glass 1·8 0,6-0·8 110 0·04 Epoxy based glass fibre filled, CIT
NU 480 Glass 1·8 90 0·04 Epoxy based, I
NU 481 1·8 90 0·04 Epoxy based mineral filled, I
NU 482 Glass 1·9 80 0·03 Epoxy based, low viscosity, I
Neonite
EG 60 30% glass 1·75 0·3 100 180 16 0·07 Epoxy based, CjT
EG61 30% glass 1·75 0·3 100 180 16 0·07 Epoxy based, CjT
EG 62 65% glass 1·78 0·05 140 300 25 0·08 Epoxy based, C
DG 10 40% glass 1·82 0·05 100 200 18·5 0·07 Diallyl phthalate based, CjT
Table 15.1 (Continued)
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ssion, transfer or injeclion moulding
43-2021 Glass 1·7 0·15 45 95 7 20 High strength, all colours but white
43-2026 Glass 1·8 Nil 45 100 9 25 Self-extinguishing, limited colours
43-2029 Glass 1·85 0·1 50 90 8·5 25 Fire retardant, limited colours
43-2035 Glass 1·8 0·05 50 95 8·5 20 Low shrink, all colours
43-2065 Glass 1·7 0·02 50 110 7 10 Bisphenol A, chemical resistant
43-2122 Glass 1·85 0·05 45 90 9 20 Low shrink, limited colours
43-2125 Glass 1·8 0·15 45 90 8·5 15 Electrical grade, all colours
43-2137 Glass 1·85 0·1 35 85 7 25 Fast cure, white, limited colours
43-2140 Glass 1·8 0·2 55 120 10 15 High strength, electrical, all colours
"Expansion
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LS 15% glass 1·85 0·1 27 96 0·2 Low cost, high strength
22% glass 1·85 0·1 34 110 0·2
30% glass 1·85 0·1 41 124 0·2
2000 BMC 15% glass 1·9 0·3 34 103 0·3 Arc resistant, electrical
30% glass 1·95 0·3 41 124 0·3
2100 BMC-
LS 15% glass 1·8 0·1 34 90 0·2 Arc resistant, electrical
22% glass 1·82 0·1 41 103 0·2
30% glass 1·85 0·1 48 117 0·2
Also available as CR-SX series
2003 BMC 10% glass 1·9 0·3 21 83 0·\ Appliance/business machines
15% glass 1·9 0·3 27 96 0·1
22% glass 1·92 0·3 34 110 0·2
30~{; glass 1·95 0·3 41 124 0·2
Table 15.1 (Continued)
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22% glass 1·77 0·1 34 117 0·15
30% glass 1·79 0·1 41 144 0·15
6000BMC 5% glass 1·95 0'2-0'4 20 55 0·1 Phenolic replacement
10% glass 1·89 0·2-0·4 27 69 0·1
15% glass 1·85 0·2-0·4 34 83 0·1
20"10 glass 1·82 0·2-0·4 41 103 0·1
6100 BMC-
LS 5% glass 1·87 0·1 20 55 0·1 Phenolic replacement
10% glass 1·80 0·1 27 69 0·1
15% glass 1·79 0·1 34 83 0·2
20% glass 1·75 0·1 41 103 0·2
7100 BMC 15% glass 1·78 0·02 27 103 Low profile, automotive
22% glass 1·80 0·02 34 117
Primi-ject
1000 series 5% glass 2·05 0-2-0'5 20 55 0·1 Phenolic replacement for existing tooling
10% glass 2·02 0'2-0'5 27 69 0·1
15% glass 1·90 0'2-0'5 34 83 0·1
20% glass 1·85 0·2-0·5 41 103 0·1
lJOO series 5% glass 2·03 0·1 20 55 0·2 Phenolic replacement for existing tooling
10% glass 2·00 0·1 27 69 0·2
15% glass 1·85 0·1 34 83 0·2
20% glass 1·80 0·1 41 103 0·2
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SX 566/9 Asbestos 1·7 0,1-0,3 50 70 5-10 Asbestos filled
SX 644 Glass 1·81 0,2-0,3 55 75 5-10 Glass/mineral filled
SX 650 Glass 1·75 0·1-0·3 55 80 5-10 Glass filled
SX 652 Glass 1·77 0·1-0·3 50 75 5-10 Glass/mineral filled
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1200 SMC- 15% glass 1-85 0-1 41 124 General purpose, low shrink
LS 22% glass 1-85 0-1 62 158
30% glass 1-85 0- I 96 200
2200SMC- 15% glass 1-75 0-1 41 110 0-3 Electrical grade, arc resistant
LS 22% glass 1-77 0-1 55 124 0-3
30% glass 1-80 0-1 69 138 0-3
2203 SMC- 15% glass 1-75 0-1 41 110 0-3 Appliance, business machine grade
LS 22% glass 1-77 0-1 55 124 0-3
30% glass 1-80 0-1 69 138 0-3
3200 SMC- 15% glass 1-75 0-1 41 lIO 0-3 Arc resistant, non-track
LS 22% glass 1-77 0-1 55 124 0-3
30% glass 1-80 0-1 69 138 0-3
4200 SMC- 15% glass 1-75 0-15 41 110 0-15 Bisphenol based, corrosion resistant
LS 22% glass 1-78 0-15 55 130 0-12
30% glass \-80 0-15 82 151 o 12
""/0 glass 1'~V V'V" O~ 1'14 V·.O
30% glass 1·85 0·02 86 172 0·25
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M 200 B Low shrink grade BS 476 pt 7 class I
M 800 series M 800 Flexible grade, medium shrinkage, based on isophthalic polyester
Resin system Flexural strength (GPa) Flexural modulus (GPa) ILSS (MPa)
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Courtaulds Ltd
Continuous unidirectional carbon fibre prepreg tape is available based on all four grades of carbon fibre manufactured by
Courtaulds Ltd: Grafil A-S; Grafil HT-S; Grafil HM-S; Grafil XA-S.
Resin systems
Epikote 21O/BF 3 400 Epoxy for use over the temperature range - 40°C to + 150°C.
Cure: 1 h at 170°C
HC 3501 epoxy For use over the temperature range - 4WC to + 180°C.
Cure: i h/175°C
Hyfil Ltd §
Continuous unidirectional carbon fibre prepreg tape made from HYFIL-Torayca-130 carbon fibre. ~
Resin systems Dwell time Cure time Post cure ~I:)
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Availability: 200 m continuous tape}
~
moulds to 60% carbon fibre volume ~V>
1·2 m sheets >
Z
2. Glass fibre prepreg This is manufactured from a lightweight square weave glass cloth from solventless resin systems. I:)
Availability: 300 m rolls based on 0·025 mm or 0·04 mm thick cloth
3. Unidirectional glass prepreg This is manufactured from E-glass rovings from solventless resin systems. ~
"C
Availability: 200 m rolls }
Resin system R 7 H ~
1·2 m sheets
\.»
0\
-..J
\;J
0'1
00
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R14A 26 13 1·2 131 60 Epoxy novolac system, low strain. Not
recommended for crossplies greater than
± 30'
Rl6A 26 60 Polyester system
Fothergill & Harvey Ltd
Carboform preimpregnated carbon fibre is supplied in the following forms based on high modulus, high strength and
intermediate modulus fibres.
Sheet Unidirectional-standard sizes up to 1220 x 920 mm; nominal moulded ply thickness, 60% fibre volume, d
0·127mm. ~
Tape Unidirectional-rolls up to 100 m long; widths from 19 mm to 500 mm. @
Woven fabric Range available based on plain weave fabric, 5-end satin and 8-end satin fabric. >
~
Code Weave Weight Thickness Threads/dm
(g/m2 ) (mm) Warp Weft
!9
~
A 001 8-end satin 374 0·40 94 91 3:
A 002 Plain 192 0·25 47 47 ~t""
A 004 5-end satin 283 0·30 70 70 d
Z
Based on Torayca T300, 3000 filament carbon fibre yarn. o
83:
Typical mechanical properties with code 69 resin
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Code Test Flexural Flexural Tensile ILSS
strength strength (;l
direction modulus
(GPa) (GPa) (GPa) (MPa)
i
~
d
A 001 Warp 0·96 65 0·55 62 ."
Product Resin type Shelf-life Maximum Composite properties, 60% carbon fibre volume,
code ( weeks) operating Type 2 fibre, 20 c C
- ISoC + 20°C temp. ('C)
Flexural Flexural ILSS Comments
strength modulus
(GPa) (GPa) (MPa)
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125°e, modified flow
control
95 Epoxy 52 4 80 1·70a 120' 90 a Low temperature cure,
0
120 e
Micanite & Insulators Co. Ltd
This company manufactures a range of prepregs to customer requirements.
a Type 3 fibre.
DOUGH AND SHEET MOULDING COMPOUNDS AND PREP REGS 371
REFERENCES
I. Brown, B. and Bowyer, G. (1978) Paper 15, Reinforced Plastics Congress 1978,
Brighton, UK.
2. Burns, R. and Pennington, D. (1978) Paper 16, Reinforced Plastics Congress
1978, Brighton, UK.
3. Anon. (1979) Modern Plastics International, May, 11.
4. Anon. (1978) Modern Plastics International, October, 52.
5. Anon. (1978) Modern Plastics International, May, 62.
6. Anon. (1980) Modern Plastics International, January, 28.
7. Seamark, M. J. (1978) Paper 26, Reinforced Plastics Congress 1978, Brighton.
UK.
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Chapter 16
16.1 INTRODUCTION
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FILLERS AND PIGMENTS 373
Additional factors which need to be taken into account are the effect of the
filler on the properties of the liquid and cured systems. Some of these
factors are listed below although not all are applicable to each filler.
(i) The effect of the filler on the liquid resin system.
Increases viscosity.
Increases bulk.
Produces thixotropy.
With polyester resins-accelerates or retards cure.
Reduces exotherm.
Abrasive fillers cause wear on moulds during processing.
(ii) The effect of the filler on cured resin properties
Reduces cost.
Renders opaque-most fillers.
Increases impact resistance.
Decreases flexural strength.
Increases rigidity.
Reduces shrinkage.
Reduces water absorption.
Increases abrasion resistance.
Modifies electrical and thermal properties.
Reduces flammability.
Raises heat deflection temperature.
Abrasive fillers make machining difficult.
Several hundred fillers are available commercially, many of which are of
specialised interest only. Those which find widespread use are the various
grades of calcium carbonate, quartz and silica flours, talc and various clays
such as china clay.
Most fillers have a particle size within the range 0·015).lm up to 80 ).lm.
The smaller the particle size the greater the increase in viscosity of the resin
system for any given filler loading. The smallest particle size fillers, such as
silica aerogel or fumed silica (0·015 ).lm), are used at about 5% addition to
produce thixotropy. The coarser fillers may be used at up to 600% addition.
Where fillers are used in laminating systems it is preferable that particle
size is kept below 10 ).lm so that the filler is not filtered out by the glass fibres
during processing. This is particularly true with sheet and dough moulding
compounds and liquid injection systems.
With non-laminating applications such as flooring, graded silica sand is
frequently used as filler. Here, particle size distribution may range from
about 53 ).lm up to 1-2 mm and filler to binder ratios of 7: 1 are common.
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Table 16.1 Some properties of fillers
Coefficient
Oil of thermal
Bulk absorption expansion
Specific density Hardness value ( in/in Particle
Filler gravity (g/ml) (moh) (g/IOO g) cC x 106 ) pH shape Principal uses
Aluminium hydroxide [AI (OHhl 2·4 0·4-1·3 2·5-3·5 20-40 8'5-9'5 Irregular f
Aluminium oxide (alumina) 3·7-4·0 1'3-1·6 9 10-50 7 3·6 Irregular a, d, S, i
Aluminium silicate 2·6 0·6-1·6 2-20 Platelike c, p, s
Antimony trioxide 5·3-5·9 1·3-1·6 10-15 2-3 Irregular f
Armospheres 0·6 0·4 Spherical I
Barium sulphate 4·3-4'5 2'5-4'5 5-15 4-5 Irregular p
Barium titanate 5,5-5·9 1·3-1·6 16-19 Irregular d
Bentonite 2-6-2·7 30-55 8'5-10 Platelike t
w Calcium aluminium silicate 2·65 6,0-6,5 g
~ Calcium carbonate-ground 2·7-208 0·8-0·9 3·0 5-15 0'5-0'9 9-10 Irregular g, p, s
- precipitated 2-6-2·7 0·8-0·9 3·0 15-60 0·5-0·9 9-10 Irregular g, p, s
-coated 2·6-2'8 0·8-1·0 3·0 5-15 0'5-0·9 9-10 Irregular g, p, s
Calcium magnesium carbonate
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(dolomite) 2·8-2·9 1·1-1·3 g
Calcium silicate 208-2·9 4'5-5'5 20-45 9-10 Acicular g
Calcium sulphate 2·4-2·9 0·6-1·0 2·0-3·5 5-10 3-5 Irregular g, s
China clay (kaolin) 2·5-2-6 1-2 25-45 4-8 Platelike p, t
Fillite 0,3-0,7 Spherical I
Glass-solid spheres 2·48 1·5 5·8 8·5 Spherical c, g
- hollow spheres 0·15-0'38 Spherical I
- flakes, C-glass 2-45 Platelike c
Graphite 2·2 0'6-4·0 Platelike b, e, p
Iron oxides 304-5·1 Irregular p
Kieselguhr 1·8-2·3 80-125 5'5-7
Lead oxides 8·8-9-4 Irregular p
Magnesium aluminium silicate
(Fuller's earth) 1-8-2-5 0-3-0-6 30-50 Irregular
Magnesium carbonate 1-8-2-8 0-15-0-6 3-0 70-80 10-4 Irregular f, p
Magnesium oxide 2-7-3-7 55-70 10-5 Irregular t
Mica 2-7-304 0-3-0-4 2-5-3-0 50-70 18-27 7-8 Platelike c, d, i
Phenolic microballoons 0-2-0-25 0-1-0-15 Spherical I
Pumice 2-2-2-3 8-9 I
Q-cell Spherical I
Silica 2-6-2-7 1-0-2-0 7 15-40 0-15-3 7-8 Irregular a, g, i, S
Slate 2-9 0-7-0-9 25-45 6-7 Irregular a, g
Talc (magnesium silicate) 2-4-3-0 1-0-2-0 1-2 20-45 7-9 9-10 Platelike g
Vol
...., Titanium dioxide 3-9-4-2 6-7 20-30 7-1-9-2 Platelike p
v. Vermiculite 2-2-2-6 0-1-0-2 6-5-7-5 Expanded I
Plates
Zinc oxide 5-6-6-0 10-15 Platelike p
Zirconium oxide 5-0-7-0 1-2-1-4 Irregular d
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Zirconium silicate (zircon) 4-6 1-7-1-9 3-0 Irregular a, c, d, i, S
Many different mineral fillers are used with thermosetting resins to modify
cured properties. These are mostly derived from naturally occurring
deposits and suitable fillers may be obtained by crushing and sieving
natural minerals or by refining and purifying.
16.2.1 Carbonates
Calcium, magnesium or mixed calcium/magnesium carbonates can be
found naturally occurring in various parts of the world. These find
widespread use as fillers both for laminating and casting applications.
Calcium carbonate
By far the most commonly used filler for polyester resin systems is
calcium carbonate. This occurs naturally as chalk, limestone and marble
and may contain traces of other minerals. High purity calcium carbonate
or whiting is prepared by precipitation from solution, particle size
depending on the method of manufacture. Ultra-fine grades, with a particle
size of 0·05 /-lm, are prepared by precipitation.
Calcium carbonate fillers, as normally obtained, have a high surface area
and hence high resin absorption. Whiting, the semi-amorphous form, has a
higher resin absorption than the crystalline calcite form. To permit higher
loadings to be used, calcium carbonate is often surface coated with
stearates or resin emulsions.
Dough and sheet moulding compounds are often filled with calcium
carbonate. Such compounds should not, however, be used where mould-
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FILLERS AND PIGMENTS 377
ings have to resist strong acids. Cured resin systems filled with calcium
carbonate can be readily machined since this filler is non-abrasive.
Crystalline forms: Calcite -rhombohedral-specific gravity
2·71
Aragonite -orthorhombic-specific gravity
2·93
(Aragonite transforms into calcite on heating)
Available fillers: Chalk or whiting -quarried, pulverised and
slurried. Varies in purity
depending on quarry.
Semi-amorphous.
Limestone -Predominantly calcite.
May be contaminated
with magnesium
carbonate, silica, clays,
iron compounds and
organic matter.
Available wet or dry
ground.
Marble - A polycrystalline calcite
formed when limestone
is subjected naturally to
heat and pressure.
Available wet or dry
ground.
Precipitated - High purity whiting. It
consists of a mixture of
calcite and aragonite.
Magnesium carbonate
This occurs naturally as magnesite (MgC0 3 ) and dolomite
(MgC0 3 .CaC0 3 ). Pure magnesium carbonate is prepared by precipitation
which, when carried out at a low temperature and from dilute solution,
produces the light carbonate. This is usually assigned the formula
MgC0 3 .Mg(OH}z.3H 20. At higher temperatures and concentrations the
heavy carbonate is formed. This is considered to have the formula
MgC0 3 ·Mg(OH)2.4H 20.
Magnesium carbonate can be used as a filler in its own right or to
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378 FRP TECHNOLOGY
Talc
Talc consists of hydrated magnesium silicate and is a very soft mineral
with a plate-like structure. When used as a filler in thermosetting resin
systems it improves their electrical insulation, heat and moisture resistance.
Talc filled systems exhibit good machinability. Talc may be used as a filler
for sheet and dough moulding compounds.
Calcium silicate
Calcium silicate occurs naturally as the meta silicate wollastonite. It is
available in a variety of grades from fibrous to finely divided particles and
forms a useful filler for thermosetting resin systems. It is frequently used in
paint compositions. It provides excellent electrical and thermal insulation
properties.
Kieselguhr
Kieselguhr or diatomaceous earth is a form of silica consisting of the
fossil remains of diatoms-microscopic single-celled plants with a silica cell
wall. It comprises some 70-90% hydrated silica with the rest made up of
impurities.
It is used as a filler in thermosetting resin compositions to improve heat
[email protected]
FILLERS AND PIGMENTS 379
Zircon
Zircon or zirconium silicate is used as a filler where very high abrasion
resistance is required. Because of this, zircon filled systems are extremely
difficult to machine. Filler loadings as high as 600 phr are possible.
Bentonite
Bentonite is a montmorillonite clay containing a number of different
metal atoms. Due to its weakly bonded structure it can be easily cleaved
and has a soapy feel. It is also highly absorptive.
Bentonite is mainly used in coating applications where it serves as a
thickening agent.
Slate
Slate consists of a highly compacted sedimentary clay with definite
cleavage planes. In powder form it provides a cheap abrasion resistant grey
filler often used to produce a hard wearing finish to GRP moulds. The
machining of slate filled compositions is difficult and requires the use of
special tools.
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380 FRP TECHNOLOGY
Mica
Mica or potash mica consists of potassium/aluminium substituted
pyrophyllite (aluminium silicate). Other substituted micas are also found.
The potassium atoms form weak bridges between silica layers resulting in a
thin sheet structure with individual sheets less than 25 flm thick. These
sheets exhibit excellent dielectric strength and low thermal conductivity,
coupled with good flexibility.
Due to its excellent electrical properties, ground mica finds wide
application in the electrical industry as a filler for thermosetting resins. It
improves electrical properties, heat, crack and moisture resistance and also
exhibits good anti-settling properties in liquid resin systems. In laminates,
mica increases rigidity, imparts better dimensional stability and reduces
cost. It can be used in spray lay-up formulations as well as hand lay-up and
moulding compounds.
Vermiculite
Vermiculite is a natural crystalline silicate material which can be split
into inelastic sheets. When heated it loses water and expands about ten
times in volume to produce a lightweight granular material. It is in this
form that it is most commonly encountered.
Vermiculite is used as a low density bulk filler for polyester and epoxide
resin systems where light weight is important, such as the backing material
for GRP moulds.
Pumice
Pumice is a very lightweight cellular volcanic silica lava ejected from
volcanoes, which floats on water. It can be used as a lightweight filler in
resin systems.
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Glass flakes
Glass flakes are used in gelcoat and topcoat systems to provide a glass-
rich finish by aligning parallel to the surface. In this way they improve
water and chemical resistance and provide high wear and abrasion
resistance. Typical flake thickness is 3-4pm with sizes of 0·4, 0·8 and
3·2mm.
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dispersed in the resin either by the use of a triple roll mill, ball mill or high
speed disperser or by one of the other methods used in paint manufacture.
In certain cases micronised grades are available for ease of dispersion.
Alumina
Pure alumina (AI 2 0 3 ), prepared from bauxite, the principal ore, is
used as a filler to improve thermal conductivity, hardness and abrasion
resistance. It is chemically inert with a low coefficient of thermal expansion.
Calcined bauxite is used as a surface dressing on polyester and epoxide
resin floors and laminates to produce a non-skid surface.
Aluminium hydroxide
Aluminium hydroxide (Al(OHh) is employed as a flame retardant filler 1
but has to be used at high loadings to achieve this. It decomposes into
aluminium oxide (alumina) above 200°C and it is this mechanism which
gives it its fire retardant properties. The water vapour thus formed
displaces oxygen and blankets the fire. This takes place without the need for
halogenated compounds to be present. It can also be used at lower loadings
in combination with other fire retardant additives.
Antimony trioxide
Antimony trioxide is used extensively in polyester resins to reduce
flammability. It is used in conjunction with halogenated compounds
since it is the volatile antimony chloride or bromide, formed under fire
conditions, which effectively blankets the fire by displacing the oxygen
necessary to sustain burning. Since it is a white powder it also acts as a
pigment and produces opaque white systems. It may also be used in
halogen containing epoxide resin systems for the same purpose.
Iron oxides
Various oxides of iron are used as pigments and fillers for resin systems.
These vary in colour from black through brown and red to yellow,
depending on chemical composition. Similarly, specific gravity varies from
5·11 for Fe 2 0 3 to 3·4 for the naturally occurring yellow oxide.
Lead oxides
Lead oxides are generally used only as pigments in resin
systems-particularly in primers for coating applications. Both litharge
(PbO) and red lead (Pb 3 0 4 ) are used.
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Magnesium oxide
Magnesium oxide can be used as a filler to improve heat dissipation in
cured thermosetting resin systems. It is also used as a thickening agent in
polyester sheet moulding compounds. Here it produces a large increase in
viscosity of the polyester resin shortly after its addition. This slight delay in
its thickening effect is necessary to enable the resin system to be processed
into sheet form. Once the sheet moulding compound has been prepared the
resin must thicken rapidly so that it can be cut into sheets and handled.
Titanium dioxide
Pure titanium dioxide has two crystalline forms-rutile and anatase. By
far the most important for plastics applications is the rutile form. Whilst
titanium dioxide can be used in high loadings as a filler, its principal use is
as a white pigment. It is generally regarded as the standard white pigment.
It also acts as an effective UV absorber and improves the weather
resistance of cured resin systems.
Zinc oxide
Zinc oxide is another white oxide used as a pigment in resin systems and
also to impart hardness and heat stability. It is not such a good white
pigment as titanium dioxide.
Zirconium oxide
Zirconium oxide is occasionally used as a filler in epoxide resin systems
to improve dielectric properties. It can also be used as a pigment.
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therefore good practice to check the effect of the intended filler on cure rate
and cured properties. This should be carried out on filler of the same type
and from the same source as that to be used for production, since fillers
from different sources may well have different effects.
Various other fillers are used which do not fall into the other classifications.
Some of these are dealt with below.
Barium sulphate
Barium sulphate or barytes (BaS0 4 ) can be used as a general purpose
filler in thermosetting resin systems. It is also known as Blanc Fixe in the
precipitated form. This form finds application as a white pigment in coating
systems. Systems filled with barium sulphate are opaque to X-rays.
Barium titanate
Barium titanate is used as a filler in epoxide resin castings where very low
stable dielectric properties are required.
Calcium sulphate
Calcium sulphate can be used as a filler both as gypsum (CaS0 4 .2H zO)
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FILLERS AND PIGMENTS 385
and as plaster-of-Paris (CaS0 4 .iH 2 0). In the latter form it can serve to
absorb traces of water in the resin system. It can also be used to intensify
some colourants used in plastics materials.
Carbon black
Various carbon blacks are used as pigments in resin systems. They may
also be used to reduce surface and volume resistivity to prevent static build-
up. In this connection acetylene blacks prove useful with epoxide resin
systems. Care must be taken with polyester resin systems since some carbon
blacks can inhibit cure.
Graphite
Graphite is used as a black pigment and to increase electrical conductivity
of cured resin systems.
Phenolic micro-balloons
Phenolic micro-balloons consist of miniature hollow spheres of phenolic
resin. They provide a lightweight rigid cured structure suitable for backing
moulds or thin laminate sections.
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FILLERS AND PIGMENTS 387
With polyester resin systems most fire retardant additives are in-
corporated by the resin manufacturer to achieve a balance between fire
retardancy and cured properties. This balance of properties is frequently
only possible by the use of more than one fire retardant additive and can
only be achieved after extensive development work.
Fire retardancy can be further increased by adding inert fillers to the
system and by reducing the overall resin content of the laminate.
With polyester resin systems, chlorinated compounds are mostly used,
whilst brominated compounds tend to be favoured with epoxide resin
systems. (It is generally preferable to keep chlorinated compounds out of
systems to be used for electrical applications, hence the use of brominated
epoxide resins.)
Antimony trioxide
This is a dense white powder used in conjunction with halogenated resins
to produce fire resistance. It can only be used where opaque laminates are
acceptable. It is equally effective with polyester and epoxide resin systems.
Under fire conditions the antimony trioxide reacts with the halogen present
in the resin to form volatile antimony chloride or bromide which blankets
the fire by starving it of oxygen.
Aluminium hydroxide
This is a white powder used alone to produce fire retardancy. It works by
decomposing to alumina and water above 200°C and it is this water vapour
which blankets th( fire. It is also known as alumina trihydrate.
Polyester and epoxide resin systems can be coloured with transparent dyes
or pigments. Where dyes are used these must be compatible with the system
and should not react with either the peroxide catalyst in the case of
polyester resins, or the amine or anhydride curing agent in the case of
epoxide resin systems.
Transparent dyes are normally dissolved in a suitable solvent, such as
styrene or dibutyl phthalate, and then added to the resin system. Levels
normally used range from about 0·01% up to 0·2%.
Pigments can be obtained commercially as powders or as dispersions in
polyester resins, epoxide resins or phthalate plasticisers. Most moulders
prefer to use pre-dispersed pigment pastes since these can be stirred into the
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REFERENCES
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Chapter 17
MISCELLANEOUS MATERIALS
With polyester resin systems cured in open moulds, air inhibition of the
exposed surface can result in a tacky surface which does not fully harden.
This is caused in part by loss of monomer and partly by air inhibition of
cure. This can be overcome by adding a small amount of a suitable wax or
similar compound to the resin. As the resin cures, the wax comes out of
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solution and forms a thin protective film on the surface. Normally between
0·01 and 0·1 %addition of paraffin wax is sufficient. Several manufacturers
offer topcoat resins, containing wax or other additives, designed to cure
fully on exposed surfaces.
One problem which can arise with the use of these materials where
bonding, coating or repairs are to be carried out is lack of adhesion of the
new material. This can be overcome providing that adequate surface
preparation is carried out first to remove all traces of wax and other
contaminants.
Air inhibition is not a problem with epoxide resin systems in general,
although amine bloom can arise with certain aliphatic amine curing agents
used under high humidity conditions. This can be overcome by either
partially adducting the amine before use or by allowing the system to stand
for a short time after mixing before it is used.
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MISCELLANEOUS MATERIALS 391
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therefore be avoided for such use, except for hot press moulding. Neither
should they be used with polyurethane foams since they may cause
defoaming. Various silicone sprays, emulsions, solutions and greases are
available.
Two silicone release agents which are very effective with epoxide resin
systems are Releasil7 Compound-a non-melting translucent grease
having the consistency of petroleum jelly up to 250°C-and DC 20 Release
Coating-a 50% solution ofa silicone compound in a hydrocarbon solvent.
This replaces Releasil 14, a similar type of material. Both materials
are manufactured by Dow Corning Ltd, and supplied by Hopkin &
Williams.
17.4.7 Nitrocellulose
Nitrocellulose solution can be used to seal the porous surface of plaster
moulds prior to application of wax polish.
17.4.8 Shellac
Shellac can be used in a similar way to nitrocellulose and cellulose acetate
solutions as a sealer for porous plaster and wooden moulds and patterns.
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MISCELLANEOUS MATERIALS 393
Core materials are used to provide stiffness, thermal insulation and light
weight to composite structures. Where such materials are used in boat
construction they also serve to increase buoyancy.
A variety of materials may be used and include balsa wood, plastic foams
and honeycombs of paper, glass fibre laminate or metal. Some comments
on the different types of plastic foams available are given in Chapter 4,
Section 17.
Fig. 17.1. A typical end grain balsa wood panel showing back and front view.
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Fig. 17.2. Firet Coremai viewed from the top and with a section through, showing
the PVDC microspheres (approx. x 25 magnification).
t Trade mark.
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17.5.3 Intercel t
Intercel is a polyester syntactic foam honeycomb lightly bonded to
300 gjm 2 glass fibre chopped strand mat (Fig. 17.3). It can be applied by
normal hand lay-up techniques with the cell side facing either up or down.
It can also be used as core material in spray applied laminates. As with
Fig. 17.3. Intercel core material showing back and front views.
tTrade mark.
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17.5.4 Honeycombs
A variety of honeycombs can be used as core materials for sandwich
construction where low weight and high stiffness is required. Such
honeycomb cored laminates find application as flooring, decking, par-
titions and furniture, where weight saving and rigidity are of prime
importance, for example in aircraft, marine structures and vehicle and
caravan bodies.
Aluminium and phenolic resin impregnated polyamide honeycombs are
available in a range of densities either alone or with glass reinforced epoxy
or bonded aluminium facing skins. These can all be used in wet lay-up
laminating or with prepregs to produce lightweight sandwich composites.
Supplier: Bonded Structures Division of Ciba-Geigy Plastics and
Additives Company.
Product availability:
Aerowebt Type 3003 Aluminium honeycomb.
Aerowebt Type Al Phenolic impregnated polyamide
honeycomb.
Aerolamt F board Aeroweb Type 3003 faced with glass
fibre reinforced Araldite epoxy skins.
Aerolamt M board Aeroweb Type 3003 with Reduxt
bonded aluminium facing skins.
All products are available in a range of densities.
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Coupling agents have also been used with fillers. One example, as might
perhaps be expected, is the coating of glass spheres (Ballotini) with
coupling agents to improve their bonding into the resin matrix. In other
cases silane coupling agents have been added to the resin system to act on
all fillers present. This tends to be a less efficient way of using them. More
recently it has been shown that silane coupling agents can offer beneficial
results when applied to aluminium hydroxide (alumina trihydrate) used as
a flame retardant filler. 3 Here the coupling agent serves to reduce the
viscosity of the system containing surface treated alumina trihydrate and
thus permits higher loadings to be used, with a resultant improvement in
burning resistance. Silane coupling agents can also be applied to other
fillers, such as clays, to enable increased filler loadings to be used. Normal
usage in this context is o· 5-1 % silane.
The coupling agents mostly used on glass reinforcements are silanes
although a chrome based size is also used. A number of different silane
coupling agents are available commercially, some of which are listed below.
A description of the chemistry and mechanism of silane coupling agents
can be found elsewhere. 4,5
Supplier: Union Carbide Corporation, USA
Product code:
A-I51 Vinyltriethoxysilane
A-I62 Methyltriethoxysilane
A-I63 Methyltrimethoxysilane
A-In Vinyltris(2-methoxyethoxy)silane
A -17 4 y- Methacryloxypropyltrimethoxysilane
A-IIOO y-Aminopropyltriethoxysilane
Other products are also available.
Other coupling agents suitable for addition to the resin matrix to
improve bonding to fillers are the organo-titanium compounds. 6 These are
used at loadings of O· 5-1 % based on filler content and permit higher filler
loadings to be used than would otherwise be possible. They are particularly
effective with clay fillers although they give similar results with most
inorganic fillers. Some of those recommended for use in polyester and
epoxide resin systems are listed below. Various related compounds are also
recommended for use in thermoplastic materials. 6
Supplier: Kenrich Petrochemicals, Inc. USA
Product code: Compound type and use
KR-41 B Tetra-isopropyl di(dioctylphosphito)titanate. Amine cu-
red epoxy.
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REFERENCES
SOME SUPPLIERS
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Chapter 18
LAMINATING EQUIPMENT
18.1 INTRODUCTION
With the wide range of moulding processes available, an equally wide range
of processing equipment is necessary. In this chapter, equipment used for
hand and spray lay-up, resin injection/transfer moulding and related
processes will be described and some suppliers indicated. More specialised
equipment such as that used for hot press moulding, pultrusion, filament
winding, injection or transfer moulding and continuous laminating
processes will not be covered.
In the case of spray equipment, most has been designed for use with
polyester resin systems, since these form the bulk of all resins applied by the
spray lay-up process. However, equipment is available which has been
designed specifically for use with epoxide resin systems. Here different
metering requirements have to be met and different viscosity materials
handled. Such equipment is described separately.
Spray equipment can be used alone for the application of gelcoats and
topcoats or in combination with a chopper unit for the simultaneous
spraying of glass and catalysed resin systems. These items are discussed
separately.
A list of suppliers has been included at the end of the chapter with code
letters to indicate who supplies which type of equipment. Full details of
such equipment can be obtained from each supplier.
18.2.1 RoUers
Rollers form an essential part of all hand and spray lay-up laminating
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'tn'"","""".,·'"
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LAMINATING EQUIPMENT 401
Laminating rollers
Laminating rollers are used to consolidate the laminate and to assist in
removing trapped air from it. Various different types are available to meet
all moulding requirements. These are described below.
(b) Dimple rollers. These are rollers covered with a fabric having
protruding dimples in it. They are used for air release and consolidation of
the laminate.
(c) Washer rollers. These consist of alternate large and small washers
made from either metal or plastic washers. In the case of the plastic washers
the large and small washers are moulded in one piece. The shaft and handle
can generally be interchanged with those used on mohair rollers. Also
available are single, double and triple washer rollers for use in consolidat-
ing the laminate in corners or along edges.
(d) Finned rollers. Various finned rollers similar to washer rollers can be
obtained. These are made from a solid block of material and have vertical
or circumferential serrations. They are available made from Teflon (PTFE)
or polyethylene coated aluminium.
(e) Paddle rollers. These are extruded aluminium rollers with thin ribs
running along the length of the roller. They give fast wet out and good air
removal and find wide application. Two different diameters are available.
(f) Spring rollers. These comprise a steel spring mounted so that it will
flex in any direction. They are useful for consolidating laminates on curved
surfaces. Cured resin can be removed by the use of suitable solvents but
should not be burnt off since this can spoil the temper of the spring.
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lengths and two or more diameters. In addition many can be fitted with
extension handles. Some types are also available specifically designed for
use on the end of broom handles.
Some suppliers: F, G, J, K.
18.2.2 Brushes
Brushes can be used for the application of gelcoat resins and also for
applying resin to reinforcements, particularly in corners and along edges.
Light coloured brushes are recommended for use with light coloured
laminating systems so that any brush hairs which become dislodged are not
visible in the cured laminate.
For gelcoat application a wide brush with long soft hairs is preferable to
avoid brush marks and streaks.
Some suppliers: F, G, J, K.
18.2.3 Catalyst dispensers
With hand lay-up and other processes which require the regular metering of
catalyst by hand, the use of a catalyst dispenser can help to eliminate
mixing errors. Various different types of unit are available. One common
type is the plastic squeezy bottle. Here a tube protrudes from the top of the
bottle and is surrounded by a graduated cylinder. Catalyst is squeezed out
until the cylinder contains the required amount. The catalyst is then tipped
into the resin. Two sizes are available, graduated from 2 to 15 ml or 15 to
60ml.
Another type is the Finn & Fram catalyst meter-dispenser. This can be
adjusted to deliver the exact amount of catalyst required on pressing a
plunger. Units are available to fit standard one-gallon plastic bottles or to
fit larger containers.
Some suppliers: F, G, J, K.
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LAMINATING EQUIPMENT 403
18.2.6 Mixers
Various mixers may be required to blend catalyst, accelerator, pigments
and fillers into the resin. These may be air driven or operated by electric
motors. Air driven motors are preferred where low flash point materials,
such as polyester resins, are to be mixed, since these eliminate the possibility
of a spark from the motor igniting the material.
Mixers of many different sizes are available, fitted with a range of mixing
heads. Mixers with speeds of up to 10 000 rpm are readily obtained.
Selection depends on specific workshop requirements.
Where stopping compounds are to be mixed, a much slower turning
dough or Z-blade mixer is required. A similar mixer is also required for the
preparation of dough moulding compounds. Such mixers are available in a
variety of sizes from bench top models up to full size production units.
Some suppliers: F, G.
Spray equipment for use with polyester resin systems can be divided into
three types, catalyst injection, catalyst spray and twin pot systems.
With each of these systems the spray gun is fitted with a chopper unit
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Catalyst
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LAMINATING EQUIPMENT 405
Catalyst
Roving Res;n +
Accelerator
Fig. 18.3. Catalyst spray system.
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takes place externally. This eliminates the need to flush the gun head
regularly with acetone and thus reduces fire risk.
Equipment is available operating on the twin pump or pressure pot
system.
Some suppliers: A, F, G, H.
Res;n +
Catalyst
Roving Res in +
Accelerator
Fig. 18.4. Twin pressure pot system.
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LAMINATING EQUIPMENT 407
time as resin and chopped glass. This can be particularly useful with
lightweight fillers which tend to float on the top of the resin if mixed in prior
to application. With this attachment the gun can be used to spray outer and
inner skins of normal polyester/glass composition without filler and an
inner core of polyester/lightweight filler with or without glass, to make a
sandwich construction.
A supplier: C.
Several ofthe spray guns on the market can be adapted, by changing the
nozzle, to spray filled systems. Where filled systems are to be sprayed,
wherever possible, non-abrasive fillers should be used to prevent excessive
wear on the gun and pumps.
A supplier: G.
Where woven rovings, continuous strand mat or chopped strand mat have
to be used or where processors prefer to use hand lay-up techniques, a
system is available which combines the advantages of automated mixing
with hand lay-up processing. This equipment is suitable for use where very
large mouldings such as boat hulls or building panels are produced.
The equipment available operates on the catalyst injection principle with
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LAMINATING EQUIPMENT 409
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viscosity systems heated resin and curing agent drums are used. Mixing is
internal in a mixing head either by static or mechanical means. A solvent
flushing system is built into the mixing head.
Some suppliers: G, L, M.
Equipment has been developed recently for the spray lay-up offurane resin
systems. This incorporates a special corrosion resistant catalyst hose and
pump, to cope with the highly aggressive catalysts used with furane resins.
It operates on the catalyst injection - internal mixing principle, with catalyst
and resin pumps interlinked to ensure accurate catalyst/resin ratios.
Catalyst level can be adjusted over the range 1-12% with an accuracy of
± 0·1 %. Pollution is kept to a minimum by the use of a controlled spray
pattern from a low-pressure airless spray gun.
A supplier: D.
SUPPLIERS
Code Supplier
A Binks-Bullows Ltd.
B BMS Plastics Ltd.
C J. Coudenhove (UK)
D CT (London) Ltd.
E The DeVilbiss Company Ltd.
F K & C Mouldings (England) Ltd.
G Newgate Simms Ltd.
H Ransburg-Peabody Ltd.
I The Shelter Island Co. Ltd.
J Strand Glassfibre Ltd.
K Vetrotex (UK) Ltd.
L Prodef Engineers Ltd.
M Spracon Equipment Services Ltd.
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Chapter 19
19.1 INTRODUCTION
Resins, catalysts, curing agents, solvents and other ancillary materials have
been used in industry for many years with complete safety. However, like
all chemical materials, they have to be handled sensibly and carefully if all
hazards are to be avoided. Material manufacturers and suppliers in-
variably give advice on handling, storage and safety precautions and this
advice should be followed.
In this chapter an attempt has been made to summarise the currently
accepted handling recommendations issued by the various material
suppliers. From time to time these recommendations may change as more
information becomes known about specific materials. Whilst the recom-
mendations given below may be taken as a general guide, specific
recommendations must be obtained from the appropriate supplier. Also
where any doubts exist or where problems arise, up to date information
should be obtained from the material supplier. Advice may also be
obtained from the Health and Safety Executive.
Disposal of most, if not all, of the resins and curing agents mentioned is
notifiable under the Control of Pollution Act 1974.
With the handling of all synthetic resins, catalysts, curing agents and
solvents, mixing and application procedures should be devised which
minimise skin contact and vapour exposure.
Skin contact can be minimised by the use of protective barrier creams
and the wearing of protective gloves. Eye contact can be avoided by the
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Eyes
First aid in the case of accidental contamination of eyes should consist of
immediate and continued washing of the eye for at least 10-15 min with
copious amounts of clean water. If other treatment is recommended for
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HANDLING AND SAFETY PRECAUTIONS 413
Skin
After accidental or unavoidable skin contact all affected areas should be
cleaned with a cleansing cream followed by washing thoroughly with soap
and water. If this is ineffective, washing with fresh clean solvent such as
acetone, methyl ethyl ketone or another appropriate solvent can be carried
out. Solvents should never be used around open wounds. The use of all
such solvents on the skin should be kept to the absolute minimum and a
refatting cream applied once the contaminated area has been thoroughly
cleaned. Contaminated solvents should never be used.
Where skin irritation, burns or other damage has occurred the advice of
a doctor should be sought without delay.
Inhalation
The individual concerned should be removed to fresh air and kept at rest
until any symptoms of respiratory irritation distress have disappeared.
Artificial respiration should be given if necessary. The affected individual
should not be left alone until recovery is complete. Where materials are
handled which are known to give off harmful fumes, e.g. certain
isocyanates, then the appropriate remedial measures must be taken. This
may well include immediate referral to a doctor. In any case, if distress
symptoms do not disappear quickly, immediate medical help should be
sought.
Ingestion
If large amounts of resin are ingested, the mouth should be washed out
with water and a large quantity of water drunk. Immediate medical
attention must be sought. With ingestion of other materials the recom-
mendations given for those particular materials should be followed and
immediate medical attention obtained.
Spillages
In the case of most spillages-resins and curing agents-these should be
soaked up with sand, sawdust or other proprietary absorbent material and
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then shovelled into drums for disposal. Where catalysed resin is spilt care
should be taken to ensure that when the material plus absorbent is placed in
a drum, excessive exotherm does not occur which could result in the
generation of fumes or ignition. This could then constitute a fire risk.
Where peroxide catalysts are spilt these must be absorbed with a non-
flammable material such as vermiculite. The area can then be thoroughly
flushed with clean water. Peroxide soaked absorbent must not be stored in
closed containers and should be destroyed immediately (see Section 19.7).
Protective clothing should always be worn when dealing with spillages.
In the main the handling and use of epoxide resins presents few hazards.
The unmodified liquid DGEBA resins are described as being mild-to-
moderate primary skin irritants whose irritation potential is increased by
prolonged skin contact. They are mild-to-non-sensitisers. Similarly most
liquid resins containing reactive diluents are mild-to-moderate primary
skin irritants. However, the diluents present may render these resins mild-
to-strong sensitisers. This depends on the chemical nature of the diluent
involved.
Solution grades of resins may be mild-to-moderate skin irritants due to
the effect of the solvents present, which give greater wetting and skin
contact. These solvents also remove natural fats from the skin and render it
more liable to attack.
The other types of resins encountered are similarly potential skin
irritants and possible skin sensitisers.
Many of the low viscosity reactive diluents used in epoxide resins are
more or less irritating and sensitising to the skin; thus additional care needs
to be taken when handling them.
Details of the effect of any particular resin on skin contact may be
obtained from the resin supplier.
Fully cured epoxide resins are practically non-toxic, non-irritant and
non-sensitising to the skin. One of the major uses of epoxide resin systems is
in the lining of containers and cans for food and drink storage.
Dust produced during the machining of epoxide resins and composites
could present a health hazard and so dust extraction procedures and
precautions to prevent inhalation of dust should be observed and dust
levels maintained within the TL V of 10 mg/m 3 recommended by the Health
& Safety Executive.
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HANDLING AND SAFETY PRECAUTIONS 415
These can be divided into several different classes. In all cases protective
clothing should be worn and the materials used in well ventilated areas.
These materials have been used industrially for many years and, providing
all sensible precautions are taken, no hazards should arise. The general
precautions (Section 19.2) should be followed unless otherwise stated.
Eye contact can result in acute eye irritation and so goggles should be
worn when handling all curing agents.
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HANDLING AND SAFETY PRECAUTIONS 417
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ORGANIC PEROXIDE
Fig. 19.1. Hazard warning label for organic peroxide. Black printing on yellow
background.
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HANDLING AND SAFETY PRECAUTIONS 419
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Carborundum
Cement
Glass and glass fibre
Iron oxide
Limestone-silica free
Magnesium oxide
Silicates other than those previously mentioned
Titanium dioxide
Zinc oxide
Zirconium oxide and silicate
Several others
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Chapter 20
TEST SPECIFICATIONS
20.1 INTRODUCTION
Most people involved with fibre reinforced plastics encounter test specifi-
cations at some time. In this chapter, some of the more commonly
encountered specifications are listed, together with brief comments about
some of them. Six series of test specifications are mentioned, although not
necessarily comprehensively, namely: ASTM-American Society for
Testing and Materials; BS- British Standards Institution;
DIN - Deutsche Normenausschuss; ISO-International Standards
Organisation; EN-European Standard; IP - Institute of Petroleum.
Wherever possible, indications are given as to the similarity or equivalence
of the various standards mentioned.
= equivalent, although not necessarily an identically worded test
method.
1= similar but not equivalent test method.
In this section are included such properties as acid value, epoxide content
and chemical resistance.
421
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422 FRP TECHNOLOGY
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TEST SPECIFICATIONS 423
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424 FRP TECHNOLOGY
A very wide and varied series of tests is available for measuring the fire
resistance of plastic materials. 2
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TEST SPECIFICATIONS 425
Laminates
BS 2782 Method 1005: 1977 = EN 63
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426 FRP TECHNOLOGY
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TEST SPECIFICATIONS 427
20.5.3 Hardness-indentation
Shore hardness
ASTM D 2240- 75
= DIN 53505
Barcol hardness
ASTM D 2583- 75
= BS 2782 Method 1001
=EN59
Rockwell hardness
ASTM D 785-65 (reapproved 1976)
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428 FRP TECHNOLOGY
20.5.4 Shrinkage
ASTM D 2566-69 (reapproved Linear shrinkage of cured
1975) thermosetting resins during cure.
ASTM D 1299-55 (reapproved Shrinkage of moulded and
1971) laminated thermosetting plastics
at elevated temperature.
DIN 16946 Shrinkage of polyester resins
during cure.
20.5.5 Viscosity
Viscosity may be determined as either dynamic viscosity or kinematic
viscosity.
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TEST SPECIFICATIONS 429
three-point load. Two stress levels may be used: (a) 1·8 MPa (264lbfjin 2 )
and (b) 0-45 MPa (66lbfjin 2 ). Rate of heating: 2 ± 0·2°Cjmin. Sample
immersed in mineral oil or silicone oil.
BS 2782 Method 121A and B
= ASTM D 648- 72
= ISOjR 75
= DIN 53461
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430 FRP TECHNOLOGY
Abel apparatus
Statutory method-BS 3442 Part 1 1974=IP 33/59
Non-statutory method-BS 3442 Part 2 1974 = IP 170170
At 10 kHz
ASTM D 150-74
= DIN 53483
At 1 MHz
BS 2782 Method 207B
~ASTM D 150-74
=j= DIN 53483
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TEST SPECIFICATIONS 431
20.8.1 Colour
In this context colour refers to the natural colour of resins and not to
standard paint or pigment colours. Two methods are used.
Gardener scale ASTM D 1544-68 (reapproved
1974)
Platinum~coba1t (Hazen) scale BS 3532 Appendix E
= BS 5339:1976
= ASTM D 1209~69 (reapproved
1974)
20.8.4 Reinforcements
BS 3396 Woven glass fibre fabrics for plastics reinforce-
ment.
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432 FRP TECHNOLOGY
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TEST SPECIFICATIONS 433
REFERENCES
1. Chalkley, N. J. and Whalley, C. (1978) Proc. Anal. Div. Chem. Soc., 15,
December, 327.
2. Flammability Test Methods for Plastics-An International List. Chemical
Industries Association (CIA), Fire Retardants Group.
3. Anon. (1978) Modern Plastics International, 8, July, 53.
4. Anon. (1977) J. Fire & Flammability, July, 300.
5. Smith, E. E. (1972) Fire Technology, 8, August, 237.
6. Barnet, F. R. (1965) Trans. J. Plastics Inst., October, 177.
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Appendix 1
TRADE NAMES
The descriptions of products and trade names given below are derived from
technical literature received from suppliers in the UK. They may not cover
all products supplied, nor is the firm listed necessarily the owner of the
name. Overseas owners of names are given in parentheses.
AEROLAM Composite honeycomb-sandwich board-Ciba-
Geigy Plastics & Additives Company.
AEROSIL Thixotroping agent-Bush, Beach & Segner
Bayley Ltd.
AEROWEB Honeycomb cores-Ciba-Geigy Plastics &
Additives Company.
ALPOLIT Polyester resins-Hoechst AG/Resinous
Chemicals.
AMPAL Polyester moulding compounds-Ciba-Geigy
Plastics & Additives Company.
ANCAMIDE Polyamide curing agents-Anchor Chemical Co.
Ltd.
ANCAMINE Amine curing agents-Anchor Chemical Co. Ltd.
ARALDITE Epoxide resins-Ciba-Geigy Plastics & Additives
Company.
ARMAFLO Centrifugally cast pipes-Johnston Pipes Ltd.
ARMOSPHERES Hollow silicate spheres-Vetrotex (UK) L!d.
ATLAC Polyester and vinyl ester resins-Honeywill-Atlas
Ltd.
AVDELBOND Adhesives-Permabond Adhesives Ltd (formerly
A vdel Adhesives Ltd).
434
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TRADE NAMES 435
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436 FRP TECHNOLOGY
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TRADE NAMES 437
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438 FRP TECHNOLOGY
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Appendix 2
439
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Appendix 3
440
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COMPANY NAMES AND ADDRESSES 441
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442 FRP TECHNOLOGY
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COMPANY NAMES AND ADDRESSES 443
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444 FRP TECHNOLOGY
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COMPANY NAMES AND ADDRESSES 445
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446 FRP TECHNOLOGY
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COMPANY NAMES AND ADDRESSES 447
Walkers (Century Oils) Ltd, Dept ofIndustrial Hygiene & Safety, Hanley,
Stoke-on-Trent.
Warwick Chemical Ltd, 54 Willow Lane, Mitcham, Surrey CR44NA.
Victor Wolf Ltd, Victoria Works, Croft Street, Clayton, Manchester Mil
4RR.
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Appendix 4
Frequency hertz Hz
Force newton N
Stress pascal Pa (= N/m2)
Pressure bar bar (= 105 Pa)
Energy joule J
Impact strength joules per square
metre J/m 2
Power watt W
Thermal conductivity watts per metre kelvin WjmK
Thermal trans- watts per square
mittance metre kelvin Wjm 2 K
Specific heat joules per kilogramme
kelvin J/kgK
Viscosity-dynamic pascal second Pa s (= 10 poise)
-kinematic square millimetre
per second mm 2 Is (= cSt)
STANDARD PREFIXES
448
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UNITS, PREFIXES AND CONVERSION FACTORS 449
deca da 101
deci d 10- 1
centi c 10- 2
milli m 10- 3
micro f.1 10- 6
nano n 10- 9
pico p 10- 12
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INDEX
Where Tables are referred to the page numbers are given in italics.
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452 INDEX
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INDEX 453
Carbon fibre-contd. Chopped strands, 315, 316
resin systems for, 293 Chrome plated moulds, 28, 55, 56, 62,
SMC, 352 67
Carbon microspheres, 385 Chrome size, 318, 320
Casting, 164-7 Citraconic acid, 143
equipment for, 403 Cleansing creams, 420
Cast moulds Cobalt accelerators, 222
single-stage casting, 23, 24-6 commercial products, 238
two-stage casting, 26-8 cure, effect on, 147,205
Catalyst(s) polyester resins, with, 54, 62, 205,
commercial data, 226-37 209,213,214,215,216,219,
dispensers, 402 224
peroxide, 204-21 vinyl ester resins, with, 300
Catalytic curing agents, 268, 283-7 Cold press moulding, 35, 61-2
IX-Cellulose, 306 moulds for, 21-3
Cellulose acetate, 16, 18, 392 Colour change indicators, 150
Centrifugal moulding, 36, 73-6 Composite properties, 8, 293
buttons, 164-5 Concrete repairs, 129-35
moulds for, 30 Contact moulding, 34, 38-48
C-Flex planking, 82 hand lay-up, 34, 41-5
Chalk,377 spray lay-up, 34, 45-8
Chemical resistance, 9 Continuous strand mat, 319
furane resins, of, 296 use of, 53, 58
polyester resins, of, 142, 153-5 Copper powder, 384
vinyl ester resins, of, 153-5 Core materials, 393-6
China clay, 64, 351, 354,374, 379 plywood,58
Chlorendic anhydride, 144,276,277 sandwich construction, in, 80
Chlorinated paraffin, 149 types of foam, 80-1
Chlorine content, 422 use of, 43, 47, 53, 58
Chloromaleic acid, 143 Cotton, 309, 330, 350
Chlorostyrene, 146 Coupling agents, 320, 396-8
Chopped strand mat, 317-9 organo-titanium; 397-8
binders for, 318 silane, 397
centrifugal moulding, for, 74 Crack repair, 130
commercial materials, 338-42 Crazing, 94
continuous sheet manufacture, for, Cresyl glycidyl ether, 249, 250, 251
77 Critical temperature, 206, 208
filament winding, for, 71 Crystallisation
foam reservoir moulding, for, 59 epoxide resins, of, 244, 248, 249
GRP moulds, in, 19 polyester resins, of, 141, 143
hand lay-up, for, 33,41 Crystic Systems process, 59
hot press moulding, for, 63 Cumene hydroperoxide, 209, 216, 231
puItrusion, for, 78 Cure, test for, 40, 135
repairs, for, 117, 119, 120 Curing agents for epoxide resins,
resin injection, for, 53 263-93
rovings for, 314 amine, 126,240,265-74
site use, for, 126, 134, 135, 288, 289 anhydride, 240, 274-82
SMC, for, 352 accelerators for, 282
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454 INDEX
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INDEX 455
Epoxide 8, 249, 250, 251 Fasteners, 43, 47, 113
Epoxide(s) Faults
content, 241, 422 centrifugal casting, with, 105
equivalent weight, 241, 249, 253, epoxide resin mOUldings, with,
422 105-8
resins, 240-62 filament winding, with, 104
bisphenol A, 242-5 polyester mouldings, with, 8fr99
bisphenol F, 244, 246 press mouldings, with, 101
brominated, 242, 247, 253, 290, resin injection, with, 102
291 translucent sheets, with, 99
carbon fibre composites, for, 292, vacuum moulding, with, 103
293 Fibre
commercial, 255-62 classification, 315
curing agents for, 263-94 finishes, 320
cycloaliphatic, 247 pattern, 91, 99
diluents for, 248-54 properties, 309
DMC, 66, 67, 68, 359 Filament winding, 13, 36, 69-73
flame retardant, 242, 254, 290 epoxy pipes, 72
gelcoat, 26, 289 glass reinforcement for, 315
gener;ll, 3, 123, 126, 134 on-site, 137
glycidyl amine, 246, 292 prepregs, with, 73, 356
glycidyl ester, 245 specifications, 433
glycidyl ether, 242 spheres, 17
hand lay-up, 44 wet lay-up, 70, 292
laminate properties, 273, 278, winding angle, 72
279, 285, 288, 305 Fillers, 26, 372-87
moulding with, 55 safety and handling, 419
moulds, 23-8, 58 Fillite, 374, 385
novolac resins, 246, 273, 290, Fire retardant
291, 292, 327 epoxies, 242, 247, 253, 254
pipes, 69, 73 fillers, 386
polyester replacement, 265, 288, furanes, 296
289 polyesters, 142, 144, 157
prepregs, 51, 65, 66 tests, 424
primer, 125, 129 Firet coremat, 394
safety and handling, 414 Fish eyes, 92
specifications, 432 Flanges, 12, 20
spray lay-up, 48 Flash point,
Epoxy Molar Mass, 241, 249, 253, 422 amines, of, 269
Ethylenediamine, 266, 267, 268, 270 monomers, of, 146
Ethylene glycol, 141 tests for, 429
Ethylene oxide, 142, 267 Flexible polyester resins, 145, 162
2-Ethylhexyl glycidyl ether, 249, 251 Foam core, 53, 55, 58, 80
2-Ethyl-4-methylimidazole, 282, 284, Foamed polyester resins, 167
285,286 Foam reservoir moulding, 35, 59-61
Eutectic anhydride blends, 275 Foams
Exotherm, 12, 25, 43, 54, 61, 205, expanded polystyrene, 80
207, 263, 282 expanded PVC, 80
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456 INDEX
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INDEX 457
Iron Magnesite, 377
oxides, 374, 382, 420 Magnesium aluminium silicate, 375
powder, 383 Magnesium carbonate. 375, 377
Iso-octyl glycidyl ether, 249, 251 Magnesium oxide, 162, 354.375, 383,
Isophorone diamine, IPO. 264, 268. 420
270,271 Magnesium silicate (talc). 351, 354.
Isophthalic polyesters. 144. 149, 151. 375.378
350 Maintenance of GRP. 115
chemical resistance of. 153-5 Maleic acid. 143
Itaconic acid, 143 Maleic anhydride. 141, 143.281
Mannitol, 142
Marble poWder. 26. 377
Marble. synthetic 167
Joints, 13, 109-114 Martens HOT, 429
Jute fibres, 331 Matched metal moulds. 29, 55. 62
moulding, 62-7
Mechanical joints. 113
K 54, 282, 284, 285, 287 Melamine formaldehyde resins, 305,
K6IB, 284. 285, 287 306
Kaolin (china clay), 351, 354, 374, Metering equipment, 402, 409
379,419 Methyl acrylate, 146
KEVLAR fibres, 327-9 Methylenedianiline, MOA, 271
Kieselguhr, 374, 378,419 Methyl ethyl ketone peroxide, 205,
209, 212, 222, 300
commercial products, 228
Methylhexahydrophthalic anhydride,
Laitance, 132 MHPA, 276, 280
Laminate I-Methylimidazole, 282
properties, 8, 285, 288, 293 Methyl isobutyl ketone peroxide, 214,
strength retention. 273 230
Laminating equipment, 399-410 Methyl methacrylate, 145,146, 151,
epoxide resins, with, 287-93 297
systems for site use, 287-9 IX-Methylstyrene, 145, 146
Lead Methyltetrahydrophthalic anhydride,
oxides, 374, 382 276,278
powder, 384 Mica, 375, 380, 419
Leno weave, 321 Milled fibres, 315,317
Light Mitex foamed polyesters, 167
polyesters, cured by, 164 Mixers, 402, 403
sources, 403 Mock leno weave, 321
stabilisers, 390 Monoforming, 59
Limestone, 377 Monomers, 144-7,146
Linings Moulding processes, 33-84
concrete tanks, for, 129-36 Mould(s),15-32
steel tanks, for, 124-9 aluminium, 31
Low profile/low shrink resins, 66, box, 24,26
160-2, 351, 352 chrome plated, 28, 30, 31, 55, 56,
Low styrene emission resins, 159 62,67
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458 INDEX
Mould(s)-contd. Outdoor weathering, 254
cold press moulding, 22
epoxide resin, 23-8, 39, 58
single-stage casting, 24 Paper, 331
two-stage casting, 26 Paraffin wax, 135, 301, 390
GRP, 18-23 Patterns, 16, 18, 21, 24, 26
matching, 21 Pentaerythritol, 142
one-part, 19 Peroxides
split, 20 commercial data, 225-36
hot press moulding, 29 diacyl,210
injection moulding, 30 dialkyl, 216
life, 15 diaralkyl,2l6
matched metal, 29, 55, 62 half-life, 208
nickel shell, 32 hazard classification, 236-7
pattern, 16, 24 hydroperoxides, 215
plaster, 16, 32, 39, 71 ketone, 212
release, 21, 44 organic, 209-21
split, 18, 20 perketals, 209, 220
steel, 28, 62 peroxyesters, 217
transfer moulding, 30 safety and handling, 417-19
wax, 32, 71 Phenol, 266, 271, 272
wooden, 18,39 Phenolic microballoons, 28, 375, 385
Phenolic resins, 68, 305, 306
Nadic methyl anhydride, NMA, 275, m-Phenylenediamine, MPD, 268, 270,
276, 277, 278, 279 272
optimum cured properties, 280 Phenyl glycidyl ether, 249, 250, 251
Phlegmatised peroxides, 204
Needle mat, 318
Phthalic anhydride (ortho), 141, 143,
NEMA laminates, 247, 290, 291
275, 276, 278, 281
Neo-pentyl glycol polyesters, 142,
Pigments, 387
149, 151, 156
safety and handling, 419
chemical resistance of, 153-5
Nickel shell moulds, 32 Pinch area of mould, 22, 61
Pinholes, check for, 127
Nitrocellulose, 16, 24, 392
Pinholing, 87, 106
Novolac
epoxide resins, 246, 290, 291, 292, Pipes
centrifugally cast, 73-6
293,327
epoxy, 292
phenolic resins, 306
filament wound, 69-73
Nylon fibres, 330
Dunlop process, 72
joints, 114, 136
Oil tank, repairs to, 120
repairs, 124--9 Usui process, 75
riveted tanks, 128 Plain weave cloth, 319-23
Orthophthalic acid, 144 Plaster moulds, 16, 32, 39, 71
Orthophthalic anhydride, 141, 143, patterns, 16, 18, 21, 24, 26
275, 276, 278, 281 Polyacrylonitrile fibres, 308, 310, 323,
Orthophthalic polyesters, 145, 149, 151 324, 330
chemical resistance of, 153-5 Polyamide curing agents, 282
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INDEX 459
Polyester fibres, 310, 329 Pot-life
Polyester resins. 139-203 epoxide resins, of, 269, 277, 281
acid value of, 421 polyester resins, of, 205
bisphenol, 149, 151, 152 Powder
chemical resistance of, 153-5 binder, 77, 318
casting, 164 coating, 280
chemical resistance of, 153-5 Preforms, 62, 64
test for, 422 Prepregs, 65, 255-8, 349
commercial resins, 168-203 commercial materials, 366-70
curing reaction, 206 diallyl phthalate, 145, 163
DMC, for, 163 furane, 297
fire retardant, 142, 157 hot press moulding of, 65
flexible, 144, 162 manufacture of, 356
foamed,167 pressure bag moulding of, 51
gelcoat, 150 systems for, 272, 274, 276, 283,
general purpose resins, 151 286,290,291,293
chemical resistance of, 153-5 unidirectional, 49, 51, 356
HET acid, 144, 149, 151 vacuum bag moulding of, 49, 50
chemical resistance of, 153-5 Pressure bag moulding, 34, 51
hydroxyl content of, 423 Pressure injection, 55
isophthalic, 144, 149, 151,350 Primers, 84, 125,133,135
chemical resistance of, 153-5 polyester, 133
light cured, 164 zinc rich, 125
low profile/low shrink, 160, 351, Printed circuit boards, 247, 286, 290,
352 291,355
low styrene emission, 159 Process selection, 10
methyl methacrylate containing, Propylene glycol, 141, 156
150 Propylene oxide, 142
neo-pentyl glycol based, 142, 149, PuItrusion, 37, 78-80
151, 156 moulds for, 31
chemical resistance of, 153-5 prepregs, 356
orthophthalic, 141, 143, 145, 149, reinforcements for, 315
151 sections, 83
chemical resistance of, 153-5 Pumice, 375, 380
pipes, 70, 73 PVA. See Polyvinyl alcohol
prepregs, for, 163 PVC and PVDC fibres, 330
primer, 133 Pyromellitic dianhydride, 276, 278,
properties of, 149, 170--203, 305 280
safety and handling, 416
SMC, for, 65, 162
speciality resins, 164 Q-cell, 375, 385
specifications for, 432
topcoat, 150, 389
Polyhydric alcohols, 142, 163 Radomes,55
Polyimides, 305 Refractive index
Polyvinyl alcohol, 16, 17, 18,21,24, cured resins, of, 77, 145
39,44, 57, 74, 84, 391 glass, of, 145, 312
Post cure, 19, 44 monomers, of, 146
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460 INDEX
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INDEX 461
Surface preparation of-contd. Triamylammonium phenate, 279, 282
GRP, III Trichloroethyl phosphate, 157
moulds, 39 Triethanolamine acetate, 386
stainless steel, 112 Triethylenetetramine, TETA, 251,
steel, 112, 125 268,270
thermoplastics, 112 Trimellitic anhydride, 276, 278, 280
wood, 112 Trimethylhexamethylenediamine, 264,
Surfacing tissue, 19,26,40,41,43, 267, 268, 270
45,47,60, 70, 126, 134, 135 Trimming, 83-4
commercial, 333-4 'green' stage, at, 19, 43
construction of, 310 mould, in, 29, 66
Triphenyl phosphite, 271
Tris-(dimethylaminoethyl)phenol, 282,
Talc, 64, 351, 354,375,378,419 284, 285, 287
Tank Twill weave cloth, 321
on-site construction of, 137
repair, 124--9
Tertiary amines as, Undercuts, 18, 20, 30
accelerators Unidirectional weave, 321, 326
anhydrides, for, 274, 280, 282 prepregs, 65, 366-70
peroxides, for, 209, 210, 211, Urea-formaldehyde resins, 305, 306
213, 214, 223 UV stabilisers, 390
commercial, 239
Test methods, 421-33
Tetrabromobisphenol A, 247 Vacuum
Tetrachlorophthalic anhydride, 144 bag moulding, 34, 49-51
Tetraethylenepentamine, TEPA, 268 impregnation, 35, 55-9
Tetrahydrophthalic anhydride, injection, 56
THPA, 275, 276, 278 British Rail process, 58-9
Tex,313 Crystic Systems process, 59
Thermoplastic additives, 161 Hoechst process, 56-8
Thick laminates, 42, 47 Monoforming, 59
Thick moulding compound, 352 Vanadium accelerators, 213,215,216,
Thin layer chromatography, 243, 244 219, 220, 222, 238
Thixotropic additives, 379, 386 Vermiculite, 28, 375, 380
Threshold limit value, TLV, 145,146, Vinyl ester resins, 3, 73, 123, 129,
159, 296, 297 299-301
Titanium chemical resistance of, 153-5
dioxide, 375, 383, 420 Vinyl toluene, 146, 161
properties of, 309 Viscosity
Tooling, moulds, 15-32 effect of diluents on, 250, 252
Topcoat resins, 43, 48, 74, 127, 135, test methods, 428
15(}-1,389
Tracking resistance, 254, 431
Trade names, 434 Water resistance tests, 423
Transfer moulding, 36, 67 Wax
moulds for, 30 additives, 151, 160, 389
Triallyl cyuranate, 146, 147 moulds, 32, 71
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462 INDEX