Professional Documents
Culture Documents
R. G. WEATHERHEAD, B. Sc.
Consultant and Resin Specialist, Epsom, Surrey, UK
(Formerly Senior Scientist with Shell Research Ltd,
Egham Research Laboratories, Surrey, UK)
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
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
v
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
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
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
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
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
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
XII CONTENTS
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
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
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
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
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
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
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.
GENERAL INTRODUCTION 3
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