Metallic Pigments in Polymers

Metallic Pigments
in Polymers
Ian Wheeler
Rapra Technology Limited
Shawbury, Shrewsbury, Shropshire SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
1MP Title Page etc 1 27/11/01, 12:08 pm

First Published 1999 by
Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©1999, Rapra Technology Limited
The right of Ian Wheeler to be recognised as author of this Work

has been asserted by him in accordance with sections 77 and 78 of the
Copyright, Designs and Patents Act 1998.
All rights reserved. Except as permitted under current legislation no part

of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
ISBN: 1-85957-166-2
Typeset by Rapra Technology Limited

Printed and bound by Polestar Scientifica, Exeter, UK
1MP Title Page etc 2 27/11/01, 12:08 pm

Contents
1 Introduction and History ................................................................................ 3

1.1 Introduction ........................................................................................... 3
1.2 Origins and history ................................................................................ 4
2 Metal Pigment Types ....................................................................................... 7

2.1 Aluminium ............................................................................................. 7
2.2 Gold bronze ........................................................................................... 8
2.3 Copper ................................................................................................... 8
2.4 Nickel .................................................................................................... 8
2.5 Stainless steel ......................................................................................... 9
2.6 Zinc ....................................................................................................... 9
2.7 Iron ........................................................................................................ 9
2.8 Tin ....................................................................................................... 10
2.9 Silver .................................................................................................... 10
2.10 Gold ..................................................................................................... 10
2.11 Other metals ........................................................................................ 10
3 Manufacture ................................................................................................. 11
3.1 Dry milling........................................................................................... 11
3.1.1 Aluminium ............................................................................... 12
3.1.2 Gold bronze ............................................................................. 12
3.2 Continuous dry milling ........................................................................ 13
3.2.1 Aluminium ............................................................................... 13
3.2.2 Gold bronze ............................................................................. 13
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Metallic Pigments in Polymers
3.3 Wet milling .......................................................................................... 14

3.3.1 Aluminium ............................................................................... 14
3.3.2 Gold bronze ............................................................................. 19
3.3.3 Silver ........................................................................................ 19
3.3.4 Nickel ...................................................................................... 20
3.3.5 Stainless steel ........................................................................... 21
3.3.6 Zinc ......................................................................................... 22
3.4 Continuous wet milling ........................................................................ 22
3.5 Spherical metal pigments ..................................................................... 22
3.6 Rapidly solidified flakes ....................................................................... 23
3.7 Vacuum deposition .............................................................................. 24
3.8 Cut foil glitters ..................................................................................... 25
3.9 Flakes with coloured surfaces .............................................................. 25
3.9.1 Chemical modification of metal surfaces ................................. 26
3.9.2 Colour formation in situ .......................................................... 27
3.9.3 Attachment of pre-formed colorants ........................................ 28
3.10 Metal coatings on non-metallic substrates ........................................... 29
3.11 Other methods ..................................................................................... 30
References ..................................................................................................... 31
4 Pigment Characteristics ................................................................................. 35

4.1 Morphology ......................................................................................... 35
4.1.1 Particle size .............................................................................. 35
4.1.2 Particle shape ........................................................................... 38
4.1.3 Aspect ratio ............................................................................. 39
4.1.4 Surface uniformity ................................................................... 41
4.2 Physical properties ............................................................................... 41
4.2.1 Specific gravity ......................................................................... 41
4.2.2 Water covering area ................................................................. 41
ii
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Contents
4.2.3 Specific surface area ................................................................. 42

4.2.4 Heat and lightfastness .............................................................. 42
4.2.5 Chemical resistance .................................................................. 43
4.2.6 Magnetism ............................................................................... 43
4.3 Visual properties .................................................................................. 43
4.3.1 Colour and brightness.............................................................. 44
4.3.2 Opacity .................................................................................... 45
4.3.3 Flop ......................................................................................... 45
4.3.4 Leafing and non-leafing ........................................................... 47
4.3.5 Sparkle ..................................................................................... 50
4.3.6 Distinctiveness of image ........................................................... 50
4.4 Glitter flakes ........................................................................................ 52
References ..................................................................................................... 53
5 Delivery Forms .............................................................................................. 55

5.1 Dry powder.......................................................................................... 55
5.2 Paste .................................................................................................... 55
5.3 Dispersion in resin and solvent ............................................................ 56
5.4 Plasticiser dispersions ........................................................................... 56
5.5 Granules .............................................................................................. 57
5.6 Dry masterbatch .................................................................................. 59
5.7 Liquid masterbatch .............................................................................. 59
5.8 Compound ........................................................................................... 60
References ..................................................................................................... 61
6 Comparison of Mass Pigmentation and Coating ........................................... 63

6.1 Advantages of coating .......................................................................... 63
6.1.1 Brightness ................................................................................ 63
6.1.2 Colour uniformity .................................................................... 64
iii
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6.1.3 Flop ......................................................................................... 64

6.1.4 Application temperature .......................................................... 65
6.1.5 Vacuum metallisation .............................................................. 65
6.2 Mass pigmentation advantages ............................................................ 65
6.2.1 Depth of coloration ................................................................. 65
6.2.2 Single stage versus multistage processing ................................. 66
6.2.3 Environmental and legislative pressures ................................... 66
6.2.4 Cost ......................................................................................... 67
References ..................................................................................................... 67
7 Mass Pigmentation Application Characteristics ............................................ 69

7.1 Colour ................................................................................................. 69
7.2 Dispersibility ........................................................................................ 69
7.3 Opacity and tint strength ..................................................................... 70
7.4 Orientation .......................................................................................... 71
7.5 Mechanical properties .......................................................................... 71
7.6 Cost ..................................................................................................... 75
7.7 Interrelationships ................................................................................. 76
7.8 Compatibility ....................................................................................... 77
7.9 Spherical metal pigments ..................................................................... 78
7.10 Metal flake pigments with coloured surfaces ....................................... 78
7.11 ‘Glitter’ flakes ...................................................................................... 79
8 Flow and Weld Lines in Mass Pigmented Applications ................................. 81

8.1 Description and origins ........................................................................ 81
8.2 Tool design for injection moulding ...................................................... 85
8.3 Orientation in multiphase and glass filled polymers ............................ 87
8.4 Orientation of metal pigments ............................................................. 89
iv
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Contents
8.5 Mould tool design for metal pigments ................................................. 92

8.6 Gates, sprues and runners .................................................................... 92
8.7 Tool texturing ...................................................................................... 94
8.8 Additional cavity ................................................................................. 94
8.9 Dynamic melt techniques ..................................................................... 94
8.9.1 SCORTEC ............................................................................... 94
8.9.2 Other techniques ...................................................................... 97
8.10 Localised mould heating ...................................................................... 98
8.11 Other techniques .................................................................................. 99
References ..................................................................................................... 99
9 Formulation of Mass Pigmented Polymers .................................................. 105

9.1 General techniques ............................................................................. 105
9.2 Optimising the formulation ............................................................... 105
9.2.1 Flake size ............................................................................... 106
9.2.2 Flake concentration ............................................................... 106
9.2.3 Polymer transparency ............................................................ 107
9.2.4 Polymer viscosity ................................................................... 107
9.2.5 Metallic/organic pigment combinations ................................. 108
9.2.6 Deep shades ........................................................................... 108
9.2.7 Spherical pigments ................................................................. 108
9.3 Incorporation in polymers ................................................................. 109
9.3.1 Low shear forces .................................................................... 109
9.3.2 Improvement of flake orientation .......................................... 110
9.4 Increasing pigment quality ................................................................. 110
9.5 Summary ............................................................................................ 111
References ................................................................................................... 112
10 Conversion Processes .................................................................................. 113
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10.1 Injection moulding ............................................................................. 114

10.2 Blow moulding .................................................................................. 115
10.2.1 Blown film ............................................................................. 115
10.2.2 Blown containers ................................................................... 116
10.3 Extrusion ........................................................................................... 117
10.4 Co-extrusion ...................................................................................... 117
10.5 Paint-less film moulding ..................................................................... 117
10.6 In-mould decoration .......................................................................... 118
10.7 Vacuum forming and thermoforming ................................................. 118
10.8 Rotational moulding .......................................................................... 118
10.9 Glass reinforced plastic ...................................................................... 119
10.10 Thermosetting polymers .................................................................... 120
References ................................................................................................... 121
11 Applications of Mass Pigmented Systems .................................................... 123

11.1 Household goods ............................................................................... 123
11.2 Sports goods ...................................................................................... 124
11.3 Agricultural film ................................................................................ 125
11.4 Sacks and bags ................................................................................... 125
11.5 Containers ......................................................................................... 126
11.6 Automotive ........................................................................................ 126
11.7 Pearl simulants ................................................................................... 127
11.8 Mineral simulants .............................................................................. 128
11.9 Fibres and textiles .............................................................................. 128
References ................................................................................................... 129
12 Metal Pigmented Coatings .......................................................................... 131
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Contents
12.1 Substrate preparation ......................................................................... 131

12.2 Coating formulation and properties ................................................... 132
12.2.1 Pigment particle size .............................................................. 132
12.2.2 Concentration ........................................................................ 132
12.2.3 Leafing and non-leafing ......................................................... 133
12.3 Dispersion and incorporation ............................................................ 133
12.4 Application to the substrate ............................................................... 134
12.5 Solvent based systems ........................................................................ 134
12.6 Water-based systems .......................................................................... 135
12.7 UV/EB cured coatings ........................................................................ 139
References ................................................................................................... 140
13 Applications of Metal Pigmented Coatings ................................................. 145

13.1 Painting.............................................................................................. 145
13.1.1 Solvent-based paints .............................................................. 146
13.1.2 Water-based paints ................................................................. 148
13.1.3 In-mould coating ................................................................... 152
13.1.4 Miscellaneous paints .............................................................. 153
13.2 Printing .............................................................................................. 153
13.2.1 Solvent-based inks ................................................................. 154
13.2.2 Paste inks ............................................................................... 154
13.2.3 Water-based inks .................................................................... 156
13.2.4 Laminates .............................................................................. 157
13.2.5 Security Inks .......................................................................... 157
13.2.6 Bronze replacement ................................................................ 158
13.3 UV cured coatings .............................................................................. 161
13.4 PVC Plastisols .................................................................................... 162
13.5 Anticorrosive and barrier coatings ..................................................... 162
13.6 Other applications ............................................................................. 163
vii
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14 Powder Coatings ......................................................................................... 167

14.1 Material types and properties ............................................................ 168
14.2 Manufacture ...................................................................................... 168
14.2.1 Dry blend ............................................................................... 169
14.2.2 Bonding ................................................................................. 169
14.2.3 Co-extrusion .......................................................................... 171
14.2.4 Coated flakes ......................................................................... 172
14.2.5 Other technologies ................................................................. 172
14.3 Formulation, application techniques and markets.............................. 173
14.4 Safety and handling ........................................................................... 175
References ................................................................................................... 176
15 Non-colouristic Applications ...................................................................... 179

15.1 Mechanical reinforcement .................................................................. 179
15.2 Microwave heating ............................................................................ 180
15.3 Electrical conductivity ........................................................................ 183
15.3.1 Product forms ........................................................................ 183
15.4 EMI shielding .................................................................................... 184
15.4.1 Origin and measurement ........................................................ 185
15.4.2 Legislative requirements......................................................... 185
15.4.3 Shielding principles and techniques ........................................ 185
15.4.4 Shielding of polymers ............................................................. 186
15.4.5 Coating techniques ................................................................ 187
15.4.6 Mass pigmentation techniques ............................................... 191
15.5 Light exclusion .................................................................................. 192
15.6 Heat and light reflection .................................................................... 193
15.7 Thermal conductivity ......................................................................... 194
15.8 Lubrication and wear reduction ......................................................... 196
15.9 Gas and moisture barrier ................................................................... 196
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Contents
15.10 UV protection ................................................................................. 196

15.11 Laser marking ................................................................................. 197
15.12 Magnetic applications ..................................................................... 198
15.13 Corrosion resistance ........................................................................ 199
15.14 Flame retardation ............................................................................ 199
15.15 Radiation absorption ...................................................................... 200
References ................................................................................................... 200
16 Health, Safety and Handling ....................................................................... 203

16.1 Health ................................................................................................ 204
16.1.1 Aluminium ............................................................................. 205
16.1.2 Gold bronze and copper ........................................................ 206
16.1.3 Other metal pigments ............................................................ 207
16.2 Safety ................................................................................................. 207
16.2.1 Aluminium ............................................................................. 208
16.2.2 Gold bronze ........................................................................... 209
16.2.3 Other metal pigments ............................................................ 210
16.3 Health and safety in use ..................................................................... 210
16.3.1 Mass pigmentation ................................................................ 211
16.3.2 Coatings ................................................................................ 211
16.4 Environment ...................................................................................... 212
16.5 Handling, storage and disposal .......................................................... 212
16.5.1 Aluminium ............................................................................. 213
16.5.2 Other metals .......................................................................... 213
16.5.3 UV grades .............................................................................. 213
16.6 Fire fighting ....................................................................................... 214
16.6.1 Aluminium ............................................................................. 214
16.6.2 Other metals .......................................................................... 215
References ................................................................................................... 215
ix
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Author Index ..................................................................................................... 221
Company Name Index ....................................................................................... 225
Main Index ........................................................................................................ 227
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Preface and Acknowledgements
The reader expecting this text to commence with the words “Much has been written
about…” will be sadly disappointed. In the case of metallic pigments, quite the opposite
is the case. The reason lies partly in the narrow nature and therefore limited appeal of
the subject matter. More importantly however, relatively few companies, generally using
the same raw materials, control the industry. It follows that one product is differentiated
from another by the process of manufacture. Much of this is the type of know-how that
is not easily patented and effectively policed. In consequence, manufacturers tend not
publish their foundation technology. When it comes to elaborating the basic pigment
however, there has been an explosion of patent literature, perhaps because such products
are now easily identified. From the mid-eighties onwards, surface coloration and
adaptation for water-based systems have been the main thrusts.
Though there is now a substantial patent literature and a modest amount of reported
academic endeavour, there remains a dearth of books on the subject. Indeed the last
book devoted specifically to metal pigments, entitled ‘Aluminium and Bronze Flake
Powders’ was written by G.W. Wendon and published by Electrochemical Publications
as long ago as 1983. Prior to that, one has to go back to 1955 to find a comparable
volume, that of Junius Edwards and Robert Wray, entitled ‘Aluminium Paint and Powder’
and published by Reinhold. Both these books were published before the recent upsurge
in interest in metal pigments.
Increasing interest is not surprising, given the range of visual effects uniquely available
from modern metal pigments. This is in addition to their many functional uses. The purpose
of this book is to bridge the technology gap since 1983 by providing a comprehensive
account of the nature, manufacture, formulation and applications of the diverse metallic
pigments commercially available today. Whilst the text concentrates on direct pigmentation
of polymers, there are also two chapters on metal pigment coatings for polymer substrates.
In addition to the familiar colouristic applications, there is a chapter on the many, often
novel functional applications in which colour is either incidental or irrelevant.
The tone is practical, rather than theoretical. The intention is to teach the features and
benefits of this novel class of pigments, to allow users to achieve the best possible visual
result with the most economical cost in use. It is also hoped that those not already
familiar with metallic pigments will be persuaded to explore their potential to add value
to their products.
3MP PREFACE 1 27/11/01, 12:08 pm

To provide as broad a perspective as possible, all the major manufacturers were invited
to contribute material, providing it was not promotional. Their contributions and those
of others are gratefully acknowledged as follows:
Jim Allan, Irvine Davidson, Sean Earnshaw and David Roach at the University of St.
Andrews, electron micrographs, optical microscopy and photographic services.
Professor Michael Bevis and Dr Keith Rawson at the University of Brunel and Steve
Jordan at Cinpres Inc., SCORTEC.
Dr Helge Friesenhan of Carl Schlenk A.G., Copper and gold bronze pigments.
Dr Anthony Hart of Hart Coating Technology, nickel, stainless steel and related
pigments. Use of photographs in Figures 3.6, 3.7, 15.2, 15.3, 15.4, 15.6 and the graph
in Figure 15.5.
Dr Margaret Henderson, John Maynard, Dr Geoff Ormerod and Joanne Mitchell of

Wolstenholme International, gold bronze pigments, including formulations in Chapter 13.
Christine Watters and Colin Hindle at Napier University, Edinburgh, EMI shielding.
Chris Williams, Permission to reproduce Figs 15.1 and 15.6 from his book, ‘The Printer’s
Ink Handbook’, Maclean Hunter Ltd, Barnet UK, 1992.
Many colleagues at Silberline Ltd., UK and Silberline Inc., USA, including David Chapman,
Russell Ferguson, Rob Gillan, John Kerr, Steven Kerr, Dr David King, Richard Knowles,
Dr Jonathan Knox, Derek Morris, Brian Seath, Dr Malcolm Stock and Dennis Thomson.
Special thanks are due to Frances Powers, my technical editor, for her encouragement,
enthusiasm and guidance during the writing of this manuscript.
Ian Wheeler
May 1999
3MP PREFACE 2 27/11/01, 12:08 pm

1
Introduction and History
1.1 Introduction
Colour is one of the key factors influencing a customer buying a retail product. In today’s
highly competitive and fast moving markets, all manufacturers are looking for the features
that will sell their products rather than those of their competitors. In what are loosely
referred to as ‘fashion’ markets, visual appeal is particularly important and tends to
come well ahead of functionality. It is in such markets that metal pigments excel.
Metal pigments are a small but important and versatile class of colouring agents, composed
of fine particles of malleable metals in elemental form. Their significance comes from
their ability to provide stunning visual effects that are impossible using traditional organic
and metal compound pigments. Their nearest relatives are the pearlescents, composed of
flakes of mica, now often coated with titanium dioxide or otherwise surface modified.
Such pearl pigments share the same lamellar form, but although potentially whiter than
metal pigments, they lack opacity. Thus each finds its place in the market according to
the envisaged application.
As might be expected, metal pigments retain many of the attributes of the bulk metal,
such as solidity (opacity), metallic colour, sheen, malleability, ductility and density. Their
use as colouring matter reflects this. Aluminium and gold bronze pigments provide the
appearance of silver and gold, respectively, with the aura of quality and prestige that
these metals imply. For this reason, metal pigments are often used in prestige applications
to add value.
The decision to replace solid metal by metal pigmented, coated or mass pigmented
polymers can be taken for several other reasons. Design flexibility, ease of fabrication,
weight saving, and of course cost reduction are all driving forces.
Strictly speaking, metal pigments are a class of inorganic pigment. Nevertheless, the
term ‘inorganic pigment’ throughout this book will be reserved for pigments in which
the metallic element is chemically combined with at least one other element. A ‘metal
pigment’ is therefore defined as a single metallic element or an alloy thereof.
In industry the term metal pigment tends to be used somewhat loosely. It encompasses
not only a range of morphology from flakes and fibres to spheres, but also applications
3
going beyond the technical definition of a pigment as an insoluble colouring agent. Thus
metal ‘pigments’ find use in many applications in which their colouristic properties are
either of limited importance or completely irrelevant. Chapter 15 is devoted to these
non-aesthetic applications.
The title ‘Metallic Pigments in Polymers’ has been widely interpreted to include not only
direct coloration of polymers but also coatings involving combination of metal pigments
with polymeric or resinous media. One area not covered in any depth is their use in
elastomers. Metal pigments are not widely used in rubbers for several reasons. Most
rubbers are inherently coloured, sometimes strongly so and this often makes it difficult
to achieve a bright metallic effect. Flexibility and mechanical properties also tend to be
adversely affected.
1.2 Origins and history
The origins of metal pigments can be traced back to the ancient art of gold beating. Early
civilisations, notably the Egyptians, would work the gold into very thin sheets and then
overlay wood, bone, or other materials with the precious metal. This art spread to the
Far East, India and eventually Europe. As trade developed and demand increased, it
became necessary to make thinner and thinner foil. Inevitably, the edges of the very
thinnest foils would tend to break off. However, it was soon discovered that by placing
these loose particles in a suitable binder, the gold leaf effect could be maintained. Carrying
this process a step further, very thin leaf was rubbed through fine screens to generate a
gold powder that could be used for ornamental artwork or printing inks. Eventually,
because of the extremely high cost of gold, substitutes were sought. Thus gold bronze
came into use, which although gold in colour, it is neither metallic gold nor bronze. Gold
bronze, the oldest of the gold simulants, is an alloy of copper and zinc, rather than the
copper-tin alloy of true bronze.
Later, silver and tin were combined to make a silver bronze powder, but the discovery of
aluminium smelting was eventually to lead to the development of the largest class of
metal pigment.
Gold bronze flake pigments were made in Germany as early as 1820. A key advance in
the process was the development of the mechanical stamping process by Sir Henry
Bessemer in the middle of the 19th century. The process consisted of steel hammers,
which fell on steel anvils, thus forming the metal into the flake form recognisable in
modern metal pigments. In this way, Bessemer was able to mitigate the very high cost of
gold and silver bronze powders. Newly developed smelting processes made aluminium
available in quantity. It was quickly introduced to the stamping process as a cheaper
4
Introduction and History
substitute for silver bronze. To prevent cold welding of the malleable metal, small quantities
of oils or fats were introduced as lubricants.
Though a technical advance, the stamping process was not without its problems. The
fine, dry flake also had a high explosion risk, as well as being a potential contaminant. It
was not until the end of the 1920s that a safe, explosion free, wet ball milling process
was developed. This manufacturing process has continued largely unchanged in its basic
features to this day. An upsurge of interest in metal pigments occurred from the late
1970s onwards, as evidenced by an explosion of patent literature. Products were tailored
to the intended application media and increasing account was taken of the need for
environmentally friendly product delivery forms. Improvements in flake brightness and
advances in flow and weld line minimisation ensured the growth of metal pigments for
the direct coloration of polymers.
The future is likely to bring further advances in optical brightness through improvements
to milling and screening technology. The goal for manufacturers remains attainment of
the reflectivity of vacuum deposited metal with the economics of the ball milling process.
The apparently insatiable desire for novel colouristic effects will also ensure a place for
metal cores with coloured or even multi-coloured surfaces.
5
2
Metal Pigment Types
Six metals and two alloys are used in significant commercial quantities, though not all as
colouring agents and not all in polymers or as a coating on polymers. The main factors
influencing their effectiveness as pigments are colour, brilliance, corrosion resistance,
malleability, specific gravity (SG) and cost. Table 2.1 compares properties for the metals,
plus the alloys gold bronze and stainless steel.
Table 2.1 Metal Properties

Corrosion
Colour Brilliance Malleability SG Cost
Resistance
Aluminium White High Moderate High 2.70 Moderate
Bronze Gold High Moderate High ~8.50 Low-moderate
Copper Reddish Medium-high Medium-poor High 8.96 Moderate
Nickel Off-white Medium Good Moderate 8.90 Moderate-high
Stainless steel Off-white Medium Good Low ~8.00 Moderate-high
Zinc Blue-white Low Good Moderate 7.13 Low
Iron Grey Low Poor Moderate 7.87 Low
Silver White Very high Fair-good Very high 10.50 Very high
2.1 Aluminium
Aluminium is a silvery, ductile metal. Although by far the most prolific metal pigment
world-wide, data on consumption are lacking. Use of aluminium in polymer related
applications is estimated at 4,000-5,000 tonnes per annum worldwide. Although mainly
used for used for its colouristic properties, aluminium pigments have a wide range of
other uses, such as light barriers, light reflectors, moisture barriers and thermal conductors.
Chapter 15 is devoted to such non-pigmentary applications.
In the plastics market, the full commercially available particle size range is used, ranging
from 5-650 µm in ball milled grades, to several millimetres for cut foil types.
7
The combination of excellent colour, low density and relatively low cost are attractive
commercial advantages, but are offset by limited corrosion resistance. Aluminium flake
is attacked by water throughout the pH range, but is most stable a few units either side
of neutrality. Dry, airborne flakes are explosive, especially the smaller particle sizes. In
this respect aluminium flake is no different to many finely divided organic materials.
2.2 Gold bronze
The pigment known as gold bronze is actually brass, i.e., a copper-zinc alloy. It remains
the prime source of gold effects for all applications except the most technically demanding,
such as automotive paints. The shade is controlled by the copper/zinc ratio, which in
practice varies between about 70/30, known as ‘rich gold’, through to ‘rich pale’ at
86/14 simulating 22 carat gold, to the redder ‘pale’ at 90/10.
Gold bronze flake is susceptible to tarnishing, so for more durable applications it requires
a protective coating, usually of silica. Gold bronze flakes are not explosive, but the finer
grades are classed as flammable. In recent years the perceived toxicity of the copper
component has prompted the replacement of gold bronze with combinations of aluminium
pigments and reddish yellow, orange or even brown organic pigments.
2.3 Copper
Copper flakes have an attractive reddish sheen, but find limited pigmentary use because
they tarnish readily in air, forming coloured salts, such as the green verdigris. For the
same reason, the metal’s excellent electrical conductivity can only be exploited if the
flakes are incorporated in a reliably impervious matrix. More stable coloured copper
flakes, created by controlled surface oxidation, are available.
2.4 Nickel
Nickel is used less for its colouristic effects than for its electrical properties. It offers a more
expensive, less bright silver than aluminium, but has the advantage of excellent corrosion
resistance. Flakes developed for electromagnetic interference (EMI) shielding have a particle
diameter of around 12-25 µm and an aspect ratio (see section 4.1.3) of about 20:1. Such
flakes may also be heat treated in a controlled atmosphere to further enhance conductivity.
For colouristic applications, nickel flake is offered in leafing types (see section 4.3.4) and
grades for water-based systems. Both of these can be used in solvent systems. With its
8
Metal Pigment Types
slightly yellowish, pewter-like hue and rich lustre, nickel is one of the brighter of the
secondary (less common) metals. It therefore finds limited application in protective
decorative paints, especially water-based systems, which can take advantage of the metal’s
excellent gassing resistance (resistance to generation of hydrogen gas when in contact
with water). Water-based grades are non-leafing and can be used to advantage in mixtures
with organic and inorganic colorants because they will not obscure the colour underneath
as leafing grades would (see section 4.3.4). Applications of nickel are influenced by its
health and safety credentials (see Chapter 16).
2.5 Stainless steel
Stainless steel is a generic term used to describe a very large range of alloys – in excess of
200 grades in total – all of which are iron based materials containing in excess of 11%
chromium. Stainless steels can be classified into four basic types, austenitic, duplex,
ferritic and martensitic. The austenitic grades, which normally contain nickel, account
for approximately 75% of total production.
There is a strong preference as a pigment material for one austenitic grade in particular
– UNS-S 31603 (formerly known as AISI Type 316 L) which has a typical composition
of 17% chromium, 12% nickel and 2.5% molybdenum. In bulk form it fulfils many
demanding roles in chemical plant construction and in food handling applications because
of its very high resistance to corrosion in many different aggressive environments.
2.6 Zinc
Zinc is a bluish-white lustrous metal. By far its main use is in anticorrosive coatings. The
flake form offers a number of technical advantages over the more common zinc powder,
such as increased surface coverage and reduced tendency to settling, but zinc flakes have
struggled for commercial acceptance due to the additional costs associated with the milling
and flake recovery stages. It has no obvious use in mass pigmented polymers.
2.7 Iron
Iron is the cheapest of the pigmentary metals. Its use as a pigment is greatly limited by its
low brilliance, pewter-like colour, high density and most severely, by rapid tarnishing
(rusting) in water-based media. It is however a useful, inexpensive core particle onto
which more attractive metals and organic or inorganic colorants can be deposited (see
section 3.9).
9
2.8 Tin
Tin is a durable, low melting, easily malleable metal, silver in colour with a pale gold
cast. It makes very attractive flakes by wet ball milling, but these are soft and therefore
tend to be poorly shear resistant in applications. The high density and cost of tin combine
to render use of these flakes uneconomic, despite their attractive colour and excellent
water resistance. Their use is made even less viable because thicker flakes are required to
provide adequate degradation resistance. Like zinc, tin is not used for the mass
pigmentation of polymers.
2.9 Silver
The high cost of silver and its very high density preclude its use as a commodity pigment.
It is used in a few critical ink applications, such as printed circuit boards and windscreen
de-misting tapes, in which its excellent electrical conductivity and good tarnish resistance
are essential. Better use is made of this high priced raw material if it is deposited onto less
expensive core particles.
2.10 Gold
The ultimate in density and tarnish resistance, but unfortunately also in cost. Real gold
has all but disappeared from use as a flake pigment. Its use is not considered further in
this text.
2.11 Other metals
Titanium is another metal with excellent durability, but it is expensive. It is also difficult
to mill, due to its brittleness relative to the other metals considered here. As a result, it
has found few if any commercial applications.
10
3
Manufacture
3.1 Dry milling
The earliest bronze and copper powders and later aluminium flake powder, were
originally produced in Germany by stamping in a two-stage process. Thin metal foil
was reduced in size in large circular vessels by pounding in a vertical plane with
heavy rods while the vessel and its contents rotated. A lubricant, generally stearic
acid, was added to prevent cold welding, i.e., the tendency of adjacent flakes to weld
together under the high pressures generated when they are trapped between the milling
rods and the body of the vessel. Coarse flakes produced in this step, known as ‘flitter’,
were then reduced to powder in small stamping units, with the addition of more
stearic acid. The resulting product was rubbed through fine screens to remove
excessively large flakes, which would be recycled for further comminution. To increase
brightness, a further treatment involved polishing in drums fitted with radially
mounted brushes. More fatty lubricant would be added, bringing the concentration
up to 4-6%.
The stamping process proved slow, cumbersome, very dusty and uneconomic. It is not
surprising that dry ball milling superseded it. Economics were further improved by
moving to a continuous process (see section 3.2).
The batch ball mill consists of a steel cylinder, a metre or more in diameter and perhaps
3-4 metres long, with its long axis horizontal (see Figure 3.1). Solid steel spheres of
3-10 mm diameter occupy around a third of the internal volume. As the mill revolves,
these milling media cascade onto the metal powder and lubricant. It is this cascading
action that causes flattening of the starting powder to generate flakes. Several narrow
steel bars running the length of the mill increase the height from which the media
cascade, thereby speeding up the milling process. The considerable mechanical energy
expended causes the mill and contents to heat up. For this reason the mill is generally
water cooled via an external jacket.
Edwards and Wray [1] and also Wendon [2] describe early manufacturing processes.
11
Figure 3.1 A typical production ball mill.

The mill is configured for draining the milled slurry through the pipe connected to
the underside.
3.1.1 Aluminium
In the case of aluminium in particular, dry milling is extremely dangerous. Although not
pyrophoric, i.e., spontaneously combustible, fine aluminium dust in air only requires an
ignition source to cause a very violent explosion. For this reason, inert gas was used in
ball mills. Even so, dry milling has declined mainly for safety reasons.
3.1.2 Gold bronze

Remarkably little literature exists on milling of gold bronze pigments in general, but there
is some information in Wendon [3]. Production begins in the foundry with fusion of molten
copper and zinc to form the gold bronze (brass) alloy. A small quantity, usually less than
1%, of aluminium is included as an antioxidant. The molten alloy is then atomised by
compressed air to form a fine powder. The stamping type of dry flake production has long
since given way to continuous dry milling in conventional ball mills (see section 3.2.2).
12
Manufacture
3.2 Continuous dry milling
As might be expected, the main advantages of a continuous process are in throughput

and improved economics, but product uniformity is also important.
3.2.1 Aluminium
The explosion hazard was reduced by the introduction of what became known as the
Hametag process, Hametag being a contraction of Hartstoff-Metall AG [4, 5, 6, 7]. This
was a continuous dry ball milling process carried out under a nitrogen purge sufficient to
maintain the oxygen content at around 5%. Such a concentration is below the lower
explosive limit for aluminium dust, but nevertheless provides sufficient oxygen for
controlled re-oxidation of the very reactive nascent aluminium surfaces created by the
milling action. Flake separation was initially provided by cyclones into which the flake
was carried by the carrier gas. This was found to give an inefficient separation of small
flakes from large and was later modified by Mandle [8] and by Carlfors [9]. Booz and
Kondis [10] at the Aluminium Company of America (Alcoa) later developed a further
variant, involving a vibratory mill. They proposed a continuous feed of aluminium powder,
stearic acid lubricant and reduced oxygen gas through a vibrating mill, with removal of
product by the carrier gas at an equivalent rate.
3.2.2 Gold bronze
Gold bronze flake pigments are manufactured by much the same ball milling processes
as aluminium, though allowance must be made for the much higher density. The flake
shape is similar. Kramer’s [11] continuous dry milling process has endured to this day,
due principally to the lower flammability of gold bronze. For this reason, an air current
rather than more expensive inert gas (see section 3.2.1) could be used to remove flakes
from the milling chamber. A dry milling process patented by Mandle featured closed
loop recycling of oversize flakes back to the mill. In practice, almost all gold bronze flake
made by this or any other process is of the leafing type, employing stearic, or occasionally
palmitic acids as lubricants.
Leafing grades predominate because non-leafing forms of gold bronze tend to have a
dull appearance. Until recently, non-leafing forms were not commercially available.
Where a non-leafing finish is required in coating applications, leafing flakes are generally
deliberately de-leafed by addition of an organic acid, such as citric acid. The terms
leafing and non-leafing are defined and further discussed in sections 4.3.4 and section
13
12.2.3. It should be noted however that the terms have no real relevance in mass
pigmented polymers.
The milling action generates fresh gold bronze surfaces. These are re-oxidised at a rate
dependent on oxygen availability. This in turn affects the colour of the resulting product,
even from a single alloy.
In the final polishing stage of production, a slow speed mill is used with a different type
of ball charge to induce a very gentle ball milling action. The flakes are smoothed and
flattened. Hiding power increases as agglomerates are broken up. Reflectivity increases
along with leafing value.
It is important that the stearic acid lubricant forms a complete chemically bound coating
on the metal surface. In freshly produced powder this reaction is incomplete. Bronze
powder manufacturers therefore have to artificially age their products by storage for a
period of time until the reaction is complete.
3.3 Wet milling
The advent of the wet milling process by Hall [12, 13] was to revolutionise metal flake
pigment manufacture. Indeed this profuse inventor also contributed to powder technology
by providing an atomising process [14].
3.3.1 Aluminium
The Hall milling process (see Figure 3.2) is desirable not only because of its efficiency,
but also because the elimination of grinding under dry conditions makes it very much
safer. The ball mills used are much the same as those described for dry milling in
section 3.1.
For aluminium flake pigment manufacture, there are three raw materials to be added to
the ball mill. The first is atomised aluminium powder, or in the case of economy grades,
foil scrap. This is added to the ball mill, which will already be part filled with the steel
grinding media. Then 3-6% (w/w of metal) of a long chain fatty acid, typically oleic acid
or stearic acid, is added. The chemical nature of the fatty acid has an effect on the
properties of the resulting flakes in coating systems. Stearic acid produces leafing flakes,
whilst those derived from oleic acid are non-leafing. Finally, sufficient mineral spirits,
otherwise known as white spirit, a high boiling aliphatic hydrocarbon blend, is added to
form a mobile slurry.
14
Manufacture
Figure 3.2 The Hall wet milling process for the manufacture of
aluminium flake pigment paste
The mill is revolved at a speed that will allow the balls to cascade onto the aluminium
metal. As aluminium is one of the more malleable metals, it is readily flattened. Figure
3.3 shows atomised aluminium starting powder. Partway through the milling process,
the particles have the appearance shown in Figure 3.4. Eventually the particles become
so thin that they begin to break up, reducing the median particle size of the mix and
producing the tiny flakes, typically less than one micron thick, that are required (see
Figure 3.5). The lubricant prevents cold welding that would otherwise occur when
overlapping flakes are trapped between the grinding balls.
15
Figure 3.3 Atomised aluminium powder [1 cm = approx. 40 µm]
Figure 3.4 Atomised aluminium powder, partly flattened by wet ball milling
[1 cm = approx. 40 µm]
16
Manufacture
Figure 3.5 ‘Cornflake’ type aluminium flake pigment, derived from the Hall process
The length of time the ball mill turns depends on the grade of flake being manufactured
and its desired particle size distribution. A milling time of 5 to 30 hours is typical.
When the grinding operation has been completed, the slurry is discharged from the
ball mill by washing it out with more solvent.
This dilute slurry is presented to a vibrating screen of appropriate mesh size. The function
of the screen is to recover the required particle size fraction. This will generally be the
flakes small enough to pass through the screen. It is this screening process together
with the milling time that differentiates one grade from another. Flakes that are too
large to pass through the screen are returned to the ball mill for further comminution.
The remaining flakes pass to a filter press. Excess solvent is removed in the press,
resulting in a filter cake having a volatile content of approximately 20 per cent.
The final step in the manufacture of a paste involves homogenising the filter cake in a
mixer. Adjustments are made to ensure that the paste meets the specification for that
grade in properties such as colour, sparkle and hiding (opacity). Colouristic properties
(whiteness, brightness and sparkle) can be influenced by mixing time and paste viscosity.
Under suitable conditions a polishing action can be made to take place. This can change
17
reflectivity and flop characteristics (see section 4.3.3) by reducing surface irregularities
and consequent light scattering. In the case of leafing grades, the leafing value is increased
(see sections 4.3.3 and 4.3.4).
Addition of an aromatic hydrocarbon solvent is often made at the mixing stage, to

alter the solvent balance of the paste, to improve compatibility in liquid coating media.
A stiff, paste-like consistency is obtained with a volatile content of approximately 25-
40%, depending on the coarseness of the flakes. The finished paste is finally packed
into drums and sealed for dispatch.
In practice it is the solids content, known as the non-volatile content (NV or sometimes
NVC) that is more generally quoted. NV affects the transport and shelf life of pastes.
If the NV is too low, the metal may sediment in transit. Weight based formulae are
then under-pigmented. Too high a NV is symptomatic of dry pastes, with reduced
shelf life.
One grade is distinguished from another by the particle size distribution, shape and
surface finish of the flakes. These features are determined by milling parameters such
as mill dimensions, rotation speed, milling time and temperature, grinding media
loading, size and density, in addition to the amount and nature of metal, solvent and
lubricant present. Particle size distribution is further modified at the screening stage.
By the time the filter cake is mixed, there are few opportunities for major adjustment
of application properties. It follows that the character of the product is formed in the
milling and to a diminishing extent, screening and mixing stages of production.
In the case of filter cakes intended for plastics applications, the hydrocarbon solvents
of manufacture are not suitable carriers for the metal flakes. It is necessary to remove
the solvent to give either dry flakes or compositions in which the solvent has been a
replaced by a polymer compatible carrier. These and other application-specific delivery
forms are described in Chapter 5.
The products of the described wet milling process have become known as ‘cornflakes’,
due to their resemblance to the well-known breakfast cereal. Developments in milling
technology in the 1980s produced thicker, more rounded flakes with smoother surfaces.
Due to their shape, these became known as ‘silver dollars’.
Silver dollars are an advance in aluminium pigment technology because they are
demonstrably whiter and brighter than cornflakes of the same particle size distribution.
Their production costs are higher because they require expensive, specialised atomised
powders and a more gentle, time consuming, milling regime, involving smaller, more
expensive grinding media. Their first and ongoing main application is in automotive
18
Manufacture
paints, but they are also used in high quality printing inks. More recently they have
begun to appear in plastics, especially in paint replacement applications where maximum
brightness comes before cost.
A related development is degradation resistant flakes or ‘Tufflakes’ [Registered

trademark of Silberline Manufacturing Co. Inc., USA]. These are also thicker flakes,
designed to be resistant to shear. A patent to Hieda [15], filed in 1987 defines and
claims such degradation resistant aluminium flake pigments and a wet ball milling
process for their manufacture.
The role of lubricant in the wet milling process was studied by Imasoto [16], using
stearic acid. The amount adsorbed increased with milling time up to a limiting
concentration of 0.135 mol/kg aluminium. The specific surface area increased up to
~8m2/g. A bimolecular adsorbed layer could be formed depending on the flake size and
therefore its surface area. If the surface area is low, the limiting concentration will be as
a double layer; if it is high it will be spread out as a monolayer. This has significance in
considering the effect of metal flake pigments on the mechanical properties of polymers
in which they are incorporated.
3.3.2 Gold bronze
As noted previously, milling of gold bronze is not well documented. Nevertheless, Hall
[17] provided a wet milling process as part of his 1919 patent, granted in 1925. Milling
solvents and lubricants were chosen to allow easy removal of the solvent whilst leaving
the flakes coated with lubricant. Stearic acid, aluminium stearate and air blown through
the mill combined to aid leafing. The product could be heated to 50 °C, though not
appreciably higher, in oxygen to prepare dry flakes with retention of leafing. The vast
majority of gold bronze flake manufactured today is dry milled.
The tarnish resistance of gold bronze in both coatings and polymers is improved by
applying a silica coating from a hot aqueous silicate bath containing a water-soluble salt
of an organic acid, followed by drying. Developments of this early process by Atlantic
Powdered Metals [18] are still in use today.
3.3.3 Silver
A process for the preparation of silver flake powders is disclosed in a patent granted to Du
Pont [19]. Precipitated silver powder is bead milled in the presence of water and a small
quantity of an unsaturated fatty acid, such as oleic acid or linoleic acid. The flakes are later
19
separated from the beads and dried. The product obtained is a silver flake substantially
covered by a monolayer of fatty acid, believed to be attached to the flake surface via the
double bond(s). Whatever the configuration, the flakes can be formulated at over
85% w/w without the high viscosity that reduced the usefulness of uncoated flakes.
3.3.4 Nickel
Nickel flakes are manufactured by milling from high purity nickel powders. They are
produced in three basic types, a leafing grade – solvent milled with a stearate lubricant,
a water compatible non-leafing grade, milled in polyhydric alcohols and a special
electrically conductive grade.
Filamentary nickel powders are manufactured exclusively by a nickel carbonyl refining

process, and their primary application is for nickel alkaline battery manufacture. Their
structure, however, also allows them to be used as pigments in electrically conductive
materials, particularly paint coatings. These are employed not only for electromagnetic
shielding but also in antistatic applications (see Chapter 15).
Figure 3.6 Spherical nickel powder [1 cm = approx. 3 µm]

Reproduced with permission of Hart Coating Technology and Novamet
20
Manufacture
Discrete spherical nickel powders can be produced in an extremely pure form directly from
the nickel refining process (see Figure 3.6). By a combination of screening and air-classification
(i.e., size segregation in air, using a hydrocyclone), the size range of a particular grade can be
carefully controlled to suit specific applications. The finest particle size material readily available
commercially is a sub-10 µm air-classified grade. Such powders are used to produce composites,
mostly for electromagnetic shielding applications.
To overcome the limited chemical resistance of aluminium flakes, Tundermann and

Harrington [20] used nickel, cobalt and related alloy flakes, including stainless steel. They
are prepared by a batch wet ball milling process, modified to reduce viscosity, to prevent
the fragmentation of these metals that takes place under normal milling conditions.
3.3.5 Stainless steel
Stainless steel flakes are manufactured by solvent milling from suitable size powder
stock. Like nickel flake pigments, they are also available as stearate milled, leafing
grades (see Figure 3.7).
Figure 3.7 Leafing type stainless steel flake [1 cm = approx. 30 µm]

21
Unlike nickel, stainless steel particulates are not produced by a basic refining process but
by melting a mixture of the necessary constituent elements to form the required alloy,
followed by water or gas atomisation. Stainless steel particulates produced in this way
are available in a very wide range of sizes from less than 10 µm up to 2,000 µm.
Commercially available flakes are virtually all produced from UNS-S 31603 (stainless
steel alloy) powder because of its superior corrosion resistance properties.
Stainless steel is more time consuming to mill into flake pigment than the softer
aluminium and gold bronze. Its colour is also inferior to aluminium. Nevertheless its
corrosion and abrasion resistance qualify it for use in both directly pigmented polymers
and polymer coatings.
3.3.6 Zinc
A batch ball milling process in hydrocarbon solvent was also the process chosen by
Marx [21] to prepare leafing zinc flakes of sub-60 µm diameter for anticorrosive
applications.
3.4 Continuous wet milling
Just as continuous dry milling evolved from the batch dry milling process, so continuous
wet milling is a later variant of the Hall process. Alcoa [22] was prominent in this
field, patenting continuous feed of metal powder, lubricant and solvent through a tubular
ball mill.
3.5 Spherical metal pigments
A variation of the wet milling process was patented by McKay, McKay and Ringan of
Silberline [23] to produce spherical metal pigments. These are polished aluminium spheres
or facetted spheres, from 1 to 300 µm in diameter, derived from substantially spherical
atomised aluminium powder.
This starting material is created by atomisation under inert gas. Processing consists of
gentle polishing in a ball mill or other apparatus in the presence of conventional
hydrocarbon solvent and oleic acid lubricant. The energy imparted is insufficient to
cause flakes to form, but has the effect of smoothing the metal surface to increase
reflectance by at least 10-30% over that of the starting material. The products are used
in coatings and mass pigmented plastics.
22
Manufacture
In summary, the range of flake particle size obtainable from the Hall process and its
developments is very wide, ranging from a D50 (see section 4.1.1) of perhaps 4-5 µm to
large, thick, so-called ‘glitter’ flakes (or in the USA, ‘flitter’ flakes) up to 600-700 µm
in diameter.
3.6 Rapidly solidified flakes
A means of preparing metal flake pigments without the need for ball milling is provided
by allowing molten metal to impinge directly on a cooled disc rotating at extremely high
speed. The molten droplets cool virtually instantaneously and are dispersed by centrifugal
force to be collected in a chamber. Rotor speeds in excess of 20,000 rpm and a cooling
rate of over 102 C°/sec are ideally required. The process is variously named spinning
disc, centrifugal atomisation, splat cooling or splatomisation.
The principle was first described in the 1960s and refined by a number of later patents.
Design of the disc and the means of cooling are critical to the quality and consistency of
the product. Advantages include compositional uniformity, especially of alloys, leading
to improved mechanical and physical properties.
Early commercial interest came from the Pratt and Whitney Co., [24, 25] through their
Rapid Solidification Rate (RSR) technology. Molten metal flowing through a funnel
onto a spinning disc is radially accelerated and dispersed into cooled, almost spherical
droplets, in a helium atmosphere.
Later, Yeh [26, 27] claimed a similar apparatus. A refinement consisted of a second
cooled rotating disc onto which the product of the first was thrown. This configuration,
combined with a very high cooling rate of 106 C°/sec produced aluminium and iron
elongated flake-like products of 10-600 µm particle diameter and a median particle size
of around 200 µm.
Boswell [28] at the Batelle Memorial Institute in Switzerland claimed a hybrid of rapid
solidification technology and ball milling. In the specification, a molten metal such as tin
or an iron alloy is rapidly cooled in contact with rapidly agitated balls. The products are
said to have greater angularity but are nevertheless suitable for paints.
Considered overall, at the present state of development, rapid solidification processes

appear ill suited for the preparation of fine particles with conventional flake geometry.
23
3.7 Vacuum deposition
Vacuum deposition for flake pigment manufacture is an adaptation of the widely used
process for the metallisation of polymer film. It involves coating polymer film, usually
polyethylene terephthalate (PET), with a resin deposited from solvent solution to form a
release layer (a dry release film that is resoluble in solvent). Under very high vacuum,
pure aluminium is deposited on the dried film from the gas phase to a minimum thickness
of 40-60 nm. In practice, the 2-3 m wide film is unspooled across the coating head, and
subsequently respooled, the whole process taking place in a vacuum chamber. The
aluminised film is subsequently run through a solvent bath at ambient pressure to dissolve
the resin and release the sheets of ultra reflective aluminium. In the final stage of the
process, the sheets are broken down to flakes. The product is offered for sale as a dispersion
in solvent containing about 10% metal.
Much early work is credited to McAdow [29]. The basic process elements described
above were operated to produce aluminium or chromium flakes of 0.075-0.6 µm thickness.
A translucent, solvent-based coating containing only 0.028 to 0.15% of these particles,
with a surface area of 40,000 to 60,000 cm2/g is claimed.
A later modification [30] claimed a larger metal flake, principally aluminium, of greater
planarity (flatness) for more efficient light reflection and sparkle. This was made possible
by supporting the flake surfaces on both sides with an insoluble film of resin, thin enough
to allow coated flakes over 30 µm in diameter to be produced from coated film by the
customary mechanical agitation. As the resin coating insulates the flakes from each other,
they have no ability to carry electrical charge. They were therefore well-suited to the
then emerging technique of electrostatic spraying. A related patent describes the process
of preparation [31].
After separating the vacuum deposited metal film from the polymer sheet by dissolving
the release layer in solvent, Roberts [32] used ultrasonic energy to disintegrate the film
to flakes, as did Levine and co-workers at Revlon [33].
The process proved to be applicable to a wide variety of deposited metals, but magnesium,
aluminium, copper, silver and gold are especially favoured. The suggested applications
of the product are paints and moulded plastics.
A more recent method, disclosed by Gray and co-workers [34], generated flakes by
allowing a vacuum deposited film to be disintegrated from the surface of an enclosed
glass cylinder following its formation by a gas plasma technique.
Miekka at the Avery Dennison Corporation [35] extended the process to create a metal
flake pigment with holographic properties. As an example, a polystyrene release coating
24
Manufacture
is laid down on a Mylar carrier film with a 200 line rotogravure roll, using a commercial
roll coater. The dried film is embossed by heating above the polymer softening point and
pressing the outer surface onto a roller engraved with a diffraction pattern. A 30 nm
thick aluminium film is then applied by vacuum deposition. The film is separated by
dissolving the release layer in a toluene/methyl ethyl ketone (MEK) mixture and
mechanically converting it to flakes which exhibit the retained diffraction pattern.
Vacuum deposition produces the brightest commercially available aluminium flake. Due
to the costs associated with providing a very high vacuum and vapourising aluminium,
the product is extremely expensive. This limits its use to the very highest quality coating
applications, such as logos, highlighting, spot colour and reflective coatings on lamps,
especially coatings on plastic for car headlights. The product appears under the trade
names Metalure, Metasheen and Star-Brite.
3.8 Cut foil glitters
Cut foil glitter flakes are easily distinguished from ball milled types under an optical
microscope. The former have a regular geometry and are available in particle sizes greater
than those obtainable from milled flakes (see Figure 4.15). Squares, rectangles, hexagons
and diamonds are the most common, ranging from 50 to over 2000 µm in diameter, with
a thickness from 15-50 µm. They are produced by stamping or cutting thin foil, usually
of aluminium. Particle size is therefore very regular. The cost of the flakes increases with
decreasing size, reflecting the increased amount of cutting required.
The delivery form is dry flake, since apart from the smallest particle sizes, dusting is not
a serious problem. Because of their large particle size, cut foil glitters are too large for
inks and all but the most specialised paint applications. They are therefore used most in
mass pigmented plastics.
Coloured glitters are also available. Their preparation is described in section 3.9.3.
3.9 Flakes with coloured surfaces
This section describes a diverse collection of novel approaches used to alter the colour of
existing metal flakes. It includes chemical modification of the metal surface, attachment
of pre-formed colorants and colour formation in situ from components reacting at the
metal surface. A wide range of flake particle size is represented, from fine, high opacity
grades to very large glitter flakes.
25
In the wider context of flake pigments, pearlescent or mica pigments are nowadays also
often coated. These will not be considered here, with the exception of mica flakes coated
with elemental metals.
Interest in surface coloured metal flakes arises because coating metal flakes with organic
and inorganic colorants provides visual effects not achievable by physical mixtures of
metal flake and colorant. These are considered further in section 7.10.
Attempts to colour the surfaces of principally aluminium flakes are recorded in the patent
literature as far back as the 1950s. The earliest technology employed was a variant of
anodisation in which dyestuffs were absorbed into the porous oxide surface coating of
aluminium. The colour was fixed by immersion in boiling water [36].
It was not until the 1980s that chemically coloured metal flakes became commercially
significant. An upsurge of research activity provided novel processes for paints, inks and
the mass pigmentation of polymers.
3.9.1 Chemical modification of metal surfaces
An early development, optionally for water-based applications was patented by

Interchemical Corporation [37]. Coloured pigments and a method for their manufacture
was the subject of work by Harakawa [38]. A quench solidified (very rapidly cooled)
pigment composed mainly of iron alloyed with specific percentages of chromium,
phosphorus and carbon is heated to 150-700 °C for 1-5 hours. The surface colour
produced is dependent on the treatment temperature and time, ranging from red at low
temperatures and times to blue and green at high temperature and times.
Knox and Green of Silberline [39] claimed preparation of coloured iron or iron alloy
flakes. Wet milled flakes are heated in a furnace at 150-700 °C for various times from 20
seconds to two hours in a reduced oxygen atmosphere. A wide colour spectrum results,
ranging from gold through copper-red to blue and eventually black at the highest
temperatures. The process is particularly suited to large flakes (~100-600 µm median
particle diameter) for the mass coloration of plastics, especially as a component of
stoneware and granite effects. The products are offered commercially under the Silcroma
trade name.
In a very recent development, Fetz [40, 41] of Eckart-Werke described aluminium flakes
with a golden hue, prepared by oxidation with a controlled quantity of water in an
alcohol medium containing a basic catalyst. Both leafing and non-leafing flakes are
suitable, but the latter give better optical properties (brightness, cleanliness).
26
Manufacture
The 20-30 nm thick oxide layer controls the colour range, from pale gold to brown.
This oxide surface is highly porous, with a surface area around five times that of the
starting material. Although UV stable and shear resistant, the products, trade named
Aloxal, are not totally water stable. They must be further protected by hydrophobic
inhibitors, such as phosphates.
An unusual process for creating colours on titanium particles was developed by

Greening and Clegg [42]. Fine particle size titanium is agitated in an aqueous
electrolyte and subjected to a voltage of 5-100 V, preferably direct current between
immersed anode and cathode. The coloration formed on the metal surface is controlled
by the applied voltage and treatment time to produce durable products suitable for
incorporation in paints.
3.9.2 Colour formation in situ
Ostertag, Bittler, Bock, Murphy and Ravella at BASF in Germany [43, 44, 45] pioneered
the deposition of metal oxides from the gas phase onto aluminium flakes in a fluidised
bed at elevated temperature. Chief amongst these were iron oxide golds formed by
decomposition of iron pentacarbonyl to ferric oxide in the presence of oxygen and
optionally, water vapour. In later variants, multiple coatings were formed to provide
interference or lustre effects, using a wider range of metals, such as titanium, chromium,
molybdenum, tin, silicon and zirconium, in addition to iron.
Schmid and Mronga [46] disclosed surface coloured aluminium flake pigments comprising
a first, colourless or selectively absorbing layer of metal oxide, a second, nonselectively
absorbing layer of carbon, metal and/or metal oxide and optionally another layer like
the first. The layers are deposited sequentially in a fluidised bed. In a further US Patent,
the order of the first and second layers is reversed and higher treatment temperatures
introduced [47]. The flakes are also claimed to be less aggregated than those of the
earlier patent because the process includes a pre-treatment to remove traces of lubricant
from the flake manufacturing stage. Extension of the process to include wet chemistry
techniques is the subject of US Patent 5,624,486 [48].
The product group, marking the outcome of the BASF work, named Paliocrome, found
its main use in paints for the top end of the automobile market, including coatings on
polymeric components.
A multi-stage wet chemistry route was used by Nadkarni [49]. Metal flakes, especially
aluminium, are dispersed in an aqueous alkaline zirconia sol to form a coating. In a
second stage the coated flakes are treated with a solvent solution of a metal salt, such as
27
cobalt nitrate or iron nitrate. Finally the flakes are heated to fix the coating. Colour
intensity can be increased by repeating the treatment cycle.
Souma [50] also used wet chemistry to hydrolyse an organic titanium ester in the presence
of metal flakes in a suitable organic medium. Claimed metals are aluminium, gold bronze,
stainless steel, tin and iron. Attractive iridescent tones are produced, the hue being
dependent on the thickness of the titanium oxide coating, which varies between 40 and
155 nm. The products are particularly useful in aqueous coating compositions because
the coating is very effective in protecting the underlying aluminium.
Interference platelets were disclosed by Philips [51] at Flex Products in the USA. They
consist of multi-layer thin films deposited on a flexible web material and subsequently
removed and comminuted. They include a metal reflecting layer. The process is akin to
vacuum deposition (see section 3.7) producing interesting, though expensive products
for prestige coating applications.
A related multi-layer technology, developed by BASF [52], generates colour-variable

pigments (CVP). In one variant, the core is a silver dollar aluminium flake of 15-20 µm
diameter and 300-500 nm thickness. A low refractive index coating of silica is applied
by wet chemistry, followed by a very thin layer of iron oxide. The thickness of the
coatings controls the visual effect. Automotive paint applications make the best use of
the pigments’ goniochromicity, i.e., the variation of colour with angle of viewing, also
known as colour flop.
3.9.3 Attachment of pre-formed colorants
Coloured metallic glitters are prepared by coating both sides of the starting metal foil
with a pigmented resin, generally epoxy or polyester, prior to cutting. Ideally both pigment
and coating resin should have a high degree of transparency to maximise metallic
brightness. A wide colour range is available.
As noted in section 3.8, such metal pigments are too large for most coatings and so are
used mainly in plastics. Unfortunately the cheaper grades offer heat stability only up to
about 230 °C. Above this temperature the coating resin melts and delaminates, causing
the pigment to disperse in the polymer matrix, discolouring it. The problem is particularly
acute in polar polymers such as polyamide. This glitter type is therefore only suitable for
lower melt point polymers such as PVC, polyolefins and some styrenics.
Recently, coloured glitters have been developed which are more durable but more
expensive. These have epoxy-based coating resins of increased transparency, providing
28
Manufacture
brighter metallic effects and increased heat stability, up to perhaps 250-260 °C in

application, depending on the polymer. Applications of these pigments are considered in
Chapter 11.
Chida [53] at the Showa company in Japan developed coloured metal pigments by
attaching finely dispersed organic or inorganic pigments to metal flake surfaces. The
process consists of heating a metal pigment such as aluminium to around 90 °C in solvent
with a thermally polymerisable fatty acid having multiple carboxylic acid groups. The
cooled slurry is concentrated to filter cake and subsequently added to a ball milled pre-
dispersion of organic or inorganic pigment in a little solvent. The colorant is fixed to the
flake surface by a short kneading step in solvent. Attachment of the colorant is improved
by a post-treatment involving free radical polymerisation to form a coating on the flakes.
The products are used in both coatings and mass pigmented plastics.
Two related processes were disclosed by Hashizume of Toyo Aluminium. The first
employed compounds having multiple amino groups rather than multiple carboxylic
functions. Aluminium, titanium and silicon compounds could be added to enhance
attachment of organic pigment particles to the metal pigment surface [54]. The second
process, apparently developed from the first, additionally used metal acids such as
molybdic acid, monobasic, aromatic carboxylic acids and polymerisable monomers to
further improve bonding of the organic pigment to the metal surface [55]. Stable coloured
metal pigments suitable for coatings and the mass coloration of polymers resulted.
Keemer [56] prepared a metallic pigment composition by treating a metal pigment, such
as aluminium or gold bronze, with a mixture of organic or inorganic pigment particles
and wax. An organometallic coupling agent, monomer and initiator were then reacted
to form a coloured polymeric shell on the metal surface. No post-treatment was required
to fix the colorant in place.
Deposition of organic pigments from the gas phase onto metal pigments, especially
aluminium, is disclosed by Suzuki [57, 58, 59]. The process is carried out under high
vacuum to give a continuous, uniform and homogeneous coloured layer some 0.01–
0.1 µm thick at the metal surface. These products can be used in masterbatches at up
to 30% concentration.
3.10 Metal coatings on non-metallic substrates
Although stretching the definition of a metal pigment, a group of flake pigments may be
obtained by forming a continuous, thin coating of elemental metal on a non-metallic
core. Such a product is described by Muller of Du Pont [60]. Nickel is deposited on pre-
29
sensitised mica or glass flake by a wet chemistry technique. Interference colours are
generated by further deposition of a thin layer of nickel oxide or titanium oxide, also
from aqueous solution. The products are suitable for use in paints and especially in the
mass coloration of plastics.
A related technique was used by Yolles [61] to deposit metals onto glass flakes by
decomposing an organometallic compound such as dibenzene chromium or a trialkyl
aluminium under vacuum at elevated temperature. Neither of these techniques found
widespread acceptance, probably due to excessive cost.
In addition to the range of pure nickel pigments, two distinct types of coated products
are also produced; one in which nickel acts as the coating, the other in which it provides
the substrate. Nickel can be applied as a coating on a number of particulate substrates.
Two types commercialised by the Novamet Corporation are nickel-coated graphite and
nickel-coated carbon fibre. The latter is manufactured using the carbonyl process and is
marketed as a resin-encapsulated product. Nickel-coated mica is also known (see section
15.4.5). All are used for EMI shielding. Use of nickel as a core particle is described in
section 3.11.
3.11 Other methods
The Mond Nickel Company [62] was one of the first to recognise the corrosion resistance
advantages of nickel over aluminium. In 1942 the company patented an electrolytic
process to deposit nickel in the form of very thin flakes on a cathode immersed in an
aqueous solution of a nickel salt, such as the chloride or sulphate. The flakes were
dislodged by mechanical action and treated if desired with a leafing agent such as stearic
acid for use in paints and inks.
Nickel particles can be coated with other metals to provide a surface that gives superior
electrically conductive properties. Two forms are commercially available, offering a
choice of particle morphology. They are silver-coated nickel spheres and silver-coated
nickel flakes.
Both forms are employed to produce electrically conductive composite products for use
in shielding applications where high performance is vital. The flake form is preferred for
coatings and inks whereas the spherical form is used in mass pigmented products such as
silicone polymer gaskets.
30
Manufacture
References
1. J. D. Edwards and R. I. Wray, Aluminium Paint and Powder, 3rd Edn., Reinhold
Publishing Corporation, New York, USA, 1955, 1-14.
2. G. W. Wendon, Aluminium and Bronze Flake Powders, Electrochemical

Publications Ltd., UK, 1983, 6-14.

Publications Ltd., UK, 1983, 13-14.
4. E. Podszus, inventor; Hartstoff-Metall AG, assignee, GB Patent 204,055, 1923.
5. No inventor; Hartstoff-Metall AG, assignee, GB Patent 341,562, 1931.
8. H. H. Mandle, inventor; unassigned, GB Patent 486,845, 1936.
9. No inventor; Carlfors Aktiebolag, assignee, GB Patent 650,818, 1947.
10. A. D. Booz and T. J. Kondis, inventors; Aluminium Company of America,

assignee, US Patent 4,115,107, 1978.
11. E. Kramer, inventor; Metallpulver AG, assignee, US Patent 2,136,445, 1934.
12. E. J. Hall, inventor; Metals Disintegrating Company Inc., assignee, US Patent

1,569,484, 1919.

2,002,891, 1935.

1,545,253, 1919.
15. T. Hieda, inventor; Toyo Aluminium K. K., assignee, European Patent 305,158
B1 (= T. Hieda, inventor; Toya Aluminium Kabushi Kaisha, assignee, US Patent
4,936,913), 1990.
16. Y. Imasoto, Kotingu Jiho, 1989, 182, 9. (Chemical Abstracts P037287E;

in Japanese).
31

1,569,484, 1919.
18. No inventor; Atlantic Powdered Metals, assignee, GB Patent 1,154,933, 1965.
19. L. W. Tyran, inventor; E.I Du Pont de Nemours and Company, assignee, US

Patent 4,273,583, 1981.
20. J. H. Tundermann and J. H. Harrington, inventors; International Nickel

Company, Inc., assignee, US Patent 3,941,584, 1976.
21. W. Marx, inventor; Walter Marx & Co. K.G., assignee, British Patent 846,
903, 1956.
22. No inventor; Aluminium Company of America, assignee, GB Patent

1,588,026, 1976.
23. C. F. McKay, A. McKay and E. S. N. Ringan, inventors; Silberline Ltd., assignee,

European Patent 0,651,777 B1, 1993.
24. P. R. Holiday and R. J. Patterson, inventors; United Technologies Corporation,

25. P. R. Holiday and R. J. Patterson, inventors; United Technologies Corporation,

26. J-W Yeh, K-S Liu, K-Y Shue and Y-C Ho, inventors; National Science Council,
Taiwan, assignee, US Patent 5,259,861, 1993.
27. J-W Yeh, K-S Liu, K-Y Shue and Y-C Ho, inventors; National Science Council,
Taiwan, assignee, US Patent 5,332,198, 1994.
28. P. Boswell, D. F. Richter and G. Haour, inventors; Batelle Memorial Institute,

29. W. R. McAdow, inventor; American Marietta Company, US Patent 2,941,894, 1960.
30. W. R. McAdow, inventor; Mobil Oil Corporation, assignee, US Patent

3,692,731, 1972.
31. W. R. McAdow, inventor; Mobil Oil Corporation, assignee, US Patent

3,697,070, 1972.
32
Manufacture
32. C. B. Roberts, inventor; Dow Chemical Company, assignee, US Patent

3,839,012, 1974.
33. S. Levine, M. E. Kamen, A. Defazio and P. Cueli, inventors; Revlon, Inc.,

34. H. R. Gray, R. P. Shimshock and M. E. Krisl, inventors; Deposition Sciences Inc.,

assignee, European Patent 370,701 B1, 1994.
35. R. G. Miekka, D. R. Benoit, R. M. Thomas, J. P. Rettker and K. Josephy,

inventors; Avery Dennison Corporation, assignee, US Patent 5,672,410, 1997.

Publications Ltd., UK, 1983, 34.
37. R. G. Frieser and P. A. Scardaville, inventors; Interchemical Corporation,

38. Y. Harakawa, inventor; Teikoku Piston Ring KK, assignee, Japanese Patent Kokai
(A) H3-277666, 1990.
39. J. J. W. Knox and W. I. Green, inventors; Silberline Ltd., assignee, GB Patent

2,288,411 B, 1994.
40. A. Fetz, K. Greiwe and H. Birner, Paint & Ink International, 1998, 11, 4, 18.
41. A. Fetz, K. Greiwe and H. Birner, Polymers Paint Colour Journal, 1998, 188,
4409, 42.
42. W. G. Greening, Jr., and N. E. Clegg, inventors; Hi-Shear Corporation, assignee,

US Patent 3,199,999, 1961.
43. W. Ostertag, K. Bittler and G. Bock, inventors; BASF AG, assignee, European
Patent 033,457, 1981.
44. W. Ostertag, K. Bittler and G. Bock, inventors; BASF AG, assignee, US Patent
4,328,042, 1982.
45. W. J. Murphy and A. Ravella, inventors; BASF AG, assignee, US Patent

5,277,771, 1994.
46. R. Schmid and N. Mronga, inventors; BASF AG, assignee, US Patent

5,364,467, 1994.
33
47. R. Schlegal, N. Mronga and R. Rieger, inventors; BASF AG, assignee, US Patent
5,374,306, 1994.
48. R. Schmid and N. Mronga, inventors; BASF AG, assignee, US Patent

5,624,486, 1997.
49. S. K. Nadkarni, inventor; Alcan International Ltd., assignee, US Patent

5,261,955, 1993.
50. T. Souma, M. Ishidoya, T. Nakamichi and N. Takai, inventors; Nippon Oil and
Fats Co., Ltd., assignee, European Patent 0,328,906, 1989.
51. R. W. Phillips, S. P. Fisher and P. G. Coombs, inventors; Flex Products Inc.,

assignee, International Patent Application WO 95/29140, 1995.
52. B. Macdonald, European Chemical & Polymer Engineer, 1998, December, 25.
53. K. Chida, T. Uemura, H. Kitamura and H. Nitta, inventors; Showa Alumi

Powder KK, assignee, US Patent 5,037,475, 1991.
54. Y. Hashizume and Kobayashi, inventors; Toyo Aluminium KK, assignee, Japanese
Patent 09124973 A, 1955.
55. Y. Hashizume, inventor; Toyo Aluminium KK, assignee, European Patent

810,270, 1997.
56. C. B. Keemer, W. S. Halbach, W. G. Jenkins and R. L. Ferguson, inventors;

Silberline Manufacturing Co., Inc., assignee, US Patent 5,558,705, 1996.
57. M. Suzuki, H. Nakaminami and S. Homma, inventors; Japat Ltd., assignee,

European Patent 0 769 535 A2, 1997.
58. M. Suzuki, H. Nakaminami and S. Homma, inventors; Ciba Specialty Chemicals

Holding, Inc., assignee, US Patent 5,718,753, 1998.
59. Nippon Chibagaigii KK, assignee, Japanese Patent 09132730 A.
60. F. Muller, W. Schmidt and H. Werner, inventors; E.I. du Pont de Nemours Inc.,
61. S. Yolles, inventor; E.I. du Pont de Nemours and Company, assignee, US Patent
3,053,683, 1958.
62. No inventor; The Mond Nickel Company, assignee, UK Patent 545,962, 1942.
34
4
Pigment Characteristics
This chapter describes the morphological, physical and visual properties of metal flake
pigments in common use in or on polymers. A description of quality control criteria and
test methods is included.
There are several important differences between metal pigments and traditional organic
and inorganic pigments. The main ones are particle size, specific gravity and particle
geometry.
4.1 Morphology
4.1.1 Particle size
The term ‘particle size’ is normally interpreted as describing the median of the particle
size distribution. This is the size above (and below) which 50% of the total volume of the
particles lie. It is also referred to as the D50 or more correctly as D[v, 0.5] to emphasise its
volume basis.
Measurement of D50 is generally accomplished nowadays by a Low Angle Laser Light

Scattering (LALLS) technique, using apparatus from companies such as Malvern or Cilas.
Metal flake is dispersed in a clear liquid, such as the white spirits of manufacture, at
around 0.03-0.05 g/l of solvent. After a short period of ultrasonic agitation, the dispersion
is allowed to relax to remove air bubbles. Laser light is then passed through the sample
and the intensity of scattered light measured at a range of scattering angles some 2000
times, as the sample passes through the measuring cell.
Computer calculation of results is based on an equivalent sphere that would produce the
same scattering intensities as the flake. This is approximately a sphere of equal volume.
Results are normally presented as ‘volume % in band’, volume % above’ or ‘volume %
below’ graphs, on a logarithmic scale.
The Malvern Mastersizer, for example, provides other useful parameters such as D10,
D90, span and surface area. The first two represent the 10th and 90th percentiles. Together
they provide an indication of the breadth of the distribution and the size of the high and
35
low particle size tails, so relevant to colouristic properties. They also contribute to a
dimensionless quantity called span, defined as
D[v,0.9] − D[v,0.1]
D[v,0.5]
Span is a useful indication of the tightness of particle size distribution in samples with
approximately the same D50.
The difference between the broad distribution envelope of a cornflake pigment and the much
tighter distribution of a modern silver dollar is illustrated by Figures 4.1 and 4.2, respectively.
Surface area measurements have absolute accuracy limitations, but nevertheless provide
useful comparisons between samples.
For all but glitter flakes, particle sizes tend to be quoted in microns. Products of wet
milling range from around 5 to 650 µm. Glitter flakes start at around 100 µm and rise to
2000 µm or more.
Organic and inorganic colorants typically have sub-micron dimensions. Metal pigments
therefore have particles two or three powers of ten larger. This has implications in printing
processes. Metal flakes with median diameters greater than about 20-25 µm are unsuitable
for all but screen printing. In injection moulding of metal flake pigmented polymers,
flake size may be constrained by the size of the pin gates.
Particle size distribution is an important determinant of application properties. A tight

distribution, i.e., a low span value, produces a brighter visual effect in a coating than a
broader distribution with the same median particle size. This is because there are relatively
few large flakes to disrupt smooth orientation or ‘lie down’ of flakes in the coating.
There are also fewer small flakes, which although contributing opacity, have a darker
appearance.
Prior to the introduction of accurate particle size analysers, distribution was measured
by washing a sample of paste through a stack of sieves using more of the hydrocarbon
solvent of manufacture, according to wet sieving test DIN 53196 [1]. Product specifications
were quoted as the percentage of particles passing through a given screen mesh size. This
practice endures in modern data sheets.
For screening test purposes, a North Gauge can be used to give a comparative indication
of the quality of dispersion of the finer grades of metal pigment in a suitable medium.
The apparatus, which consists of a recessed wedge down which the dispersion is drawn,
is well known in the coatings industry.
36
Figure 4.1 Particle size distribution curve of a traditional ‘cornflake’ aluminium

flake pigment
Figure 4.2 Particle size distribution curve of a modern ‘silver dollar’ aluminium
flake pigment
37
4.1.2 Particle shape
The flake shape of most metal pigments is in contrast to the more spherical appearance
of most other colorants. This gives rise to unique visual effects, such as ‘flop’ in coatings
(see section 4.3.3).
The ‘cornflake’, whose manufacture is described in section 3.3.1, has traditional flake
geometry. Its ragged edges are caused by fracture of the flakes during milling (see Figure
4.3). The more modern ‘silver dollars’ (see Figure 4.4) and degradation resistant flakes
exhibit much more rounded edges. A comparison of the two illustrations clearly shows
these differences.
Pearlescent pigments share the same flake shape as metallic pigments. They are
distinguished by much lower opacity and in uncolored forms, much increased
whiteness. Their visual effect, as their name suggests, is of mother of pearl, rather
than a metallic sheen.
Figure 4.3 A typical ‘cornflake’ type aluminium flake pigment

38
Figure 4.4 A typical ‘silver dollar’ type aluminium flake pigment

4.1.3 Aspect ratio
Aspect ratio is defined as the ratio of the largest dimension to the smallest. For commercial
spherical pigments, the aspect ratio is therefore close to unity (see Figure 4.5). For metal
flake pigments, typical aspect ratios range from 10:1 or 20:1 for degradation resistant or
glitter flakes (see Figure 4.6), through 30:1 to 100:1 for silver dollars, to 150:1 or even
200:1 for high opacity cornflake types. The most effective method of estimating aspect
ratio is from low magnification electron micrographs.
Degradation resistant flakes were developed in response to a need for improved ‘ring
line’ stability in car plants. The ring line carries paint in a continuous loop from mixing
tank to spray gun. Paint not applied by operating the gun is returned to the mixing tank.
By maintaining the paint in motion, settlement of the heavier metal flakes in the lines is
avoided. Thicker flakes are necessary to withstand the shear that occurs in the pumps
when paint is circulated for lengthy periods.
A frequent characteristic of low aspect ratio flakes is their low concentration of flakes of
small particle size. Such flakes contribute disproportionately to opacity and appear dark.
39
Figure 4.5 Spherical aluminium pigment [1 cm = approx. 15 µm]
Figure 4.6 Degradation resistant aluminium flakes [1 cm = approx. 25 µm]
40
Their elimination helps to maintain brightness. Low aspect ratio flakes also provide
cleaner tints and softer tones when combined with pearlescent (mica) pigments [2].
4.1.4 Surface uniformity
The last feature of particle geometry, surface uniformity, refers to the degree of surface
smoothness. Although not readily measurable, an indication of surface condition is easily
gained from a good optical microscope or an electron microscope operating at low
magnification. It is a property that can be improved during pigment manufacture.
The process used for ‘silver dollar’ flakes (see section 3.3.1) provides a higher degree of
surface polish. Brush polishing in the case of dry milled flakes, or controlled mixing of
wet milled pastes will increase the degree of surface polish. The visible outcome in
application is a brighter and in the case of aluminium, whiter appearance.
4.2 Physical properties
4.2.1 Specific gravity
The term specific gravity tends to be used interchangeably with density in describing
metal pigments. Values reflect the specific gravities of the metals on which they are based,
since any coatings, such as lubricant, tend to be very thin (see Table 2.1). A test method
is described in DIN 53217 [3]. In all cases, values are greater than those of organic or
organometallic pigments. The ramifications of this are that much higher concentrations
of metal pigments are required in applications and the tendency for settlement in liquid
coatings increases.
4.2.2 Water covering area
The water coverage or water covering area (WCA) of a metal pigment is the value in
m2/g of metal, obtained by the method described by Edwards and Wray [4]. The method
is based on the fact that if the flakes in a known weight of dry flake powder are spread in
a compact monolayer on the surface of water, the area they cover is linked to the flake
thickness. The apparatus described by Edwards and Wray consists of a shallow rectangular
tray, 75 cm x 15 cm x 1.5 cm deep. Two glass sheets are used to sweep the water filled
tray to remove impurities. With one sheet at each end, a known weight of dry flakes is
gently and evenly sprinkled onto the water. One glass plate is slowly swept back and
forward, sweeping the flakes before it and gradually forming continuous film, free of
41
visible water. The exercise is repeated with the second plate, until a coherent,
monomolecular, wrinkle free film is formed. The distance between the glass plate barriers
is measured. The whole sequence is repeated until consecutive measurements are constant.
The area covered by one gram of powder is then calculated from the known weight of
powder used and the area it occupied. A skilled operator can achieve measurements
reproducible to within about 4%. Typical values range from 0.5–6 m2/g, depending on
the coarseness of the material.
A limitation of the technique is the leafing ability of the flakes. Should they become
wetted by the water, the flakes will sink and no measurement will be possible. Accuracy
may also be reduced by agglomeration of the particles. Measurement of WCA of metal
flake pigment pastes is best achieved by washing out the hydrocarbon solvents with
acetone and evaporating the residue to dryness.
4.2.3 Specific surface area
Although surface area is a parameter provided by modern laser particle size measuring
apparatus (see section 4.1.1), specific surface area (SSA) is a well-established technique
in the pigments industry in general. The so-called BET (Brunauer, Emmett and Teller)
method of measurement involves degassing the pigment surface and subsequently allowing
nitrogen gas to re-coat it. From the volume of gas produced, the SSA can be calculated,
expressed as m2/g of metal flake.
4.2.4 Heat and lightfastness
A key attribute of metal flakes as pigments is their fastness properties. Whereas organic
and inorganic pigments fade with continued exposure to light and may discolour with
heat, metal pigments, in some cases with appropriate protective coatings, are immensely
resistant. As none of the metal pigments in significant commercial use melts below 420
°C, their physical integrity will comfortably survive the highest temperatures attained in
polymer processing equipment. Visual changes that occur are associated with chemical
reactions of the metal surfaces with components of the polymers or coatings in which
they are incorporated. Gold bronze and copper have some deficiencies in this respect
above 200 °C during polymer processing, unless they are of the coated type.
Lightfastness of all metal pigments is generally good. In trials, an organic or inorganic

pigment will normally fail well before a metal pigment.
42
4.2.5 Chemical resistance
The inherent chemical resistance of the various metal pigments has been mentioned in
Chapters 2 and 3, but there are a few instances in which the metals also interact with the
polymers in which they are incorporated. Of these, PVC is the most notable. Both aluminium
and gold bronze, and indeed many of the other metal pigments, can react with the small
quantities of hydrogen chloride released when PVC is processed at too high a temperature.
In the case of gold bronze, decomposition of PVC is actually accelerated by the presence of
copper and zinc ions. In such instances, silica coated, tarnish resistant grades of metal flake
are recommended. Such grades are also specified to avoid colour shifts when gold bronze
is used in the higher melt temperature polymers. Even so, it is wise to carry out trials before
recycling reground scrap. When processing gold bronze pigments, the dwell time at the
processing temperature should not exceed five minutes. Ideally, uncoated grades should
not be allowed to exceed 190-200 °C and tarnish resistant grades 260 °C.
Polyolefin wax carried granules, formulated with aluminium flake, can be successfully
incorporated in polyacetal, providing the recommended moulding temperatures are not
exceeded. Polyacetal can be difficult to mould and also decomposes at high temperatures,
so care is needed when using it. Any formaldehyde formed by breakdown of the polymer
at high temperature will attack the metal.
Polymers with appreciable moisture content should not be co-dried with aluminium
flake powders. The combination of water vapour and elevated temperature will cause
oxidation and possible aggregation of the metal. The carrier component of aluminium
flake pigment granules generally provides sufficient protection of the metal to permit
simultaneous drying of the metal pigment and the polymer, without problems.
4.2.6 Magnetism
Of the major metallic pigments, only iron flakes are magnetic. Stainless steel flakes tend
to be of the austenitic type which have no inherent magnetism. It follows that in plastics
applications, hopper magnets used to catch ferrous contaminants must be removed or
electromagnets switched off when iron based pigments are in use.
4.3 Visual properties
Metal pigments provide unique visual effects, derived from their chemical composition
and physical characteristics. Depending on particle size and flake orientation, they can
display a smooth, lustrous and uniformly metallic finish from fine particle sizes, through
to the bright, highly sparkling finish obtained from coarser flakes.
43
4.3.1 Colour and brightness

With the exception of alloys of variable composition such as gold bronze pigments,
use of the word colour in the context of metal flake pigments is not interpreted in the
same way as for their organic and inorganic counterparts. There is no property
corresponding to colour shift, which would for example distinguish a red-shade yellow
from a green-shade yellow. Metal pigment colour is a property of the pure metal itself.
Only the cleanliness or brilliance can change, depending on particle size and its
distribution, flake shape, surface finish and concentration.
A colour shift is possible in the special case of gold bronze. A red-shade bronze results
from a high copper to zinc ratio, whilst increasing the zinc content moves the shade
towards the green. Even at a fixed ratio, it is possible to obtain a shift towards the green
or red, depending on the oxidation conditions during and after milling.
Until recently, colour measurement of metallic pigments was subjective and based on visual
comparison of coatings or mass pigmented articles by trained colour technicians. The
introduction of computerised colour measurement apparatus suitable for such pigments in
the early 1990s by such companies as Optronik, Datacolor, X-Rite and Macbeth has allowed
numeric description of colour. Figure 4.7 shows a typical printout from such a piece of
Figure 4.7 Colouristic comparison of a batch of aluminium flake pigment against its
master standard. Typical commercial tolerance is ±1 ‘L’ unit.
44
equipment. As the technology has advanced, lighter, more portable instruments have been
developed to measure colour in situ, for example on an automobile paint spraying line.
Although colour matching of solid colours is widely practised, the special properties of
metal pigments and the relatively limited size of their market has delayed the introduction
of a corresponding system for matching metallics.
4.3.2 Opacity
Opacity, also called hiding power or coverage in the specific case of coatings, refers to
the ability of a pigmented coating to obliterate a substrate or mass pigmented polymer.
After colour, it is arguably the most important property of metal pigments, due to its
large influence on formulation cost. The role of opacity in formulating is considered in
section 7.3. Here is it sufficient to mention that opacity increases with decreasing flake
size, flake thickness and specific gravity.
The property is rarely measured in absolute terms or by instrumentation. It is most

commonly compared visually with a master standard material incorporated at the same
concentration by the same technique. Measurement of the opacity of aluminium flake
pigments in printed ink films is described by Kern [5]. The relationship of opacity to
flake characteristics and flake concentration in the film is also discussed.
4.3.3 Flop
A property not available from conventional organic and inorganic pigments is variously
called ‘flop’, ‘flip’ or ‘travel’. It is the apparent change of colour depth with angle of
viewing, characteristic of all flake pigments. The effect is readily seen on any metallic
pigmented coating applied to a curved surface in sunlight. Surfaces at right angles to the
viewer appear bright. Those more parallel appear dark. The article is then said to have a
bright face and deep flop.
The origin of the effect lies in the almost two-dimensional nature of metal flakes.
When incident and reflected light incline towards the normal, the path length of the
light is minimised, as a high proportion of flakes are oriented for light reflection. The
combination of these factors provides a minimal contribution from the coloured matrix.
In contrast, at low angles of viewing, light travels between the flakes in a longer path
length. In the case of a coloured formulation, more of the colorant is seen. A deeper
shade then results (see Figure 4.8). The presence of an excessive proportion of ‘fines’
(small particle size flakes) in the coating reduces flop by reducing light transmission
45
Figure 4.8 The principle of flop
Figure 4.9 The effect of fines on flop
Fines curtail the passage of light through the film at low angles (the flop angle) and
they inhibit reflection.
through the matrix (see Figure 4.9). Thus the best flop effect is derived from pigments
with tight particle size distributions.
46
4.3.4 Leafing and non-leafing
Those metal flakes used mainly for their aesthetic effects, such as aluminium or gold
bronze, are available in two forms, called leafing and non-leafing. The terms strictly
refer only to coatings and describe the appearance of flakes in the application medium.
They are determined by the nature of the lubricant used in the manufacturing process.
Leafing pigments, as their name implies, have the ability to cover the surface of a suitable
vehicle with layers of overlapping flakes much as leaves cover the ground in autumn (see
Figure 4.10). The visual effect is of a particularly bright, continuous and uniform
reflectance. There is very little light scatter, because the flakes are almost all oriented
parallel to one another.
In the flake manufacturing process, the lubricant generally employed to make a leafing
pigment is a saturated fatty acid, such as stearic acid. When absorbed on the surface of
the flakes, it exhibits both oleophobic and hydrophobic characteristics. The degree of
leafing in any vehicle system will depend on the ability of that system to wet the flakes;
the greater the wetting, the poorer the leafing.
Solvents play a major role in developing the full leafing capability of the pigment, in
both manufacture and application. The acid functions of the lubricant react with oxide
or hydroxide groups on the metal surfaces to form a monolayer of protruding hydrocarbon
chains. The poor wetting of these chains by many application media is responsible for
what is observed as leafing. Surface tensions of solvents correlate with leafing ability.
Toluene is one of the best solvents for the promotion of leafing. For health and safety
reasons its use has given way to alcohols and esters, which are better wetting agents, but
Figure 4.10 Leafing metal flake pigment
47
poorer leafing agents. Secondary alcohols and esters have lower surface tensions than
their primary equivalents and so are less effective. Glycol ethers assist leafing because
they have high surface tensions.
As evaporation of volatile compounds takes place in a coating, convection currents are

set up. These, combined with the oleophobicity of the flake surfaces, cause them to rise
to the surface of the film. Surface tension holds the flakes in place. As further evaporation
takes place, the viscosity increases, completely immobilising the flakes and leaving a
layer of resin beneath the flake layer.
Location of the flakes at the film surface makes leafing formulations extremely difficult
to colour. The very opaque leafing film will mask any other colorant present in the
system. For this reason, leafing finishes are almost always uncolored. On the other hand,
the same interlocking orientation protects the vehicle and substrate. This almost
impenetrable film greatly inhibits the passage of moisture or oxygen. Because the flakes
are metallic, they are completely opaque to visible light and exhibit very high reflectivity
for both UV and IR radiation. These properties make leafing films especially suitable for
weather resistant and anticorrosion coatings.
The degree of leafing is measured on a scale from 0 to 100. A leafing test was developed
specifically for metal pigments and is not used elsewhere in the pigment field. Before
measuring leafing value, a test medium must be prepared according to ASTM D480-88
[6] or the related DIN 55923 [7]. This is a solution of coumarone-indene resin in mineral
spirits. It has very specific properties to ensure good reproducibility.
In the leafing test, 1.5 g, or in the case of coarse grades 3.0 g, of metal pigment are
dispersed in 25 ml of the vehicle and added to a test tube. A spatula of specified dimensions
is inserted and rotated for about ten seconds (see Figure 4.11). Immediately on removal
the spatula is suspended in a stoppered cylinder. After three minutes, two measurements
are taken. The first is the height of immersion of the spatula. The second is the height of
the bright leafing area on the spatula. The leafing value is determined by dividing the
second measurement by the first and expressing the result as a percentage. Most
commercially available metal flake pastes will have leafing values between 50 and 65%,
but exceptionally up to 95%.
The effect of the thickness of a stearic acid layer on leafing properties was investigated
by Imasoto and Suzuki [8]. They found that as the stearic acid level was increased, a
limiting concentration formed at the surface, corresponding to a trimolecular layer. The
leafing value of this material was greater than that of either a bimolecular or
monomolecular layer.
48
Figure 4.11 Leafing test apparatus
Non-leafing metal pigments are coated with oleophilic lubricants, the preferred one being
oleic acid. Unlike leafing grades, there is good wetting of each flake by the medium in
which it is incorporated. The flakes are thus dispersed uniformly throughout the coating
(see Figure 4.12). Evaporation of solvent during drying will tend to orient the flakes
more parallel to the substrate. The process is generally incomplete, so light tends to be
scattered. The visual effect is therefore sparkling rather than uniformly reflective.
In mass pigmented polymers, the terms leafing and non-leafing have no meaning. The
melt viscosity of polymers is too high to allow true leafing to take place.
Figure 4.12 Non-leafing flake pigment
49
4.3.5 Sparkle
The sparkle of a metal flake pigment is determined by its particle size and orientation.
Applied to both metal flake pigmented coatings and mass pigmented systems, the term
describes the ability of flakes to reflect light in a non-uniform manner. Flakes that all lie
parallel to one another, as in the case of leafing pigments in a coating, will reflect incident
light at the same angle. They therefore appear continuously, uniformly brilliant and
exhibit no sparkle. Where flakes make a more random angle with the substrate, as in a
non-leafing coating, a proportion will be oriented in such a way as to reflect light falling
on their flat surfaces into the eye. Such flakes appear brighter than their neighbours. It is
these pinpoints of light that collectively provide sparkle.
Particle size is relevant because flakes need to be greater than 30 µm median diameter to
be visible to the naked eye. Smaller flakes will show negligible sparkle, irrespective of
their orientation, unless subject to high light levels.
There is no commercial apparatus for accurately measuring sparkle or providing numerical

comparison of samples exhibiting different levels of the property. It is another property
determined by comparison with a master standard, a task for the experienced metal
pigment technician.
4.3.6 Distinctiveness of image
The next property to be considered, called distinctiveness of image (DOI), provides what
is currently the closest approach to the measurement of sparkle. DOI is another property
specific to metal flake pigmented coatings. Whereas gloss describes how much incident
light is reflected from a coating surface, DOI refers to the uniformity of that reflection.
Gloss is controlled by the nature of the coating as well as the pigmentation. DOI is
influenced by flake orientation and particle size. Very random orientation and large
particle size flakes will generate poor DOI.
The property is measured by allowing light to shine through text of decreasing point size
onto a metal pigmented coating (see Figures 4.13 and 4.14). The text is read by reflection
from the surface of the coating until it can no longer be distinguished. A numerical value
between 0 and 100 is assigned on an ascending scale corresponding to increasing DOI.
50
Figure 4.13 Apparatus used to measure distinctiveness of image. Part of the paint
panel whose DOI is being measured is visible below the light box
Figure 4.14 Text screen from the DOI apparatus of Figure 4.13. It lies horizontally in
the base of the light box, below the lamp
51
4.4 Glitter flakes
The production process described in section 3.8 provides cut foil glitter flakes of regular
geometry (see Figure 4.15). As mentioned previously, the hiding power of a flake decreases
as its size increases. Eventually, the flakes are so large that even when incorporated in a
polymer at a loading of several percent, there is a negligible contribution to opacity. In
such cases, the visual appearance is of sparkling reflection of light from randomly oriented
flakes, i.e., a glitter effect.
The wet milling process described in section 3.3 can also be used to generate large flakes.
Median particle diameters in the range 100 to 600 µm are feasible, but flake shape will
never match the geometric regularity of cut foil grades. The process can however generate
lower aspect ratios. Thicker flakes are necessary to withstand processing without bending
or fracturing. Such a process can be operated more economically than that used for cut
foil glitter, especially at the low particle size end of the spectrum.
The apparent limitation of lack of geometric regularity is not a constraint in practice, as

the eye is not easily able to detect the difference in particle shape up to about 300 µm. It
is the light reflecting ability of the flake that appears to be the important factor. For an
Figure 4.15 ‘Glitter’ flake obtained by cutting aluminium foil [1 cm = approx. 50 µm]
52
equivalent visual effect, it is generally necessary to use a wet milled flake of a rather
greater diameter than a cut foil square. This is effectively because a disc has a lower
surface area from which to reflect light than a square of the same width.
The popularity of glitter flakes at low concentrations to provide sparkle in coloured

polymers may be due in part to the observation that such formulations are virtually free
of the flow line visibility problems discussed in Chapter 8. The flakes have such a low
opacity and are so separated from each other that shadows between flakes are eliminated.
References
1. DIN 53196
Testing of Pigments: Determination of Residue on Sieve Using Organic Solvents
as Washing Liquid.
2. Y. Imasato and M. Suzuki, inventors; Asahi Kasei Metals Ltd., assignee,

European Patent 0451785 B1, 1991.
3. DIN 53217
Determination of Density of Paints and Varnishes and Similar Coating Materials
Part 1: Survey of Test Methods
Part 2: The Pyknometer Method
Part 3: The Displacement Float Method
Part 4: The Hydrometer Method
Part 5: The Vibration Method
4. J. D. Edwards and R. I. Wray, Aluminium Paint and Powder, 3rd Edn., Reinhold
Publishing Corporation, New York, USA, 1955, 16-22.
5. G. M. Kern, et al., American Ink Maker, 1991, 69, 10, 60.
6. ASTM D480-88
Standard Test Methods for Sampling and Testing of Flaked Aluminium Powders
and Pastes.
7. DIN 55923
Pigments; Aluminium Pigments and Aluminium Pigment Pastes for Paints;
Technical Delivery Specifications.
8. Y. Imasoto and M. Suzuki, Kotingu Jiho, 1991, 190, 19, in Japanese.
53
5
Delivery Forms
This chapter considers the forms in which metal pigments are sold by their
manufacturers. It also describes the processes by which they are customised by those
who purchase them for onward sale to an end user. Metal pigment manufacturers
typically add value by supplying the metal in a form compatible with the end use. This
specialisation has spawned an enormous number of variants, falling into eight broad
categories as follows.
5.1 Dry powder
Although dry powder is still sold, its market share is steadily declining, as safer and
more environmentally friendly delivery forms evolve. For safety reasons, dry powder
is sold in steel drums. Steel drums are less easily damaged than paperboard cartons
and without the electrostatic hazard of plastic containers. Aluminium flake powder
packaging must in particular retain the powder, even if roughly handled, as escaping
powder, apart from being contaminating, is an explosion hazard. A greater percentage
of gold bronze than aluminium is still sold in dry form, since bronze is both less
combustible and less dusty due to its greater density. Dry powder is used in both coatings
and mass pigmented systems. Its popularity in the latter is additionally limited by its
poor wetting characteristics. For this reason it is sometimes damped with plasticiser by
the manufacturer or end user before incorporation in polymer.
5.2 Paste
Pastes have the consistency of butter and contain 60-90% metal, the exact percentage
depending on metal density and particle size. The balance of the paste is solvent. Again
the product is normally supplied in steel drums.
The high volatile content makes the paste form unsuitable for the mass coloration of
polymers. Solvent volatilises in the injection moulder or extruder barrel and cannot be
adequately removed, even from vented extruders. Mouldings and extrusions are highly
vesicular, covered in surface craters, resulting in an unacceptably poor surface finish.
55
Pastes are however the traditional delivery form of metal pigments destined for surface
coatings. Products intended for solvent-based automotive paints are generally sold in the
white spirit of manufacture, blended with an aromatic hydrocarbon of similar boiling
point to improve solvency in the application system. Variants targeted at the inks market
have ‘faster’, i.e., more volatile solvents. These avoid the slow drying and residual odour
problems associated with traditional hydrocarbon pastes in this application. Lower esters
and ketones, such as ethyl and propyl acetate and MEK are common. These have no active
oxygen atoms to react with aluminium. Lower alcohols and ether-alcohols are also used.
Aluminium pastes in isopropyl alcohol are commercially available. Contrary to expectation,
such pastes are fairly stable, implying that such alcohols have some passivating action.
These pastes are also useful in water dilutable systems, since they are water compatible.
Recent technical advances have produced aluminium flake pigments passivated against
reaction with water. The various chemistries involved are listed in section 12.6. Such
products are normally also offered as pastes in water miscible solvents.
Water-based aluminium pigment pastes are also available, although there is some unease
about their widespread introduction due to the unpredictable nature of the gassing reaction
and the risk and financial consequences of any incident. It is more likely that solid,
granular forms will become the norm in this market.
In handling pastes containing faster solvents, it is important to keep the container well sealed
when not in use. Any paste that dries out causes the flakes to aggregate. The paste is then
very difficult to reconstitute. Appearance becomes gritty and the opacity is greatly reduced.
This is another reason why in the longer term, granular product forms may predominate.
5.3 Dispersion in resin and solvent
A dispersion of metal pigment, not in solvent alone, but in a low viscosity resin solution,
constitutes a part finished paint or ink. A patent application by Eckart-Werke describes a
process for preparing such a product form by milling in the presence of resin and solvent in
the ball mill [1]. No fatty acids are employed. The products are directed to printing inks.
Resin dispersions are not universally popular with coatings manufacturers as they are
perceived as denying them formulating flexibility and an opportunity to add value.
5.4 Plasticiser dispersions
Though appropriate for coatings, as noted previously, solvent-containing delivery forms

are unacceptable for mass pigmentation of polymers. Even low boiling point solvents cannot
56
Delivery Forms
be adequately removed by the heat of polymer processing. Indeed overpressurisation of

barrel and screw by volatilised solvent can be potentially dangerous. Replacement of the
solvent component of pastes by a non-volatile liquid eliminates this danger.
After dry flakes, the next delivery form specifically for metallic pigmentation of polymers
is the plasticiser dispersion, introduced in the 1950s. Unlike solvent, the liquid plasticiser
is sufficiently high boiling to remain in the processed polymer. Heat stability is nevertheless
limited, making them inappropriate dispersions for the highest melting polymers.
A further drawback of plasticiser dispersions is their lack of versatility. Thus whereas

dry flake pigments can be incorporated in most polymers, albeit with difficulty, plasticiser
dispersions are more polymer specific. Typical types in current use include phthalate
esters, such as di-octyl phthalate (DOP) and di-isodecyl phthalate (DIDP) for rigid and
flexible polyvinyl chloride (PVC), PVC plastisols and styrenics. Mineral oil is a popular
choice for the polyolefin group, the more so because grades suitable for direct food
contact are available. Polyolefins processed with high concentrations of mineral oil pastes
can be prone to screw slip.
Concern over the toxicity of phthalates is prompting a search for substitutes (see section
16.1). Adipates and sebacates are contenders despite higher cost.
5.5 Granules
The logical development of the plasticiser dispersion is the granule (see Figures 5.1 and
5.2). It consists of a high concentration of metal pigment, generally 70-90%, immobilised
by solid carrier resins and/or polymers. It may be regarded as a concentrated masterbatch,
but as it is not manufactured by the conventional masterbatch technique, it should more
properly be called a colour concentrate.
Introduction of metal pigment granules was pioneered by Silberline in the 1980s. Kern [2]
claimed a specific composition for the mass coloration of polymers. The products, which
took the trade name SILVET®, were combinations of terpene resin, a low density polyethylene
and a metal flake pigment, preferably aluminium. The function of the terpene resin was to
prevent the agglomeration of aluminium flakes which otherwise took place over time.
A more broadly based patent was obtained by Wheeler [3, 4]. Low- or non-dusting,
essentially non-volatile metal pigment granules were derived from a process which
combined metal pigment, carriers and solvents. Either the mixture was formed into
granules or alternative shapes and the solvent removed, or vice versa. Depending on the
nature and concentration of the carrier, the products of the invention are used in water-
and solvent-based paints and inks and in mass pigmented plastics.
57
Figure 5.1 Granular form of metal flake pigment
Figure 5.2 SILVET® aluminium flake pigment granules [13 x actual size]
Typical granules are cylindrical with a length of 3-15 mm and diameters of 3-6 mm.
They offer several advantages over all the foregoing product forms. Chief amongst these
are colour quality, safety and ease of handling. Unlike conventional masterbatch
preparation (see section 5.6), SILVET® is manufactured by a low shear process. This
maintains all the brightness and reflectivity of the original flakes.
Granules are free flowing and low- or non-dusting. It follows that as well as being safe to
handle, they can be easily metered in modern, automatic dosing equipment. This is a
particularly useful feature in mass pigmentation of polymers, since it may avoid the need
for an intermediate masterbatching or compounding stage. As granules are solvent-free,
there is no possibility of them drying out in storage, with consequent loss of dispersibility.
58
Delivery Forms
Carrier resins are chosen for compatibility with the intended end use, be it inks, paints or
mass pigmented polymers. Those selected for polymer coloration generally have lower
melting points than the polymers into which they are incorporated. This ensures that
they melt and coat the polymer pellets before the pellets themselves melt. In this way, an
excellent dispersion can be achieved without the use of high shear forces.
Carriers for solvent-based ink and paint grades are synthetic aldehydes, ketones, acrylics,
or less commonly, hydrocarbons or coumarone-indene resins. For water-based coatings,
Silberline’s Aquavex ‘S’ and ‘P’ ranges, featuring surfactant and polypropylene glycol
carriers, are widely used for inks and paints, respectively.
5.6 Dry masterbatch
A masterbatch, otherwise known as a colour concentrate, is intended for dilution with

uncolored (‘virgin’ or ‘natural’) polymer prior to conversion. Loadings of 20-50% are
common in the industry, the balance being made up of other colorants, universal or
polymer-specific carriers and various additives, such as antistatic or flame retarding agents.
Typical metal pigment masterbatch concentrations are 1-5% w/w on polymer, the exact
level being heavily dependent on the pigment’s particle size, density and concentration in
the masterbatch.
Masterbatch is divided into dry and liquid types. The latter is small in relation to the
former. As entry barriers were low and distribution tended to be localised, there were
until recently a large number of masterbatch makers, over 200 in Europe alone. More
recently that number has reduced through acquisitions by the major players. Pan-
European converters are increasingly looking for pan-European suppliers who can
provide a local supply, technical support and innovation via local subsidiaries. The
total Western European masterbatch market in 1996 was estimated at 550,000 tonnes,
worth around £1 billion, the majority being white and black [5]. The metallic pigmented
sector probably accounts for less than 1% of the total, but is growing rapidly. So also
is masterbatch in general, mostly at the expense of compound. Masterbatch coloration
of previously difficult polymers such as acrylonitrile-butadiene-styrene (ABS) has become
much more reliable.
5.7 Liquid masterbatch
As the name implies, liquid masterbatch consists of colorants and optionally additives,
incorporated in liquid carriers to give a fairly viscous pre-dispersion. The carrier, which
is incorporated in the polymer, is often a plasticiser.
59
Liquid masterbatch is added to the polymer by dosing pumps. Given suitable equipment,
the technique allows very accurate addition levels and a high level of dispersion. Early
drawbacks in clean down (the displacement of a (coloured) polymer from the equipment
by using another polymer or else allowing it to run out) and colour change have also
been largely overcome.
Metal pigments present some difficulties, due to the combination of particle size and
density. These conspire to induce settling in transit and in delivery lines. Nevertheless,
lighter flake pigments such as aluminium are successfully used in smaller particle sizes.
5.8 Compound
Compound, in this context, describes the combination of polymer and pigment (and
possibly other performance enhancing additives in proportions such that the resulting
mass is converted without further dilution into a finished article. As in masterbatch, the
manufacturer may add antistatic or flame retarding agents, UV stabilisers and the like.
For inexperienced converters, the use of compound gives fewest problems. All the work
necessary to control colour, dispersion and other application characteristics has already
been done. The main disadvantage is cost, though this is mitigated by the fact that
compound producers also tend to be primary polymer producers. They therefore have
the advantages of scale.
The compound market in Western Europe is around three times that of masterbatch.
Coloured compound production in 1996 amounted to over 1.5 m tonnes [6]. Again,
metal pigmented compound has a very small, but growing market share. Key players are
GE with their Magix range and DSM with Fantasy Colours.
A potential disadvantage of using masterbatch or compound is that when the metal flake
pigment appears in the final application, it will have been subjected to two potentially
severe dispersion regimes. The first is to prepare the compound or masterbatch, the second
to incorporate it in the finished article. Direct use of metal pigment granules reduces
dispersion energy encountered by the flakes during incorporation, thereby maintaining
metallic brightness. If the dispersion energy is too vigorous, flake damage results.
60
Delivery Forms
References
1. Eckart-Werke, assignee, International Patent Application WO 94/28087, 1994.
2. G.M. Kern, inventor; Silberline Manufacturing Company Inc., assignee, US

Patent 4,544,600, 1982.
3. I. R. Wheeler, inventor; Silberline, Limited, assignee, European Patent 134676B1,

1984.
4. I. R. Wheeler, inventor; Silberline, Limited, assignee, US Patent 4725317, 1986.
5. Plastics and Rubber Weekly, 1998, No.1750, 7.
6. Thermoplastic Compounding Industry in Western Europe, Applied Market

Information Ltd., Bath, 5th Edn., 1997.
61
6
Comparison of Mass Pigmentation and Coating
Mass pigmentation is the incorporation of the pigment in a molten polymer mass

during processing into compound or masterbatch, or when an end user or converter
prepares a finished article, for example an injection moulding. There is growing
interest in replacing coatings by mass pigmentation. There are several reasons for
this and in the following sections the advantages and disadvantages of the two
techniques are compared.
6.1 Advantages of coating
The two key advantages of a metallic coating over a mass pigmented equivalent are
reflectivity, i.e., brightness or brilliance, and the potential uniformity of the coating. Use
of the word potential is deliberate since poor application techniques can still cause surface
blemishes requiring expensive repair. The appearance of metallic pigmented coatings is
additionally influenced by the manner in which the flakes lie down in the dry film. If this
is not uniform, the overall effect can appear mottled.
6.1.1 Brightness
The issue of brightness or brilliance of metallic effect is one of the few in which coating
has a very distinct advantage. This arises from the orientation differences between flakes
in a coating and those in a polymer mass.
A large proportion, sometimes over 80% by weight of a liquid surface coating is solvent.
When applied to a substrate, the orientation of metal flakes will be somewhat random.
As solvent evaporates, film thickness is reduced. This forces the flakes into an orientation
broadly parallel to the substrate surface, because the flake diameter is comparable to the
film thickness (see Figure 6.1). The result is a high proportion of flakes with their large
surface oriented parallel to the substrate. They are therefore capable of maximising light
reflection. In practice, flakes do not lie exactly parallel. An angle up to about 10° with
respect to the substrate is common. This is sufficient to scatter light and provide the
sparkling effect characteristic of metallic painted automobiles.
63
Figure 6.1 The influence of solvent evaporation on flake orientation in a dry coating
In contrast, a metallic flake pigmented injection moulding melt generally has limited
flake orientation. Unless there is a mechanism to improve alignment of flakes parallel to
the polymer surface, such as the biaxial stretching of polymer film, light reflection from
these randomly oriented flakes will be lower.
6.1.2 Colour uniformity
Almost irrespective of the method of application to a polymer substrate, a metallic coating

exhibits uniformity of visual effect across the coated surface, providing it has been properly
applied. Any visible imperfections of the substrate, such as flow or weld lines are obliterated.
The best results are obtained by spraying or printing. Dipping is less satisfactory and the
only real exception is brushing. Unless care is taken to ensure that brush strokes are all in
the same direction, the result can look mottled. This is most acute with self-colours based
on fine particle size flakes. It is seldom a problem with deep shades, such as black, hammer
finishes, where other pigments provide the majority of the necessary opacity.
6.1.3 Flop
Flop is a phenomenon characteristic of all lamellar particles including metal flakes. The
observed effect is a change of colour with the angle of viewing. Its origin and effects are
discussed in section 4.3.3. Here it is only necessary to note that it is characteristic of
coatings which cannot be accurately replicated by a mass pigmented system. Stylists
regard flop as a desirable property, that enhances the appeal of coatings.
64
6.1.4 Application temperature
For pigments that will not withstand polymer processing temperatures, coating may be the
only suitable technique. Many organic pigments have insufficient heat stability. Those that
do, tend to be much more expensive than their coating counterparts, thereby incurring a cost
penalty. The temperature stability of metallic pigments is not generally a problem. Unless
surface modified, they have the thermal properties of the metals themselves. An exception is
gold bronze, which has limited stability in high melting polymers (see section 4.2.4).
6.1.5 Vacuum metallisation
Although strictly outside the scope of this book, vacuum metallisation must be mentioned
as it is a coating providing the ultimate in metallic reflectiveness. The technique involves
allowing vapourised metal to impinge on an article in a high vacuum. The coating thickness
is very low, being of the order of tens or a few hundred nanometres. Uniformity of finish
is dependent on the surface contours of the article, as metal deposition faithfully follows
its contours. Its quality cannot be matched by either a metallic coating or mass
pigmentation. This very high reflectivity is harnessed in metal pigments, vacuum deposited
onto a release film and subsequently disintegrated to flakes. The technique is described
in section 3.7.
Vacuum metallisation is expensive, due to the high construction and operating costs of a
large, high vacuum chamber. Nevertheless, it is used where maximum reflectivity is essential.
6.2 Mass pigmentation advantages
The advantages of using a mass pigmentation route over a coating route divide into
colouristic, processing, environmental, legislative and cost issues.
6.2.1 Depth of coloration
Coloration throughout a mass pigmented article is preferable to a relatively thin surface

coating that can chip or delaminate to expose the often contrasting colour of the polymer
substrate. This is a particularly important consideration in the manufacture of automotive
lower body parts such as wheel and body trims.
Mass pigmentation may also have advantages for complex moulded shapes, for example,
where a sprayed coating cannot evenly fill recesses. The reverse is the case if the part
65
requires tool inserts or sudden changes of thickness. Here the presence of flow and weld
lines will disfigure the surface and a more uniform effect can be achieved by coating.
Methods of reducing or eliminating flow and weld lines are described in chapter 8.
6.2.2 Single stage versus multi stage processing
The main processing issue relates to the number of stages involved in the two techniques.
Painting requires careful preparation of polymer substrates that in some cases are difficult
to wet. This is particularly true of low energy surfaces such as polyolefins. Flame or
chemical treatment may be required to activate the surface sufficiently to give adequate
adhesion of the subsequent coating. A considerable technology, involving silane, titanate
and zirconate bonding agents has grown up to address this problem. In this area, Kenrich
Petrochemicals Inc., [1] is both a prominent supplier and provider of formulation guidance.
In the case of metallic pigmented paints, there will usually be two coats; a basecoat of
10-20 µm in thickness, containing the metal pigment and a 30-50 µm thick clearcoat to
provide protection. In contrast, mass pigmentation is achieved simultaneously with
polymer processing in a single step.
6.2.3 Environmental and legislative pressures
Environmental constraints are increasingly being attached to solvent emissions and the
laundering and disposal of paint residues. The most significant recent legislation is the
proposed EC Solvents Directive [2]. This suggests that the contribution of solvent use to
the 12 million tonnes per annum of volatile organic compound (VOC) emissions in the
EC is around 30%. VOCs would have to be reduced by 70-80% from 1990 levels to
bring atmospheric ozone levels down to acceptable levels for the long term.
Disposal of solid paint residues by landfill now incurs an additional tax, calculated by
weight. The tax rate is likely to increase in real terms to encourage recycling schemes.
Legislation is likely to tighten further in the future. Though there are moves towards
water-based coatings, the capital costs of corrosion resistant plant are high. In contrast,
mass pigmentation has negligible emissions. In most cases there is also no waste disposal.
Sprues, runners and flawed mouldings or extrusions can be ground up and recycled, in
either the same or a different product.
66
6.2.4 Cost
This is arguably the most important factor in today’s highly competitive marketplace.
The capital and operational costs of paint application lines and drying tunnels are
considerable. Repair of blemishes in the paint film, by rubbing down and re-coating, is
labour intensive and therefore also expensive. Anecdotal evidence suggests that up to
40% of the cost of a moulded item such as a television cabinet or car wheel trim is
associated with the painting operation.
Against this background it is not difficult to see why mass pigmentation is gaining ground.
This trend would have been more rapid but for the difficulty of matching the appearance
of a painted part by mass pigmentation. The painted part always looks brighter for the
reasons given in section 6.1.1. The extent to which the gap can be closed by optimising
the formulation and incorporation of metallic, mass pigmented polymers is covered in
Chapter 9.
Where a coloured metallic effect is required, the cost advantage of mass pigmentation is
reduced by the use of generally higher cost organic pigments with sufficient heat stability
to survive processing.
References
1. Ken-React Reference Manual, Kenrich Petrochemicals Inc., Bayonne, New Jersey,

USA, 2nd Revised Edition, 1993.
2. Proposed Council Directive, Commission of the European Communities,

COM(96) 538 Final; 96/0276 (SYN), November 1996.
67
7
Mass Pigmentation Application Characteristics
This chapter looks at the effect of the inherent properties of metal flake pigments, described
in Chapter 4, on mass pigmented systems. The term ‘mass pigmentation’ encompasses
all the processes by which metal flakes are combined with polymer to ultimately form a
finished article. Of these techniques, injection moulding is the most technically challenging,
because it has the most variables requiring control.
7.1 Colour
As discussed in section 4.3.1, colour in the context of metal pigments generally means
brilliance, otherwise referred to as brightness. It broadly corresponds to cleanliness in
organic pigments. Metallic colour is influenced by the surface finish of the pigment, its
tint strength (see section 7.3) and its concentration. In the specific case of aluminium
pigments, improved colour equates to increased whiteness. These properties are in turn
dependent on the particle size distribution and the surface smoothness of the flake.
There is a complex relationship between colour, particle size, opacity, loading and cost.
This is summarised in section 7.7, after these factors have been considered individually.
7.2 Dispersibility
The process of dispersion starts with a combination of metal flake and polymer in the
dry state. The hazards of blending dry aluminium flake with polymer are sufficiently
well known for this practice to have given way to masterbatch pre-blending. Masterbatch
in this context covers metal flake pigment damped or carried by any suitable organic
material, such as a plasticiser or a polymer.
A short period of dry tumbling, for example in a double cone blender, should be sufficient
for most commonly available aluminium pigment masterbatches. High speed powder
blenders are not recommended for two reasons. Firstly, there is a danger that the high
shear will break down the masterbatch, releasing single flakes with a consequent danger
of explosion. Secondly, the same high shear can bend or break the flakes, leading to a
loss of metallic brightness.
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For most applications, it is not necessary to pre-dry aluminium flake masterbatches.

Where polymers are routinely dried, the masterbatch-polymer premix may be dried
together, unless the masterbatch carrier becomes molten at the drying temperature.
Most metal flake pigments are very resistant to heat. The flakes themselves remain stable
well above the highest polymer processing temperatures. In practice, the maximum
processing temperature is often dictated by either the masterbatch carrier or the polymer.
7.3 Opacity and tint strength
Opacity or hiding power is a function of flake diameter, thickness and the density of the
metal. At constant thickness and density, opacity is roughly proportional to the inverse
square of the diameter. The smaller the diameter and/or thickness, the greater the number
of flakes per unit weight and the higher the total surface area. With more surface area
available to obliterate the substrate, opacity is higher. This relationship is explored further
in section 7.7.
Tint strength refers to the ability of a metal pigment to modify the colour depth of a
colorant with which it is incorporated. Thus, a deep blue metallic effect will become
paler if further metal flake pigment is added to the formulation. ‘White’ pigments such
as aluminium will cause little change in hue. Gold bronze moves the effect towards the
green. A fine particle size flake will create a greater colour shift than the same weight of
a coarser flake.
Increasing the flake thickness, i.e., reducing the aspect ratio, is practised to improve
degradation resistance. It is inevitably at the expense of opacity. Flake damage can have
an ambivalent effect on opacity. On the one hand, folded and bent flakes have reduced
effective surface area. On the other hand, if the flakes become thinned and break, effective
surface area is increased. This is however accompanied by loss of brightness, due to both
the increased concentration of fine particles and the disruption of uniform orientation
caused by bent and folded flakes.
Loss of opacity becomes very marked at large particle diameters. For this reason, very
large aluminium flakes are generally used to provide a random sparkle effect in
combination with other colorants.
The large density range encountered with metal flakes greatly influences opacity. About
two to three times as much gold bronze as aluminium flake of comparable geometry
would be required for equal opacity. The relatively low density of aluminium is
undoubtedly a contributing factor to its popularity.
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Pigment concentration or loading is determined by the visual requirements of the

pigmented article. It is also likely to be linked to whether opacity is essential, desirable
or irrelevant. Commercial concentrations of metal flake pigments are much higher
than organic or inorganic colorants. Even the finest metal flake can require 0.2% or
more to make a 1 mm thick section of transparent polymer opaque. Larger flakes need
considerably more, so that in practice, concentrations of 1-4% are common. Organic
and inorganic pigments tend to be used at around a tenth of these levels, due to their
much smaller particle diameters, as well as higher inherent tinctorial strength.
7.4 Orientation
For a metal flake pigment, orientation influences brightness and to some extent opacity.
The terms ‘leafing’ and ‘non-leafing’, so relevant to coatings (see section 4.3.4), have no
relevance to mass pigmented polymers because the melt viscosity is too high for leafing
to take place. Flakes that reflect light from the full area of their faces appear very much
brighter than flakes presenting their edges. In mass pigmented articles, orientation is
determined by polymer flow characteristics. Flakes tend to align themselves to reduce
their resistance to flow.
7.5 Mechanical properties
Metal flakes in polymer melts tend to cause an increase in viscosity if added as dry flake.
This is attributed to poor wetting of the flake surface. In elaborated products, such as
plasticiser dispersions and granules, the carrier can have a more marked effect than the
metal flake itself. Many carriers have a lubricating action, which serves to decrease the
melt viscosity and therefore increase the melt flow index.
Low loadings of metal flake pigments in polymers generally cause a very little change in
tensile and impact strength. Indeed in certain polymers, particularly polyolefins, these
properties may be enhanced.
Tables 7.1 to 7.7 show the effects of including granular aluminium flake pigments in a
range of common polymers at loadings between 0.5 and 6% by weight of polymer. A
number of conclusions can be drawn. For example, the degree of mechanical strength
loss is broadly proportional to metal flake loading. Larger flake particle sizes are less
prone to strength loss, whilst the more polar polymers, such as ABS and polyamide,
show the greatest percentage loss at higher loadings.
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Polyolefins exhibit the best mechanical property retention. This may be because the thin
fatty acid lubricant coating on the flakes has a largely hydrocarbon structure, similar to
that of the polymer. This would be expected to enhance chain entanglement in the melt.
However, even in polyolefins, mechanical properties are usually reduced at higher loadings.
Table 7.1 Percentage change in mechanical properties as a result of

pigmentation of PP by aluminium flake pigment granules
Metal particle size Metal % Tensile break Elongation
10 µm 0.7 -4 -42
1.4 -5 -47
2.8 -5 -63
5.6 -6 -86
30 µm 0.7 -1 -38
1.4 -2 -65
2.8 -3 -67
5.6 -4 -79

pigmentation of elastomer modified PP by aluminium
flake pigment granules (NC = no change)
Metal particle Metal % Impact Tensile Elongation
size strength break
1 0 µm 1.0 +15 NC -23
1.5 +24 NC -64
2.0 +29 +4 -76
3 0 µm 0.5 -5 +4 -63
1.0 -4 +1 -51
1.5 -5 -1 -61
2.0 NC -2 -59
7 5 µm 1.0 -20 +1 -59
1.5 -26 +3 -69
2.0 -34 +4 -74
3.0 -36 +1 -75
4.0 -30 +4 -74
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pigmentation of high impact PS by aluminium flake pigment granules
(NC = no change)
size strength break
36 µm 1.0 NC -8 -25
5.0 NC -11 -30

pigmentation of crystal PS by aluminium flake pigment granules
size strength break
10 µm 0.7 -38 -13 -64
1.4 -13 -21 +62
2.8 -21 -20 +136
3 0 µm 0.7 -17 -16 -4
1.4 -18 -18 +22
2.8 -3 -20 +64
5.6 -14 -22 +118
75 µm 0.7 -18 -12 -18
1.4 -24 -12 -16
2.8 -5 -14 -6
5.6 -2 -23 +12

pigmentation of ABS by aluminium flake pigment granules
size strength break
36 µm 0.7 -20 -2 -52
3.5 -60 -4 -56
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pigmentation of polyamide by aluminium flake pigment granules
size strength break
3 0 µm 0.7 -27 -2 +4
2.8 -34 -5 +2

pigmentation of plasticised PVC by aluminium flake pigment granules
Metal particle size Metal % Tensile break Elongation
10 µm 0.7 -8 -3
1.4 -7 -4
2.8 -7 -5
5.6 -7 +3
Figure 7.1 Electron micrograph showing capillary channels at a fracture surface

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Microscopic examination reveals the reasons for loss of mechanical properties. Figure
7.1 is an electron micrograph of the fractured surface of an impact test specimen pigmented
by metal flake. The lack of bonding between the metal flake and the polymer matrix is
clearly visible.
At least part of the reason is believed to be the difference in the coefficients of thermal
expansion of metal and polymer matrix. Thus, as a pigmented polymer cools from the
melt phase, differential shrinkage occurs. Unless there is efficient bonding between metal
and matrix, capillary channels are formed as in Figure 7.1.
These interfaces are sites of mechanical weakness, allowing crack propagation to take
place more readily. The result, at a sufficient flake concentration, is the observed reduction
in mechanical properties, particularly impact strength.
7.6 Cost
The cost of a metal pigment in a formulation depends upon the metal concentration in
the pigment, the loading and the unit price. Unit prices for both aluminium and gold
bronze pigments are comparable with the least expensive classical organic pigments.
Although comparably priced at the commodity end of the market, the range of aluminium
pigment prices reaches a ceiling well above that for gold bronze. Cost in use has to take
account of the greatly reduced tinting strength of metal pigments, controlled by their
density and particle size. As described in section 7.3, loading has an inverse relationship
with particle size. The unit cost of the pigment is less influenced by particle size than by
the tightness of the particle size distribution and by its colour. Particle size only influences
cost in the respect that from any given starting atomised powder, finer particle size grades
tend to be derived from a longer and therefore more costly milling regime.
A tight particle size distribution implies that more of the milled product is rejected at the
screening stage. Thus the process yield is low. Pigment colour is improved by a slower
speed, more gentle milling action and a reduced metal charge in the mill. If taken with a
low process yield, the result is an increase in unit production costs that have to be recovered
by a higher selling price.
Dry granular forms attract a further price premium for their handling advantages. This
helps to offset their production costs, which are inevitably higher since granules are derived
from pastes. Compared at equal metal content, the granule must bear the higher unit cost
of carrier compared to solvent, plus the extra processing costs associated with granulation
and drying. In coating systems, the carrier is generally also a film former. Its use reduces
the amount of solid binder required, which in turn offsets the higher cost of the granule.
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7.7 Interrelationships
The complex relationship between colour, particle size, opacity, loading and cost referred
to in section 7.1 is illustrated for aluminium flake pigments in Figure 7.2. The y axis
displays some measure of colour (brilliance). Pigment concentration (loading) is plotted
on the x axis. Small, medium and large median particle size grades are displayed.
Figure 7.2 Relationship between colour, particle size, opacity (decreases with
increasing particle size), loading and cost
The smallest particle size material with its high opacity requires a low concentration to
reach colour saturation, defined as the point at which even with increased pigment loading,
no further increase in brightness is obtained. A medium particle size grade requires a
higher loading to attain saturation, but the colour at that point is brighter. The same
applies to the coarsest grade. Cost also increases with loading, so in practice, cost-effective
formulating demands that a compromise be reached.
Although generally less expensive per unit weight than organic or inorganic colorants
sold for mass pigmentation of polymers, metal pigment loadings can be five or ten times
higher. Coloured metallic formulations may contain large flake grades which are more
cost-effective. The colorant can provide the opacity that the large flakes lack.
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The foregoing relationships may be summarised as follows:
Fine particle size Coarse particle size

Dark colour and less bright White colour and increased brightness
High opacity Low opacity
Low sparkle High sparkle
0.25%-1.5% loading 1.5%-5% loading
Low cost in use High cost in use
7.8 Compatibility
The metals used as metallic pigments are compatible with most polymers, however there
are a few combinations to avoid. No pigments except tin have any problem with heat
stability at normal thermoplastic moulding temperatures.
Aluminium pigments can react with PVC at high temperatures. The metal does not appear
to promote polymer decomposition but will react with the hydrogen chloride breakdown
product. In the case of polyacetal, generation of formaldehyde at high temperatures does
appear to be exacerbated by the presence of the metal. In both cases, processing is
successful if normal operating temperatures are not exceeded. Lead stabilisers should be
avoided, as they reduce the metallic effect. Tin stabilisers are satisfactory.
When incorporating high loadings of aluminium or gold bronze flake into polyolefins,
for example when preparing masterbatch, an unpleasant smell can be caused by
decomposition of the fatty acid lubricant on the flakes. This can be eliminated by addition
of antioxidants. Only 0.1-0.2% is generally necessary. A 1:1 combination of Irganox
1010 (Ciba) and MD 1024 (Ciba) is a popular choice.
Gold bronze also presents some challenges when used with polyolefins (generally processed
at lower temperature). At high temperatures the polymers become oxidised and brittle if
processed with copper, either as copper flake itself or from that present in gold bronze.
Surface coated grades, such as the Tarnish Resistant range from Wolstenholme
International, provide improved stability. Ideally, however, articles in which strength is
important and/or which are intended for extended service should not be pigmented with
copper-containing pigments. Alternatively, an aluminium flake with a red shade, yellow
colour or an orange organic pigment could be used to achieve gold shades.
Other instances of incompatibility are a consequence of the nature of the carrier. It is one
of the few merits of dry metal flakes that such compatibility issues do not exist. In all
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other product forms, such as plasticiser dispersions and granules, some constraints apply.
The historically popular phthalate ester carriers are most compatible with PVC and
styrenics. Mineral oil types are best restricted to polyolefins, not so much because of
chemical compatibility as limited heat stability. Processing with mineral oils above 250 °C
is not recommended. Similarly, phthalate esters begin to degrade above about 260 °C.
This precludes the use of such materials in the newer engineering polymers.
Commercially available granules generally have modified polyolefin carriers, stable to

around 300 °C. They do not have truly universal compatibility, but do find use in all the
common polymers, including styrenics, polyolefins, polyesters, polyurethanes, polyamides,
polycarbonate, acrylics and polyacetal. Of the common polymers only PVC and ethylene-
vinyl acetate copolymer (EVA) occasionally give problems. In the former case, this is
more likely to be a result of incompatibility with additives in the polymer than with the
polymer itself.
7.9 Spherical metal pigments
Being almost true spheres, these pigments have no orientation in plastics and therefore
do not accentuate weld and flow lines by conventional orientation mechanisms. Spherical
metal pigments offer pinpoint light reflection (sharp points of light, reflected from a
small area of a sphere’s surface). The remainder of the surface area is non-contributory.
If used alone, such pigments have very low opacity and appear less bright than flakes of
comparable diameter.
A combination of flakes and spheres can capitalise on the beneficial properties of each.
The flakes contribute the brightness and opacity that spheres lack.
The ratio of flake to spherical pigment is critical. As flake pigment is introduced into the
formulation, it contributes brightness. Due to the mitigating effect of the spherical pigment,
a higher flake loading can be achieved before flow and weld lines become visible. The
overall effect is brighter and more uniform.
A useful advantage of spherical pigments in processing terms is their high degree of shear
resistance.
7.10 Metal flake pigments with coloured surfaces
Pigments in this category cover a wide range of visual effect and particle size. Together
with coloured glitter flakes considered in the next section, they have become known as
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‘effect’ pigments. Many are supplied in dry powder form, especially in the larger particle
size ranges. As a result, wetting into a polymer can present challenges. Extended mixing
or compounding promotes detachment of the coloured surface, as can excessively high
processing temperatures. In the latter case, the coloured coating can melt and disperse in
the polymer matrix. It is therefore important to incorporate these products with the
absolute minimum of shear and at the lowest possible temperature.
When used in coatings, bleed of the colorant into the application solvent is likely to be a
greater problem than shear damage. More modern products have improved properties
in this respect.
7.11 ‘Glitter’ flakes
The most influential characteristics of glitter flakes are their high sparkle and lack of
opacity. Adequate wetting can be a problem with large, dry flakes in low surface energy
polymers. For this reason they are best added as granules or plasticiser dispersions.
Glitter flakes have very low surface areas, so elaborated forms require very little carrier
to meet dispersibility requirements. They therefore provide greater formulation flexibility
and have wider polymer compatibility than conventional flakes.
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8
Flow and Weld Lines in Mass Pigmented
Applications
8.1 Description and origins
Together with poor colour, the prominence of flow and weld lines in metal flake pigmented
polymers is cited by plastics converters as one of their main problems. Indeed flow and
weld lines arguably present the greatest challenge to the wider introduction of flake
pigments in general. The assignment of a whole chapter to this topic demonstrates the
importance of the subject.
This chapter describes the origins of flow and weld lines and explains why they are more
visible with metallic flake pigmentation. Overcoming flow and weld lines can be split
into three distinct areas. Methods are described that reduce or even eliminate them by
optimising equipment design and operation. Weld lines can also be mitigated by skilful
formulation, whilst the third technique is improved pigment design. Techniques in these
last two categories are described in Chapter 9. In practice, the best results are obtained
by combinations of all three techniques, rather than using any of them in isolation.
Flow and weld lines are principally a phenomenon of injection mouldings, but can also
be seen in extrusions, blow mouldings and other less common polymer processing
techniques. Flow lines may occur where a localised discontinuity in polymer flow alters
polymer chain orientation. They may also be caused by moulding defects which allow
frozen off (solidified) polymer, perhaps from the barrel tip, to be carried into the cavity
with the next shot.
Flow lines may be present, though not necessarily visible, in mouldings from natural or
virgin polymer. However, pigmentation can increase visibility markedly, especially with
high aspect ratio pigments, such as fibres or flakes. Common locations for flow lines are
on the cavity side of pin gates, in thinned sections of an injection moulding or where the
melt is required to undergo sharp changes of direction (see Figure 8.1).
Heuzey and co-workers [1] studied flow marks in injection moulded linear polyethylene
(PE). They concluded that injection speed was the main controlling factor. A previously
suggested cause, wall slip, was found to have no influence on the generation of flow
marks. Microscopic observation instead suggested that flow lines result from filamentation
and stretching of semi-solidified material.
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Figure 8.1 Flow lines in an article pigmented by metal flakes
Weld lines are also known as meld lines, knit lines, flow defects or flow aberrations. A
comprehensive review of the subject is presented by Malguarnera [2]. Weld lines are
described as complex, three-dimensional areas of finite dimensions, occurring whenever
two or more molten polymer interfaces are brought into contact. They have aesthetic,
morphological and mechanical properties which are generally inferior to those of the
polymer making up the rest of the component, even though processing conditions are
the same. If appreciable melt cooling has already occurred in the cavity, the melt fronts
may not even fuse completely on contact, thereby exacerbating mechanical weakness.
The term ‘meld line’ merits further comment. It is used interchangeably with weld line,
but strictly refers to the type of weld line in which broadly parallel melts fuse laterally.
Thus ‘weld line’ describes the collision of opposing polymer melt fronts. The distinction
is somewhat arbitrary, but a meeting angle between two melts of 130°-140° is generally
accepted as the boundary (see Figure 8.2) [3].
Figure 8.2 Weld and meld line formation in metal flake pigmented polymer
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Flow and Weld Lines in Mass Pigmented Applications
The weld line phenomenon has been increasingly studied from the early 1980s. Three
types of weld line are identified. Multiple-gated injection mould tools create melt fronts
that have to impinge at some point. This is the true weld line, occurring by impact of
melt fronts coming from opposite directions (see Figure 8.3). The second arises from
recombination of two melt fronts derived from a single melt front that has divided around
an obstacle in the tool. The fronts are moving parallel to each other in the same direction,
eventually coalescing laterally to form a meld line (see Figure 8.2). The mould filling
sequence that generates this type of weld line is shown in Figure 8.4.
Figure 8.3 Weld line arising from the impact of opposing melt fronts
Figure 8.4 Mould filling sequence showing the generation of weld and meld lines by
division and recombination of melts
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Figure 8.5 Weld lines caused by jetting
The third type of weld line is less common, since it results from a moulding defect.
Jetting or squirting of melt into the tool cavity causes a snaking appearance in which the
melt fronts again coalesce from a parallel orientation (see Figure 8.5). In this case, however,
the directions of flow are opposed.
In extrusion, weld lines result whenever there is an internal mandrel in the die head.
Such a configuration typically occurs in producing hollow objects with a constant cross
section, such as pipes. Weld lines of the parallel flow type occur where the melt flows
divide around the die supports to recombine downstream. The number of weld lines is
defined by the number of die supports or ‘spider’s legs’ used.
In blown film, weld lines are deemed satisfactory if the appearance and weld strength are
adequate for the packaging applications for which they are mainly used. In blow moulded
containers, welds form by a similar mechanism to extrusion, since the first stage of blow
moulding is extrusion of a slug of polymer known as the parison. Where this melt is split
by the mandrel support or the mandrel itself, recombination generates a weld line which
may incompletely fuse during the inflation stage. A fault known as parison pleating, in
which polymer emerging from the extruder has the appearance of a frilled skirt, is similar
to jetting in injection moulding. Weld lines also form when the parison is pinched off by
the closing mould halves, immediately prior to inflation.
Despite the many different polymer conversion techniques, Malguarnera contended that
the physical nature of weld lines that exist in almost every manufactured plastic item is
essentially the same.
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8.2 Tool design for injection moulding
The performance of flow and weld regions can be changed by modifying tool design and
moulding parameters. The essential requirement is to employ any mechanism that
encourages molecular entanglement of impacting polymer chains to re-establish the
morphology characteristic of areas remote from the weld region.
Hobbs [4] studied isotactic PP using a mould containing a pin in the cavity around
which the melt was forced to divide. The mould temperature was varied from 25 °C to
220 °C whilst holding the melt temperature constant. As the mould temperature was
raised, the surface appearance of the weld line formed beyond the pin improved until at
180 °C it was invisible. Hobbs was also able to show that air entrapment in the weld
region should be avoided as it can cause a surface notch coincident with the weld line.
Hagerman [5] concurs, based on his study of four grades of ABS by electron microscopy.
Sufficiently high melt and tool temperatures assist recovery of mechanical properties at
the weld line.
Weld lines produced by melt flowing past inserts in an injection moulding tool were also
studied by Barrick [6]. He observed that the relative tensile strength of weld lines in high
melt flow index materials was greater than that for low melt flow index polymers. Weld
strength decreased as the distance from the gate increased. This was interpreted as being
due to melt cooling which progressively occurred as the melt moved away from the gate
region. The study concluded that melt index and density were the most important material
properties affecting weld line strength.
Malguarnera [7] investigated the effect of melt temperature, mould temperature, injection
speed and cooling time on the weld strength of freshly moulded and annealed specimens
of a high flow and a low flow rate PP. It was found that annealing and higher melt and
mould temperatures strengthened weld lines in both materials. Higher injection speeds
had only a slight positive affect on the low flow rate material at low melt temperatures.
Cooling time had little effect. A later study of four commercially available grades of PP,
also involving Malguarnera [8], concluded that melt and mould temperatures and
annealing had the greatest influence on the weld region’s tensile properties.
Confirmation that weld line impact strength is directly related to the extent of diffusion
across the weld line during processing came from Pecorini and Seo [9, 10]. They developed
a model describing polymer self-diffusion which correctly predicted the relation between
weld line healing and injection moulding temperature for a plasticised cellulose acetate
propionate (CAP) resin.
The 42nd SPE Annual Technical Conference in 1984 provided two contributions to weld
line knowledge. Kim [11] was able to predict and experimentally correlate the strength
85
of weld lines from PS processing parameters by determining the effect of molecular

orientation and bonding. In a study of tensile properties of polymethyl methacrylate
(PMMA), styrene acrylonitrile copolymer (SAN), polystyrene (PS) and polycarbonate
(PC), Mosle [12] suggested that the influences of weld lines could be minimised by lowering
the viscosity of the melt during injection moulding.
This theme was continued by Piccarolo [13] in a comparison of the weld line performance
of PS and Nylon 6 under a wide range of processing parameters. The width of grooves
forming at weld lines was mainly related to the operating conditions influencing flow
front temperature. The mechanism of weld line formation was determined by the viscosity
of the layers, which squeezed towards the mould wall after the melt fronts collided.
Janicki and Peters [14] of Dow Chemical Co., claimed that mould temperature had no
effect on amorphous, general purpose PS. The average molecular weight however was
significant, a higher molecular weight leading to increased weld line strength.
The relationship between weld line properties and the relaxation behaviour of the polymer
melt was studied by Hamada and co-workers [15]. A polymer melt with a relatively
short viscoelastic relaxation time was found to have superior weld line strength. This
means that such polymers can relax, and entanglement in the weld line region increases
smoothly before the melt is frozen off. The relaxation behaviour was also demonstrated
by optical data that corresponded to molecular orientation.
Two studies by Merhar [16, 17] looked at the influence of processing parameters on weld
line formation in PVC. Taguchi design of experiments was used to show that mould
temperature was the most important factor affecting weld line strength. Reductions in
strength were observed at the highest temperature and injection rate, but this was ascribed
to thermal degradation or the complex morphology of the material. Higher melt and mould
temperatures produced more brittle parts, while higher injection rates increased the ductility,
thought to be due to variations in crystallinity at the weld line. Overall, the grade of PVC
studied was insensitive to both strength loss at the weld line and to processing conditions.
As early as 1951 an ingenious glass faced injection mould allowed Gilmore and Spencer
[18] to observe the behaviour of molten polymer flow inside the mould. They were able
to photograph severe retardation of the melt as it passed a cavity insert. More significant
was the pocket of air entrapped when the flow fronts recombined. Air entrapment at the
weld may be at or below the surface, the latter as voids. Both affect the appearance and
strength of the weld region.
Yokoi [19] later used a similar glass faced mould to analyse weld line formation. A method
was developed which clearly determined a specific meeting angle between two melt fronts
and where a weld line vanished. The flow-front meeting angle could be used to predict when
86
a weld line would disappear, almost regardless of moulding conditions or cavity shape. The
vanishing angle ranged from 118° to 148°, depending on the nature of the polymer.
In the early 1990s, the rapidly increasing power of computers allowed ever more sophisticated
models to be constructed to predict flow behaviour in injection mould tools. It was not long
before companies such as C-Mold, and Moldflow turned their attention to developing an
automatic weld line interpretation algorithm. Lautenbach [20], described such a programme
in 1991. It accurately predicts the correct number and location of actual weld lines on two
production moulded parts. A slight discrepancy in predicted weld line length versus actual
visible length was noted, but satisfactory refinement of the model is anticipated.
The following year, Kuvshinikov [21] reported the application of a Moldflow programme
to successfully predict the appearance of a weld line in a low gloss ABS automotive
dashboard panel.
A theory to predict the tensile strength of weld lines, based on the effects of molecular
orientation and bonding at the melt front interface, was presented by Jong, Chan and
Wu [22]. The theory is integrated with computer aided engineering results and the
interpretation of weld line locations to predict weld line strength. The results obtained
showed good agreement with experimental data.
Mekhilef [23] developed a model for the prediction of weld line strengths of amorphous
polymers based on diffusion and free energy concepts. The concept was extended to a
study of weld line strength of injection moulded polycarbonate/high density polyethylene
(PC/HDPE) blends. Specimens were tested for tensile strength and phase morphology
studied by scanning electron microscopy (SEM). These showed the importance of blend
morphology in characterising the structure and adhesion at the melt interface. Acceptable
agreement between prediction and experimental results is claimed.
Lubricants may have a modifying influence on weld line strength. A study by Herten
[24] proposed that lubricants reduce the viscoelastic stresses at the plastic/mould interface.
The flow behaviour of lubricated ABS was correlated with weld line strength measurements
of injection mouldings.
8.3 Orientation in multiphase and glass filled polymers
There is very little literature describing the flow and weld line performance of metal
flakes. Much work has however been carried out on traditional filled polymers, including
short cut glass fibres. Some pointers to metal pigment performance can be derived
from these.
87
In 1990, Miller [25] cited injection speed, barrel and mould temperatures, back pressure
and screw speed as the critical parameters to note, to avoid the pitfalls in moulding
reinforced thermoplastics. The following year, Lalande [26] reported on a study of PP
reinforced by 30%, 40% and 50% of long glass fibre. Fibre orientation in the matrix
governed mechanical properties. Morphology at the weld line gave a parallel orientation
of the fibres to the flow front and to the weld line. This orientation gave a low tensile
strength because the stress at the weld line must be borne by the matrix alone.
Thamm [27] studied the phase morphology of PP/EPDM and PP/HDPE/EPDM blends,
which are expected to have high impact strength. The PP has a well defined skin and core
structure. Within the core region, the dispersed EPDM has a spherical or globular shape.
In the skin region, however, the dispersed discontinuous phase is sheet or disc like, oriented
parallel to the surface of the moulding. Where weld lines occur, these discs orient vertically
to the flow direction, parallel to the weld line. In extreme cases, they prevent the tangling
of molecular chains of the matrix necessary to achieve high weld line strength. Indeed
they may act as stress concentrators, leading to the observed loss of weld line strength.
Thamm found that this behaviour could be minimised by using high viscosity, less easily
dispersed EPDM compositions. A key observation relevant to metal flake pigmented
mouldings is that no elastomeric particles were observed at the centre of the weld line.
Later work by Savadori [28] also tested samples of PP/EPDM, this time filled with short
glass fibres or glass spheres. It was shown that the weld line had poorer mechanical
properties when it was due to opposing flows. The tensile strength decreased with an
increase in rubber or filler content and with a decrease in rubber molecular weight.
However Peacock [29] claimed that addition of low concentrations of low molecular
weight rubber to rubber modified PP reduced the severity of flow marks.
Further pointers to the behaviour of metal flakes in polymers come from work by Lim
[30] on polycarbonate (PC) and polyphenylene sulphide (PPS), reinforced by short glass
fibres. Microscopy was used to study microstructure. The weld region showed flower-
and volcano-like patterns. Crack growth rate was shown to be dependent on fibre
orientation. Akay and Barkley [31] found similar effects in short fibre reinforced PP and
polyamide. At the weld line there is a discontinuity in fibre-orientation profile, the fibres
aligning themselves along the weld line, preventing reintegration of the flows.
Support for this conclusion has come more recently from Kim and co-workers [32].
They used a mould cavity with a rectangular insert near the gate. Tensile strength and
elongation at break in glass fibre filled polybutylene terephthalate (PBT) with a weld
line, were about half those of specimens without a weld. This was attributed to the fibres
near the weld lines being oriented parallel to the weld line direction, i.e., perpendicular
to the tensile force direction, due to stretching flow.
88
Hashemi [33] claimed that short glass fibre filler had a more adverse effect on weld line
strength than talc in the same PP polymer. The effect was also more pronounced for weld
lines produced by impinging flows than those produced by joining of two parallel melt
fronts.
8.4 Orientation of metal pigments
Although flow and weld lines can be visible in mouldings coloured by organic and in
organic pigments, metal flake pigments do tend to make the effect more prominent.
Much of the reason lies in the flake shape. Non-flake pigment particles have three broadly
similar dimensions. Therefore their orientation in the polymer has relatively little effect
on their perceived colour. The same is not true for flake pigments.
Other relevant factors are the relative inflexibility of metal flakes and the considerable
differences in the coefficient of thermal expansion compared to polymer matrices.
Flow lines in metal flake pigmented mouldings also occur where there is a constriction of
flow. A typical example is where the gate causes the flakes to orient to minimise their
resistance to flow. This is particularly pronounced where the gate dimensions are of the
same order of magnitude as the flake particle size. If the flake orientation happens to be
at right angles to the surface of the moulding, the result is a dark line created by the
relatively low reflectivity of the flake edges, coupled with the absence of reflected light
from the spaces between such flakes. The line may well tail off on the other side of the
gate as the pressure drop imposes a more random flake orientation.
Any localised differences in the concentration of metal flakes may also contribute to
flow lines, the areas of lower concentration appearing darker. This effect is often seen at
pin gates, where larger flakes can pack like a log jam behind the gate. When they are
released, for example by an injection pressure increase, a localised high flake concentration
is created in the cavity. As described in section 7.7, the higher the flake concentration
below colour saturation, the brighter it appears. This area will therefore appear brighter
than its surroundings and will be interpreted by the eye as a flow line.
The relationship between flow and weld lines and flake orientation is illustrated by Figure
8.6. Flakes which are parallel to the plane of the photograph are bright. Those at right
angles to the plane of the photograph appear dark. The dark clusters of particles, similarly
oriented vertically with respect to the surface can be clearly seen. This illustration is not
metal flakes but pieces of slate on a beach. Each of the ‘particles’ is many centimetres in
diameter. Whether on a large or small scale however, the optical effect is the same. Flake
edges appear dark.
89
Figure 8.6 Pieces of slate on a beach, illustrating the appearance of flow and weld
lines in flake pigmented polymers [1cm = approx. 12 cm]
Sanschagrin [34, 35] was amongst the first to seriously study flake pigments. In a study
involving many different particle shapes, he found that high aspect ratio flake and fibre
reinforced polymers exhibited the greatest loss of strength.
The study covered weld lines formed both as a result of head-on collision and those
resulting from division of a melt front around an insert in the tool. In the case of the
former, a V-notch, absent from moulding of unfilled PP, was formed at the weld for all
filled mouldings, despite good venting in the immediate area. The notch became wider
and deeper as the particles went from spheres to fibres to flakes.
In flake filled polymers, Sanschagrin observed a surface layer in which flakes were broadly
oriented parallel to the surface. At the core, the orientation was more random. After
melt recombination, the distance required to reimpose uniform flow was long. This was
explained not by rotation hindrance due to neighbouring flakes, but to the consequences
of the ‘fountain flow’ mechanism of injection mould filling [36]. In terms of strength,
Sanschagrin concluded that a weld line will always be much weaker than other areas of
the part as long as differences in filler orientation remain.
It appears from optical and electron microscopy of injection moulded parts exhibiting
weld lines that there is orientation of the long axes of the flakes parallel to the weld and a
relative absence of flakes at the tip of the melt front (see Figures 8.7 and 8.8) [27]. This
90
Figure 8.7 Electron micrograph showing the relative absence of flakes in the weld
region, between the parallel lines. The orientation of flakes on each side of the weld is
shown by arrows. [1 cm = approx. 60 µm]
Figure 8.8 Schematic diagram of the melt front region of which Figure 8.7 is a part.
complements Thamm’s observations above. The concept of flake inertia, consequent upon
their very much higher density relative to the polymer melt, is proposed to explain the
relative absence of flakes at the tip of the advancing melt front.
91
The effect of polymer viscosity on flow and weld line visibility was studied by Watters,
Kerr and Ringan at Silberline. Their unpublished work is described in section 9.2.4.
Mechanical properties reduction is also observed in polymers containing other flake

pigments. Mica filled polymers exhibit very low weld line strength, probably due to
delamination of the mica flakes themselves [37].
Whilst flow and weld lines are undeniably a challenge, there several ways of mitigating
or even eliminating them. The first of these is improving the tool design.
8.5 Mould tool design for metal pigments
Very often a plastics converter without previous experience of metal flake pigments will
attempt to use them in a mould tool designed for non-flake organic or inorganic pigments
and be disappointed by the results. The best cure for flow and weld lines lies in imaginative
tool design. The aim should be to avoid as far as possible, any constriction of the flow of
molten polymer, particularly any sharp changes of direction at any point in the melt’s
journey from barrel to the furthest recesses of the mould cavity. Designing moulds where
the melt front expands laterally after the weld line is formed will help to reduce its
visibility [37].
One possible remedy is to move the flow and weld lines to positions in which they
are not seen. Modern, computer aided design packages, such as those offered by
Moldflow, C-Mold and others go a long way to achieve this, but are only generally
applicable to new tools. Where an existing tool has to be used, options for modification
may be very limited.
Rosato [38] has published an introduction to the subject which contains a large section
on all aspects of injection mould tool design, with 25 references.
8.6 Gates, sprues and runners
Wilkinson at Du Pont [39] produced useful guidance on optimising the gate position in
injection mouldings. The flow front profile and the consequent effectiveness of the holding
pressure determine the strength and other properties of the moulding. More recently,
Bradley [40] also discussed the importance of gate location and numbers.
Multiple gates are claimed to offer a number of processing advantages. Catoen of Husky
Injection Moulding Systems [41] cited faster injection times, lower melt temperatures, less
92
solid layer build up, thinner walls and the possibility of being able to process higher viscosity
resins. Attractive as this may be, multiple gates mean multiple head-on weld lines.
Bryce at Texas Plastic Technologies [42] offers guidelines for the design of gates, runners
and vents for injection moulding.
In considering formulations containing metal flake pigments, the size of the gate is
particularly important. Pin gates may be suitable for formulations incorporating non-
metallic colorants, but fail to allow the much larger metal flakes to pass unhindered into
the mould cavity. If the gate is too small, irregular cavity filling can occur, as the larger
flakes tend to pack in front of the gate. In general, the largest possible gate size, consistent
with the other constraints, is preferred. This will create the least disruption to smooth
polymer flow. An absolute minimum dimension at least three times that of the largest
flake diameter likely to be used is recommended. Strip gates are often advantageous
where other considerations permit their use.
Hatch [43] describes flow and sink marks in injection moulded ABS parts. Undersized
sprue and gates and almost non-existent venting were found to be the main causes. On
rectifying these, cycle time was slightly extended, but no sink marks were produced.
The size and location of runners is critically important in metal flake pigmented mouldings.
They should be as large a diameter as possible and preferably free of sudden changes of
direction, especially close to the gate. If a sharp change of direction is unavoidable, the
runner should have a generous radius.
Hot runners are very useful in preventing the melt from freezing off before weld lines
have fused. They also help to avoid the need to turn up barrel heat, with the consequent
possibility of burn off of the additives package and plate out of degradation products on
the tool surfaces. Two ways to mitigate weld lines using hot runners are described in
Injection Moulding International [44]. The article notes the trend to decreasing wall
thickness in moulded parts, which tends to increase the visibility of flow and weld lines.
Actively influencing mould filling improves control of mould front formation.
One of the advantages of metal pigmentation is that the excellent thermal conductivity of
metals allows more efficient and uniform heat conduction throughout the melt. In some
cases, introduction of metal pigment can allow the barrel temperature to be reduced by
several degrees. When granular metal pigments are used, the contribution from thermal
conductivity is enhanced by the effect due to the lower melt viscosity of the carrier component.
Advances in runnerless moulding technology are reviewed by Bernhardt and Bertacchi

[45]. Underlying principles are discussed with practical examples. Aspects examined in
detail include use of insulated runners, internally heated insulated runners, purely hot
93
runners, valve gates, sequential filling, gas assisted injection moulding with hot runners
and displacement and strengthening of weld lines.
8.7 Tool texturing
Another technique for reduction of flow and weld line visibility is texturing the article.
This is most readily achieved in injection mouldings by treatment of the mould tool
surface. Stippling and crosshatching are usually the most effective.
8.8 Additional cavity
Additional cavities, into which the melt can be displaced, can relocate and reduce the
visibility of weld lines. Hamada [46] suggests an additional cavity as a means of linearising
the flow of fibre reinforced thermoplastics (FRTP). These otherwise displayed very poor
visual quality, coupled with reduced mechanical strength. Strength increments were
significant in a multicavity tool, due to realignment of fibres to the flow, caused by ‘back
flow’ of the material during the holding stage.
8.9 Dynamic melt techniques
Many large injection mouldings are conspicuous components with high specifications
for surface quality. In recent years the drive for ever lower unit costs has seen typical wall
thickness reduced from 4-6 mm to only 2-3 mm. This places critical constraints on both
the tool maker and the moulder. To fill large components of such thin section, multiple
gating has become more common. As already noted however, the resulting proliferation
of melt fronts induces multiple weld lines.
This section describes several relatively recent techniques for weld line suppression, all
of which rely on keeping the polymer melt in motion to minimise the opportunity for
flow and weld line formation in these injection moulded parts.
8.9.1 SCORTEC
One of the earliest means of keeping melt in motion during the cooling phase used the
injection moulding machine screw to produce an oscillating pressure [47]. This overcame
mould filling difficulties such as poor mould packing and dimensional instability of the
moulded part.
94
A more refined development by Bevis and Allan at Brunel University, was originally
known as Multiple Live Feed Moulding [48]. Later SCORTEC, or Shear Controlled
ORientation TEChnology was coined as a generic name for a family of technologies, all
capable of improving the appearance and strength of the moulded part [49, 50, 51, 52].
Grossman of Scortec Inc., has described the SCORIM (Shear Controlled ORientation in
Injection Moulding) process as offering an economical answer to flow and weld lines in
both thick and thin sectioned parts [53]. Mechanical properties are improved and sink
lines, voids and dimensional instability in filled and unfilled polymers eliminated.
The technique requires that a processing head is inserted between the nozzle of an injection
moulding machine and the rear of the tool. The head, shown in Figure 8.9, directs a split
melt to opposite ends of the tool cavity. Hydraulic pistons act on the melt to keep it in
motion during the cooling phase of the cycle. A controller linked to the injection moulding
machine’s own electronics, synchronises the operation of the pistons. The most usual
initial configuration is out of phase, i.e., one pushing as the other pulls. In this way an
oscillation of the melt takes place. Screw pressure is maintained, depending on the part
shape and thickness. As the melt cools, in-phase compression may be applied to fill any
sink marks or voids.
Mould tool Hyraulic

pistons SCORIM head
Barrel of injection
moulding machine
Runner
Component system
Figure 8.9 The SCORIM process
95
Figure 8.10 Comparison of a conventional moulding (bottom) and a moulding prepared

with SCORIM. The weld line, visible in the lower moulding, is absent in the upper.
Figure 8.11 Styling possibilities with SCORIM. The designs are produced by varying
the piston action, using melts of contrasting colours.
96
Figure 8.10 shows the effect of SCORIM versus conventional moulding of a tensile test
specimen simultaneously injected from opposite ends. Experiments with fibres confirm
that they too orient to minimise their cross section in the direction of movement.
Another commercially useful spin-off from this technology is its potential for moulding
multi-coloured parts in a controlled and reproducible manner. Two injection barrels are
required, each providing a differently coloured melt. Use of SCORIM then creates
mouldings comprising the original two colours and their mixture. The degree of mixing
and the shapes obtained are controlled by the SCORIM processor (see Figure 8.11).
SCOREX (Shear Controlled ORientation in EXtrusion) is the application of the technique

to extruded tubes and other profiles that inevitably involve recombination of flows on
the downside of the die supports.
8.9.2 Other techniques
Sequential injection moulding, proposed by Gazonnet, is suitable for large, two-

dimensional parts. It operates by opening and closing the needle valve nozzles of a hot
runner system to displace weld lines into non-critical areas of the moulding. Nozzle
action is controlled pneumatically or hydraulically. Effective venting is essential. Gazonnet
[54, 55] describes the principles and advantages of this technique, together with some
applications covering both elimination and relocation of weld lines. Software developed
by Pole Européen de Plasturgie and SISE to control the process is also discussed.
Through the related technique of cascade injection, mouldings free from weld lines are
produced by arranging injection nozzles in series. Injection commences at the central
nozzle, adjacent nozzles then being opened stepwise within the series as they are reached
by the melt front. Relocation of weld lines through displacement to less critical areas of
the moulding can again be achieved [56].
Gardner and Malloy [57] describe a moving boundary method, providing melt mixing in
the weld region. The process uses a cam operated reciprocating pin, or two such pins, to
displace the melt during mould filling. The technique is claimed to be very effective in
strengthening weld lines in glass fibre reinforced polymers.
Kazmer and Roe [58] successfully used a hot manifold with timed valve gate control of
flow into the cavity to improve weld line strength.
A mould with flow diverters was used by Walker [59] to create reversible transient flow
in injection moulded PP and PS. This shifted the flow under the frozen surface layer of
the moulding and increased both the tensile strength and flexural modulus. Flow analysis
software determined the effects of subsurface orientation.
97
8.10 Localised mould heating
As noted in section 8.2, any mechanism that encourages molecular entanglement of

impacting polymer chains will relieve weld lines. Extending the period of time during
which the polymer is molten contributes to this aim.
Wada [60] of the Asahi Chemical Industry Company built on this concept to patent a
novel injection moulding technology called Bright Surface Moulding (BSM). The technique
involves robot insertion of a high frequency induction heater between the tool cavity
surfaces after ejection of the moulded part. The cavity surface temperature rises very
rapidly, whereupon the heater is retracted and the moulding cycle continues in the
conventional way. As injected polymer touches the heated part of the cavity, its temperature
is temporarily raised. If the heated section coincides with a weld line, the opportunity for
knitting of molecular strands is much increased, with a corresponding reduction in weld
line visibility and an increase in weld strength.
Simultaneous use of this technique with SCORIM has been conducted with aluminium
flake pigments by Rawson, Allan and Bevis [61, 62]. The combination gives a less visible
weld line than either technique used alone (see Figure 8.12). The technique is effective
Stylac AT-30 ABS, with SILVET® 764-30-E1 aluminium flake pigment. (90 µm median diameter)
Figure 8.12 Weld line visibility as a function of moulding technique. A combination

of SCORIM and BSM renders the weld invisible.
98
and reproducible. An optimum heating time, corresponding to an optimum mould surface

temperature, facilitates controlled re-alignment of the aluminium flakes at the moulding’s
surface. Such melt manipulation, as well as removing weld lines, imparts uniform surface
reflectivity across the weld region, thereby removing any tendency for flop characteristics.
Weld strength is also increased.
8.11 Other techniques
Two other ingenious solutions to the flow and weld line problem can be discussed here.
An injection moulding with continuous thin sections promotes smooth flow of metal
flake pigmented polymer. The unwanted thin sections are subsequently punched out.
This approach has been used on car wheel trims as an alternative to spray painting an
unpigmented moulding. Though giving a blemish-free surface, the disadvantage is the
cost of the additional process step. The technique has similarities to thermoforming (see
section 10.7).
Robot placing or spooling of uniformly pigmented extruded film or sheet in an injection

moulding tool, followed by injection of natural polymer can also provide a solution.
This technique, sometimes known as in-mould decoration, has also been applied to wheel
trims. It is appropriate where only one side of the moulded part is visible in the final
application. The technique is considered further in section 10.6.
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9
Formulation of Mass Pigmented Polymers
This chapter concentrates on formulation skills and metal pigment developments. It also
brings together elements of equipment design and pigment incorporation introduced in
previous chapters.
9.1 General techniques
There are many ways to improve the visual effect of metallic, mass pigmented polymers. It
is important to reiterate that in most instances, the best results will be achieved from
combinations of the materials and techniques described here, rather than from any single
factor. The full arsenal of methods employed comprises: optimising the formulation,
improving pigment incorporation and the equipment used to achieve this and finally
improving the quality of the metal pigments themselves.
A few principles are common to all metal flake pigments and incorporation techniques.
These are examined first. Techniques for specific processes, such as extrusion or injection
moulding, are described later. A recurring theme in the latter is reducing the visibility of
flow and weld lines.
9.2 Optimising the formulation
A cornerstone of formulation with metal pigments is a sound understanding of the

relationships between particle size, colour and colour saturation, opacity, sparkle, pigment
concentration and cost. These characteristics are defined in Chapter 4 and their
interrelationship described in section 7.7.
Competitive pressures in the plastics market demand ever increasing cost-effectiveness.

It therefore becomes even more important to choose the correct pigment for the envisaged
application. Cost is linked to concentration, so it follows that concentration must be
minimised, consistent with other factors.
105
The ideal metal pigment will have the following attributes:
Lowest density = more opacity (more flakes per unit weight)

Thinnest flakes
Smallest flakes
Smooth surfaces = best colour

Rounded flakes
Largest flakes
Good orientation
Thickest flakes = best colour retention (degradation resistance)
Rounded flakes = easiest dispersion

Largest flakes
It is immediately apparent that some of the requirements are contradictory, the more so
when cost considerations are added.
The lowest density is provided by aluminium at 2.7 g/cm3. The thinner cornflakes offer
the greatest opacity, providing dispersion forces are minimised to prevent flake damage.
For commodity applications, the constraints of small flakes may be acceptable because
their high opacity reduces the concentration required. This in turn reduces the cost per
unit weight of pigmented polymer. The better colour demanded of prestige applications
requires the more expensive round-edged, smooth surfaced silver dollar flakes. If a degree
of sparkle is specified, this can only be achieved from larger flakes. Higher concentrations
and therefore cost will be the penalty to achieve equivalent opacity.
9.2.1 Flake size
As a general principle, the largest possible flake should be used, consistent with cost and
appearance. In mass pigmented polymers, the unaided eye is barely able to distinguish flakes
below about 20 µm median diameter, no matter how bright they may be. As median flake
size increases above 30 µm, a random orientation of the flakes will begin to appear sparkling.
9.2.2 Flake concentration
The pigment loading should be adjusted so that the moulded part appears just opaque in
its thinnest section. This does not necessarily mean that the part is actually opaque,
merely that it appears so. A bottle for example, can appear opaque when viewed from
106
the side, but appears remarkably translucent when viewed through the aperture. Such an
approach allows the maximum metallic reflection from deep within the polymer. This
adds to the richness of the effect in cases where solidity is also important. It also has the
added benefit of being very cost-effective.
9.2.3 Polymer transparency
Where possible, an optically clear grade of polymer should always be used. Inherently
coloured polymers, such as ABS will require 10-40% more pigment for an equivalent
visual effect. In extreme cases, they may never reach the brightness and gloss of the same
pigment in a transparent polymer.
9.2.4 Polymer viscosity
The viscosity of a polymer influences its ability to carry the metal pigment at the tip of
the advancing melt in an injection moulding. This phenomenon was investigated by
Watters, Kerr and Ringan [1] who moulded iron flakes in three grades of PP of widely
differing melt flow. Iron flakes were selected because of their particularly high density,
which it was hoped would make any effect more easily visible.
Figure 9.1 shows the weld line formed by division of melt round a pin in the tool. The
two mouldings are distinguished only by the viscosity of the polymer grade used.
Figure 9.1 The effect of polymer viscosity on weld line appearance. Low melt flow
polymer (A), left, exhibits a sharper weld line than a high melt flow polymer (B) when
pigmented by 2% iron flake of 110 µm median particle diameter
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The higher viscosity PE (A), with a low melt flow index of 20 g/10 min at 190 °C, carries
the metal flakes well, producing a narrow, but very prominent weld line. The flake-free
band at melt contact is very narrow. A less viscous grade (B), of 200 g MFI has a greater
ability to flow past the high inertia flakes. The resulting weld line is much more diffuse.
It is also very wide, as is the area free of flakes where the melt fronts combine. These
results confirm Mosle’s [2] findings for fibres.
The effect is much less marked with the lower density aluminium pigment and the normal
MFI range of commercial polymers.
9.2.5 Metallic/organic pigment combinations
The most severe instances of flow and weld lines come from fine particle size flakes at
concentrations high enough to confer opacity on the moulded article. If low concentrations
of larger flakes can be used, in combination with organic and inorganic colours to provide
opacity, unsightly lines can normally be avoided. Considerable skill is required from
formulators to achieve optimum results.
In certain polymers, dyestuffs may provide a richer effect, if their relative transparency
can be tolerated.
Large glitter flake pigments can be used to advantage in combination with organic and
inorganic colorants. The latter provide the opacity that the glitters lack.
9.2.6 Deep shades
In coloured metallic formulations, for a given metal pigment and loading, deeper shades
mask weld and flow lines better than pale shades. Though not always an option, it is a
mitigating factor that can be combined with others in this section.
9.2.7 Spherical pigments
Manufacture of these pigments is described in section 3.5. Being almost true spheres,
spherical metal pigments have no orientation in plastics and therefore cannot generate
weld and flow lines by conventional orientation mechanisms.
It has been commercially confirmed that their introduction into metal flake pigmented
formulations reduces the visibility of flow and weld lines. This is believed to be both because
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the spherical pigments disrupt the orientation of flakes in the region of flow and weld lines,
and because a lower concentration of flake pigment is required. This is another area in
which skilled formulators can significantly improve the appearance of the moulded part.
The ratio of flake to spherical pigment is critical. Spherical metal pigments offer pinpoint
light reflection. The remainder of the surface area is non-contributory. If used alone,
such pigments have very low opacity and appear less bright than flakes. For this reason,
they are best suited to deeper shades.
As flake pigment is introduced into the formulation, it contributes brightness. Due to the
mitigating effect of the spherical pigment, a higher flake loading can be achieved before
flow and weld lines become visible. The overall effect is brighter and more uniform.
The combination of a 30 µm diameter spherical aluminium pigment with a 50 µm average

particle diameter aluminium flake pigment gives particularly good results. A useful attribute
of spherical metal pigments in processing terms is their high degree of shear resistance.
9.3 Incorporation in polymers
9.3.1 Low shear forces
This is the most important processing factor. In order to manufacture flakes, all the
metals used as pigments must be malleable. Aluminium, for example, is a soft and ductile
metal. Derived flakes are easily deformed by the high shear forces commonly encountered
during plastics processing. Bent or broken flakes have reduced surface area from which
to reflect light. The visual result is then dull, grey and non-metallic.
Figure 9.2 shows aluminium flakes carefully isolated from a commercial masterbatch.
Broken and folded flakes, with their characteristic straight edges, can be clearly seen.
Where it is necessary to disperse other colorants using high shear, as in a twin screw
extruder, the metal pigment should be introduced close to the die, perhaps via a degassing
port. Though a batch apparatus, the Banbury type of mixer is ideal for metallics, as
shear can be controlled throughout the dispersion process.
Modern metal pigment delivery forms, such as Silberline’s widely patented SILVET®
aluminium flake pigment granules, are designed for low shear incorporation. The metal
flakes are immobilised in 20-30% of a widely compatible carrier resin, which melts
below the melt point of the polymer granules. The pigment is thus distributed as a pre-
dispersion over the polymer granule surfaces. Thereafter there is only a requirement for
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Figure 9.2 Electron micrograph of aluminium flake, damaged by high shear processing
mixing, rather than shearing, to fully disperse the metal flakes throughout the polymer
mass. The granule dimensions have been carefully chosen to minimise the stratification
in the hopper that would otherwise occur due to the substantial density difference between
metal pigment and polymer.
9.3.2 Improvement of flake orientation
Advantage should be taken of any mechanism that helps to increase the proportion of
flakes orienting with their faces parallel to the polymer surface. This includes mono and
biaxial stretching, as, for example, during sheet extrusion or blown film manufacture.
Modern injection-stretch-blow moulding machines give particularly good results.
9.4 Increasing pigment quality
A key method of achieving mass pigmented polymers approximating a painted appearance

is to use new, highly polished, extremely bright flakes specially designed for the purpose.
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In practice, such pigments tend to be derived from aluminium flakes originally developed
to meet the very exacting requirements of the automotive paint market. These are the
silver dollar flakes whose production is described in section 3.3.1. It is ironic that pigments
originally developed for automotive paints should now be instrumental in forcing a move
to mass pigmentation.
For this application it has been found that flake diameters almost twice those of the
corresponding paint grades are required to compensate for the lack of orientation in the
moulding. Typical automotive and bicycle paint pigments have median particle sizes of
14-20 µm and 25-35 µm, respectively. Corresponding grades for mass pigmentation require
diameters of 25-35 µm and 45-60 µm. Loadings of ~2.5% and ~3.5% w/w, respectively,
are then required for colour saturation in clear polymers.
Work by Sanschagrin [3] showed that as the aspect ratio of a filler in injection moulded
polypropylene decreased, strength retention increased. It follows that spherical metal
pigments and thick, degradation resistant metal flakes should offer better mechanical
strength retention than conventional, high aspect ratio flakes.
9.5 Summary
The following points are provided as a quick reference summary. They collect together
all the techniques from this and Chapter 8 which provide the brightest, most cost-effective
visual effects, with minimised weld line visibility and increased weld strength in metallic
pigmented mouldings.
Tool design
• Move weld lines out of sight at the design stage where feasible.
• Locate unavoidable welds as close to the gate as possible.
• Ensure good venting in the weld region.
• Texture the tool surface.
• Investigate dynamic melt techniques.
Formulation
Use:
• the largest, thickest, preferably silver dollar flake, consistent with cost and appearance.
• the minimum pigment concentration for opacity in the thinnest section of the moulding.
• deep organic or inorganic colorants.
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• spherical pigments, where the effect required is a deep shade.

• the most transparent polymer possible.
• the polymer with the highest possible melt flow.
• the highest molecular weight polymer, consistent with other constraints.
• a polymer with a relatively short viscoelastic relaxation time.
Processing
• Minimise shear.
• Increase mould temperature.
• Increase injection speed, but beware of jetting.
• Increase melt temperature within the heat stability limits of melt components.
References
1. C. Watters, S. Kerr and E. Ringan, unpublished work, Silberline Ltd.
2. H. G. Mosle, R. M. Criens and H. Dick, Proceedings of the Antec 84 Conference,

New Orleans, USA, 1984, 772.
3. B. Sanschagrin, R. Gauvin, B. Fisa and T. V. Khank, Plastic Compounding, 1987,

10, 3, 37.
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10
Conversion Processes
In this context, the term conversion describes the process of transforming uncoloured,
i.e., natural or virgin polymer powder or granules into an optionally coloured, finished
article by melting and fusing the polymer. In its widest sense conversion includes the
manufacture of masterbatch or compound precursors to the finished article. In this chapter,
a number of the most important conversion processes will be covered with particular
reference to the role of metal pigments in their coloration.
Techniques for combining metal pigment with the polymer are common to most of the
conversion processes described here. The key requirement is a homogeneous dispersion
achieved without the use of high shear forces. The quality of the pre-dispersion must be
good enough to accommodate any deficiencies in the mixing action of the conversion
equipment.
The physical form of the raw materials is the determinant of the mixing process. Polymer
may be supplied in powder, spherical, flake or granule forms, with metal pigment present
as dry flake, plasticiser dispersion or granule.
Dry flake is the least technically satisfactory product form. Incorporation is by tumbling
or gentle mixing by a blade capable of moving the whole mass. Dry flake should not be
mixed in any form of high speed powder blender for two reasons. Firstly, the shear is too
great, causing darkening and loss of metallic effect. Secondly, it is extremely hazardous
in the case of some metals, especially aluminium, even if carried out under a blanket of
inert gas. Dry flake will mix well with polymer powder, but it is difficult to wet it
adequately into the polymer melt.
Plasticiser dispersions have better wetting characteristics, but have a tendency to form
into balls during mixing with polymer. If double cone blenders are used, the polymer
should be charged first. A small further addition of plasticiser, allowed to coat the polymer
surfaces, is sometimes beneficial before addition of the metal pigment. Polymer powder
is the least preferred physical form here as it tends to form lumps itself under these
conditions.
Metal pigment granules offer a means of avoiding premixing altogether because they are
easy to handle and incorporate. In mass pigmented plastics they overcome the main
deficiencies of plasticiser dispersions, offering easier handling and meterability in modern
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automatic dosing systems. For most applications, dry tumbling with polymer granules
followed by extrusion or moulding will provide a satisfactory degree of dispersion. For
the most demanding applications, where a high degree of dispersion is required, for
example, in blown film applications, low metal content granules are available.
Commercially available pigment granules tend to have a low melting carrier system. It
melts first in the processing equipment, coating the surface of polymer pellets, granules
or spheres before the polymer itself melts. In this way, good pigment wetting and efficient
pre-dispersion is obtained. This in turn allows the essential low shear incorporation
equipment to be used for a full dispersion. Because of the high metal content, granules
can, if desired, be co-dried with the polymer without premature break up. With care,
even temperatures above the carrier softening point can be used.
Organic and inorganic pigments, unless pre-dispersed in a polymer or carrier resin, are
usually aggregates of primary pigment particles. To achieve the maximum colour strength
from such pigments, shear may be required to break down the aggregates and disperse
the primary pigment particles. It is therefore tempting for the converter to use the same
equipment to disperse metal flake pigments as for dispersing such colorants, in the belief
that this too will give rapid and efficient dispersion.
This is wrong, as the disappointingly dark, dull and non-metallic results will testify.
High shear processing has bent, folded or fractured the very thin metal flakes, dramatically
reducing their colour, brightness and metallic lustre. If high shear is required to disperse
other components of a plastics formulation, that step should be complete if possible,
before the granule is added to the system. In twin screw extruders it may be possible to
meter granules into a downstream de-gassing port, or via a side feeder near the die, as is
current practice for other shear sensitive fillers such as glass fibres.
When using metal pigments in general, it has been found that the thermal conductivity
through the molten polymer mass improves. This can allow a barrel temperature reduction
of 5 °C or more, with consequent energy savings and reduced tendency for thermal
degradation of the polymer.
10.1 Injection moulding
Injection moulding accounts for approximately one-third of all polymers processed. The
technique is versatile and has relatively low set up costs. As a result, injection moulding
companies tend to be small and numerous.
A very comprehensive introduction to the theory and practice of injection moulding is

provided by Rosato and Rosato [1]. It includes information on the design of the moulded
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part for optimum performance, ease of manufacture and lowest cost. Choice of polymer
is considered as well as moulding techniques themselves.
Points to consider in injection moulding with metal pigments are mainly related to the
avoidance of flow and weld lines. These issues are considered in detail in Chapter 8.
Colour retention is less of a problem in injection moulding than it is in extrusion, as the

barrel and screw are generally configured for mixing rather than applying high shear.
Nevertheless, screw return times (the time taken for the injection moulder’s screw to
return with plasticised material, ready for the next shot) should be minimised, consistent
with a satisfactory dispersion.
10.2 Blow moulding
The term blow moulding refers to both container and continuous film production. The
production processes are different, but they share the use of air to expand the polymer
melt, hence the name.
10.2.1 Blown film
Blown film extrusion is a continuous process in which a tube of extruded polymer melt
is drawn up into nip rollers. Air is injected to create a bubble whilst maintaining tube
integrity as the polymer rises and cools. A detailed description of the apparatus and its
operation is provided by Knittel [2].
Polyolefins are the most commonly used polymers, producing film thicknesses around
0.1-0.5 mm. The main markets are rubbish and shopping bags and agricultural film for
silage, weed suppression, etc. Co-extruded films have food packaging uses, by virtue of
internal barrier layers.
The most commonly used pigment is carbon black, since it is the most cost-effective
source of opacity. Metal pigments, principally aluminium, but also gold bronze, are used
in applications in which appearance takes precedence over function, for example, plastic
shopping bags.
Due to the extreme thinness of blown films, only fine particle size grades of metal flake
pigments can be used. They must be free of grossly oversize flakes that could otherwise
cause the film bubble to pinhole. Dispersion is also very important, as any undispersed
flake aggregates will have the same effect. In practice therefore, grades of 6-12 µm diameter
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Figure 10.1 Uniform orientation of aluminium flakes in biaxially stretched polymer

film [1 cm = approx. 15 µm]
with fairly tight particle size distributions are specified at loadings of approximately 0.5-
1%. They may be offered as compound or as a low metal content masterbatch.
The biaxial stretching that occurs automatically in this process orients metal flakes parallel
to the film surface, thereby increasing brightness (see Figure 10.1).
10.2.2 Blown containers
Blow moulding is extensively used for a wide range of shapes and sizes of containers, the
most notable being cosmetic and toiletry containers, beverage and oil bottles. Its usefulness
lies in the wide variety of shapes of container that can be accommodated, many impossible
to produce by the other common moulding techniques. A comprehensive review of the
subject is provided by Fritz [3].
The process involves extruding a slug of molten polymer into a mould, constructed
somewhat like an injection mould. The polymer is expanded against the walls of the
closed mould by air pressure. A larger wall thickness than blown film permits a wider
pigment range. Metal pigment grades with median diameters over 200 µm have been
successfully moulded by this technique.
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Because blow moulders are not primarily designed for dispersion, compound, or less
commonly, masterbatch is the preferred form of feed. Occasionally, metal flakes,
especially coarse particle sizes, rub off the surface of blow moulded containers. Weld
strength of the seam or parison line may also be reduced. In both cases, this is generally
a symptom of insufficient wetting, which in turn points to insufficient energy input at
the compounding or masterbatch stage. It can sometimes be overcome by raising the
melt temperature of the blow moulder, but the real remedy is the responsibility of the
compound or masterbatch manufacturer.
Metal flake concentrations can be quite low, as only translucency, rather than opacity, is
required to hide the eventual contents of the container. The technique is particularly
suited to the creation of coloured pearlescent effects (see section 11.7).
10.3 Extrusion
Comparable with injection moulding in volume, extrusion is the other main polymer
processing method. It encompasses sheet, film and profile production and extrusion
coating. This process is well suited to metal pigments.
A uniform extrudate assists flake alignment. This provides one of the main attributes of
this technique, a uniform metallic effect. Brightness is assisted by any mono or biaxial
stretching that takes place. Flake particle size distribution is less critical, as the extrusion
process helps to align the particles parallel to the surface. Very large flakes should still be
avoided in the thinner films, as they can still cause pinholing.
10.4 Co-extrusion
Co-extrusion allows the core layers to be composed of different materials to the skins.
High opacity metal pigments with median particle sizes below about 10 µm can be used
in outer layers, where they will obliterate differently coloured core layers. Scrap or regrind
can then be more readily recycled in the core.Without special treatment, metal flakes
have limited barrier properties. Their use in co-extrusions therefore tends to be cosmetic
rather than functional.
10.5 Paint-less film moulding
Paint-less Film Moulding (PFM) is a new concept for the production of mass coloured
automotive body components without the costs associated with painting [4]. It was
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developed jointly by four industrial partners, BASF, Senoplast, Rohm and Engel, by
bringing together injection moulding, co-extrusion and thermoforming techniques. An
outer layer of abrasion and weather resistant PMMA acrylic is coextruded with
acrylonitrile/styrene/acrylate (ASA) copolymer or an ASA/PC blend. After thermoforming,
a backing polymer, such as ABS, polybutylene terephthalate (PBT)/PC or ASA/PC is
applied by injection moulding, using the thermoformed part as a mould insert.
10.6 In-mould decoration
There are several variants under this name involving both coating and mass pigmentation.
The principle governing both is that a thin, pigmented layer is inserted into an injection
moulding tool. Uncoloured virgin or reground polymer is then injected to bond to the
pigmented layer. The technique is only applicable to articles such as automobile wheel
covers that have a limited number of visible surfaces.
In-mould decoration by mass pigmentation involves insertion of a thin sheet or film into
the cavity of an injection mould tool. In the case of sheet, placement may be by robot.
Film is generally spooled through the tool. The mould faces are closed and molten polymer
injected. Under heat and pressure, the insert assumes the shape of the mould tool.
The advantage of this technique for metal flake pigments is that flakes can be oriented
by biaxial stretching during extrusion of the sheet or film. In this way a more uniform,
brighter visual effect, closer to that of a paint and free from flow and weld lines is
obtained. The thickness of the pigmented layer can be controlled through a wide range,
for example to provide stone chip resistance in wheel covers. These advantages help to
offset the higher cost of this technique over direct mass pigmentation.
10.7 Vacuum forming and thermoforming
These two related techniques are useful for metal flake pigments because they too eliminate
weld and flow lines. The extruded sheet starting material, with its oriented metal flakes,
offers increased brightness and uniform appearance. Very deep draws should be treated
with caution because non-uniform stretching of the sheet can alter metallic appearance.
10.8 Rotational moulding
Rotational moulding or rotomoulding is one of the fastest growing polymer processing

methods. It is a cost-effective alternative to blow moulding, especially for large mouldings.
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Very short production runs are economically possible. PE is by far the major polymer
used for this technique.
The process is particularly simple. A weighed quantity of plastic powder is heated inside
a closed mould that slowly rotates in two planes. The melting polymer forms a skin over
the mould’s inside surface. There follows a cooling phase during which the polymer
solidifies. The tool is then opened and the moulding removed.
Tooling costs are low since high pressures are not required. This also means stress free
mouldings. Versatile design options allow hollow shapes to be moulded without seams,
sprues, runners or ejector pin marks. Wastage is therefore also low.
Low pressures are an advantage where metal flakes are concerned, since flake damage is
minimised. The flake orientation is likely to be fairly uniform, but with little orientation.
Nevertheless, flow lines are minimised and with no converging melts, weld lines are
completely eliminated.
A potential disadvantage of the technique is that powdered polymer is used. Ideally the
metal flake is incorporated in the polymer powder, as a masterbatch route tends to
give poor uniformity. It is difficult to avoid flake damage as the compounded polymer
is powdered.
In practice, all sizes of metal flake are used. Large glitter flakes in coloured formulations
often give the best results in the large mouldings for which rotomoulding is most often
used. Concentrations are comparable to those of injection moulding.
10.9 Glass reinforced plastic
Bright metallic silver effects can be achieved in glass reinforced plastic (GRP) using non-
leafing aluminium flake pigment grades. A wide range of particle sizes and therefore of
visual effects is possible, from fine, smooth finishes with high opacity, to an attractive
sparkle. The technique tends to demand good pigment durability, both in service and
also because some of the components are acidic or otherwise aggressive to metals. Thus
higher purity, acid resistant metal pigments are generally specified. Small quantities of
organic or inorganic colorants may be added, providing their lightfastness and bleed
resistance are adequate.
Dry flake, plasticiser dispersions and granules formulated with solvent soluble carriers
can all be used. In the last category, aldehyde, ketone and hydrocarbon resin carriers are
all suitable. Formulation involves dispersion of any non-metallic pigments in the gel coat
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resin, which is usually styrene-based. Unless a predispersed colorant is used, this step
should be completed first, as high shear may be required for complete dispersion and
colour strength development.
For the best results, the metal pigment should be allowed to soak in the liquid GRP
medium for several hours with occasional gentle stirring. This allows sufficient time to
release and wet individual metal flakes. Dispersion is thereafter best achieved by low
energy stirring, using a slow speed blade capable of moving the whole mass. High shear
should be avoided as it bends and breaks the flakes, reducing their brightness. The
pigmented mix should be gently agitated before and preferably also during use to avoid
settlement of the metal flakes.
To produce the brightest effects, the metallic pigmented GRP resin should be applied to
the mould by spraying. This has the advantage of allowing the pigments to flow naturally
and has the additional benefit of ease of use. Application by brush will also give a metallic
effect, but may cause local differences in flake orientation and consequently an uneven
appearance.
The suggested sequence is an initial coating of the mould by a clear resin coat, followed
by application of the metallic pigmented resin layer and finally laying up with the fibreglass
reinforcing material. On ejection from the mould, the component should display a clean
metallic finish, comparable to a painted article. The quality of the visual effect will depend
on the thickness of the initial clear layer, the smoothness of application and the metal
pigment particle size and concentration. Brightness increases with loading up to colour
saturation. This could be 0.5-2% for a fine grade but 5-7% or more for a coarse type.
An alternative dispersion method involves the addition of acetone directly to the metal
pigment. This accelerates the dispersion process. When fully dispersed and homogeneous,
the premix can be added directly to the GRP resin.
Like rotational moulding, GRP is useful for manufacturing large structures incapable of
production by any of the other thermoplastic processes in this section. Use of metal flake
in GRP boat hulls has the incidental advantage of improving their visibility on radar.
10.10 Thermosetting polymers
Unlike thermoplastics, which can undergo any number of melting and re-solidification
cycles, thermosetting polymers, once reacted, cannot be re-melted.
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Metal pigments are not widely used in thermosets. One reason is that many such polymers
are inherently coloured, sometimes strongly so. As in similarly opaque elastomers, the
metallic effect is then diluted or even lost altogether.
For thermosets prepared from liquid components, dry flakes and plasticiser dispersions
can be used. Granules with resin rather than polymeric carriers are also suitable. Powder
precursors can be combined with dry flake or plasticiser dispersions.
References
1. Injection Moulding Handbook, 2nd Edition, Eds., Donald V. Rosato and

Dominik V. Rosato, Chapman and Hall, New York, 1995.
2. R. Knittel, Proceedings of the SPE Antec 96 Conference, Indianapolis, USA,

1996, Vol.I, 92.
3. H. G. Fritz, in Plastics Extrusion Technology, Ed., F. Hensen, Hanser Publishers,

Munich, 1988, 363.
4. Plastics and Rubber Weekly, 1998, No. 1750, 1.
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11
Applications of Mass Pigmented Systems
This chapter describes at the most common colouristic applications of metal pigments in
mass pigmented polymers. Non-colouristic applications are described in Chapter 15.
11.1 Household goods
Metal pigments, principally aluminium, are very effective in breaking up the uniform
appearance of large areas of solid colour, especially dark colours. There is increasing
interest in this technique in the teletronics market. Traditional black TV and video
cabinets are being subtly pigmented by metal pigments to give renewed customer appeal.
Most recently, the technique has spread to shavers and mobile telephones. Aluminium
flakes in the 20-60 µm range predominate. Many of these appliances require cut-outs
for switch and cable attachment, which are a source of flow and weld lines. These
challenges are being met by combinations of flake and spherical pigments and by
SCORIM (see Chapter 8).
Larger flakes are used in footwear, especially in thermoplastic elastomers for soles and in
trims for trainer shoes. Glitter flakes appear in transparent or tinted children’s sandals.
Their sparkling appearance increases the appeal of toys.
Pigmentation by coarser aluminium flake is also feature of larger articles, such as vacuum
cleaners, coffee makers, toasters, suitcases and the like. To mitigate the reduced opacity
of coarser pigments, they are generally formulated with organic and inorganic colours.
A selection of metal flake pigmented articles is shown in Figures 11.1.
Although more often surface printed, floor coverings are also pigmented by extrusion
coating over a foamed polymer substrate. The main advantage is uniform coloration
throughout a layer of increased thickness and therefore increased wear resistance [1].
For the garden, lawnmower and hedge trimmer housings, patio sets and hand tools are
produced with metallic finishes. Some are painted, the others pigmented. Many traditional
white patio sets are now coloured with low concentrations of black glitter flakes to give
a good contrast with the white.
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Figure 11.1 Metal flake pigmented mouldings
11.2 Sports goods
This is very definitely a fashion driven market. Styles therefore come and go in cycles. A
particularly prominent application for aluminium flake pigments in the mid 1990s was
ski boots. Coarse flakes in the 70-230 µm range were used with solid colours to provide
sparkle and avoid weld lines.
Bicycle parts and accessories, such as chain guards, mud guards, brake mechanisms and
cycle helmets are also mass pigmented by metal pigments. A key consideration for
functional parts is the effect of such pigmentation on mechanical properties. Chip
resistance is also important. Bicycle frames continue to be made from steel or lightweight
alloys and are increasingly painted with effect pigments.
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11.3 Agricultural film
The light reflecting and opacifying properties of aluminium flake pigments offer several
potential advantages in agricultural film applications. These include crop ripening, silage
wrapping and weed suppression.
Black, grey and white and pigmented plastic sheets were some of the first to be patented
for their plant mulching properties [2, 3]. Mica flakes for this application are claimed in
US Patent 3,099,897 [4]. An early use of aluminium flakes is disclosed in US Patent
3,382,610 [5], in which the flakes are combined with an asphalt binder.
PE film, mass pigmented by around 1% of a particularly fine particle size aluminium

flake pigment, has been spread on the ground under soft fruits. The reflection of sunlight
and heat by the metal flakes is believed to retard the rate of plant root development. This
has the effect of delaying the onset of ripening by a few weeks, providing a significant
commercial advantage. The more diffuse reflective properties of this type of film are said
to be an advantage over vacuum metallised film, which can concentrate the sun’s rays,
causing scorching of the plants. Although metal pigment offers some inherent UV
protection, UV inhibited polymer should be used to ensure maximum film life.
In a modification of this process, Fawcett [6] of Transmet Corporation patented a mulch

sheet to be placed on the soil around the stalk of a plant. The mulch comprises a woven
mesh with aluminium flakes which will reflect the sun’s rays up onto the underside of the
leaves. The mesh retains moisture that has seeped into the ground through the porous
mat. The aluminium flakes are applied to the upper tacky surface of thermoplastic woven
mat and pressed into position. They are fixed there when the polymer cools. A pod
containing a seed may be secured to the underside of the matting in the open hole. A
layer on the underside of the mat could include a layer of fertiliser.
In weed suppression film, fine grades of aluminium flake exclude light, but unlike black
pigmented films, which absorb heat and stimulate growth, aluminium flake pigmented
films appear to discourage weeds more effectively by reducing soil temperature. The use
of such film for wrapping silage for temperature modification to control storage properties
is a related potential application.
The main parameters affecting the service life of PE agricultural films are discussed by
Henninger [7].
11.4 Sacks and bags
This application area comprises rubbish bags, carrier bags and general flexible packaging.
Cost is the main factor in determining the products used. Both aluminium and gold
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bronze are employed, generally relatively low quality, wide particle size distribution
‘cornflake’ grades, in particle size in the range 5-12 µm diameter for maximum opacity.
Even the finest grades of metal flake do not compete on price with carbon black for
garbage bags. Applications tend to be restricted to the relatively up-market areas of
carrier bags, or where the non-pigmentary attributes of metal pigments are needed, i.e.,
light exclusion to hide the contents or light reflection to keep the contents cool.
11.5 Containers
Containers of all types are a major target for ‘effect’ pigments, particularly where their
use has a fashion component. Thus injection and blow moulded cosmetic and toiletry
containers, extruded toothpaste tubes and the like are frequently styled with metal
pigments. Containers for car engine oils are another major, though less fashion driven
outlet in this sector. Even PET beverage bottles have been launched which contain a low
concentration of a coarse, food contact grade aluminium flake.
Toiletry bottles are a popular application. This is at least partly due to reduced opacity
requirements. A rich, deep metallic effect can be obtained from a relatively low pigment
concentration, yet there is sufficient opacity to obscure the bottle’s contents.
Plant pots, tubs and containers are a consumer of ‘effect’ pigments, especially coloured
glitter flakes. These are formulated with white, cream, beige, pink and grey to provide
simulations of stoneware and marble (see section 11.8).
11.6 Automotive
It has been estimated that up to a quarter of the roughly 1,150 kg weight of a modern
mid-range car is made from synthetic polymers [8]. The largest element of this is the 125
kg comprising body parts, interior trim, instrument panels and headlights; all applications
in which visual quality is important.
Metal automotive components are increasingly being replaced by polymer, especially

where mechanical properties are not critical. Corrosion resistance and weight saving are
the two main driving forces for the use of polymers in general.
In addition, the need for a prestige appearance and the perceived strength attributes of
metals demand that polymers be made to look like metal. This applies not just to internal
and exterior trim components, but also to engine compartment parts such as air filter
housings and battery mountings. Thus, for example, Fritzsche describes metal pigments
for polyamide engine components, without surface marks, stable to 300 °C and required
to look like diecast aluminium [9].
126
Figure 11.2 Accelerator pedal; Nylon 66, pigmented by 2% of a 33 µm median

diameter aluminium flake pigment
A recent example of the replacement of a cast metal accelerator pedal by a metallic

pigmented polymer equivalent is shown in Figure 11.2. Skilful design allowed the necessary
mechanical properties to be retained with a considerable weight reduction.
Extension of metallic pigmentation to larger and more visible components is frequently

hampered by flow and weld lines and by the difficulty of colour matching to painted
body panels. One solution is to move to mass coloured body panels. This has already
occurred with the launch of a mass market automobile in China [10]. The so-called
‘Smart’ car, a joint venture between Mercedes Benz AG and the Swiss SMH AG company,
will feature easily replaceable, mass coloured body panels and bumpers [11].
The very new technique of paint-less film moulding, described in section 10.5, provides
the high quality of finish demanded by the automotive industry. The all-polymer panels
have high surface uniformity and brilliance, toughness, good long-term durability and
an attractive price/performance ratio to add to the obvious weight-saving advantage.
11.7 Pearl simulants
By reducing the concentration of very high quality, fine particle size, surface polished
aluminium flakes to very low levels in optically transparent polymers, it is possible to
achieve light reflection from deep within the polymer. This is a characteristic of pearlescent
(mica) pigments, which have much less inherent opacity than metal pigments.
127
Thus the visual effect of using 2-6% of pearl pigment may be reproduced from as little as
0.01 to 0.2% w/w aluminium flake. This ensures extremely cost-effective formulations.
It must be emphasised however, that because of the inherent colour of aluminium metal,
this approach is limited to silver and deeper coloured pearl effects. Aluminium flake
pigments are available that have been specially designed for this application. They will
typically have much lower metal contents than general purpose metallic pigment
masterbatch. This is to ensure the high degree of dispersion required at the very low
concentrations required. Toiletry and cosmetics containers are typical applications of
this approach.
11.8 Mineral simulants
The aim in this group of effects is to simulate in a mass pigmented polymer, the visual
effect of such minerals as granite and marble.
These formulations generally consist of two or more coarse metal flake pigments of
contrasting colour in a white or coloured background. Thus the black and white particulate
appearance of granite is simulated by a 200-600 µm diameter aluminium flake, mixed
with a black surfaced flake of similar dimensions. Chopped foil glitters can be used, but
the visual effect can look overly uniform. Milled flakes, with their irregular geometry
can often provide a more natural appearance. Lightly pigmented white, cream, ochre
and pink polymers with good surface gloss give the best results as hosts for the metals.
PMMA and PP are the popular choices. Because the hiding power of large flakes is so
low, a 1-2% loading of each may be required.
The technique can also be extended to the simulation of man-made products such as
stoneware. Together with the mineral simulations, these effects are found in resin bonded
laminate sheets for kitchen and bathroom work surfaces and in plastic flower pots, tubs
and other garden applications [12, 13].
11.9 Fibres and textiles
Due to their very much larger size compared to organic and inorganic pigments, metal
pigments have limited application in fibres. Indeed the diameter of a fibre strand can be
less than that of many flake pigments. At the very least, mechanical strength is lost.
Brightness and metallic effect are also compromised because only the smallest and therefore
darkest flakes can be used. Nevertheless, Blechschmidt [14] has described the preparation
and properties of polyolefin tape yarns, coloured by metallic coloured masterbatches
during extrusion.
128
A more common application involving textiles is coating onto a textile substrate for the
manufacture of synthetic leather, or leathercloth. The coating is generally a PVC plastisol,
applied by knife coating and thermally cured.
References
1. C. Cussot and D. Delage, inventors; Societe Francaise Bitumastic SA, assignee,

European Patent 296,976 A1, 1988.
2. H. A. Lemaire and C. d’Azergues, inventors; US Patent 3,252,250, 1964.
3. N. J. Smith, inventor; US Patent 3,955,319, 1976.
4. H. A. Letteron, inventor; General Electric Company, assignee, US Patent

3,099,897, 1961.
5. R. L. Ferm, inventor; Chevron Research, assignee, US Patent 3,382,610, 1968.
6. S. L. Fawcett, M. S. Fawcett and D. L. Cullen, inventors; Transmet Corporation,

7. F. Henninger and E. Pedrazzetti, The Arabian Journal for Science and

Engineering, 1988, 13, 4, 473.
8. K. Grace, British Plastics & Rubber, 1996, November, 26.
9. T. Fritzsche, W. Pankewitz and P. Wolf, Kunststoffe, 1997, 87, 3, 297.
10. M. C. Gabriele, Modern Plastics International, 1998, 28, 8, 28.
11. Financial Times, 1997, 1st July, No. 33331, 16.
12. M. Yoshioka and H. Fukuda, inventors; Tochu Plastic Kogyo KK, assignee,
Japanese patent 01/14138, 1987.
13. Kawanami and Yasutaro, inventors; assignee unknown, JP 02170847, 1988.
14. D. Blechschmidt, W. Kittelmann and H. Halke, Chemical Fibers International,

1996, 46, 5, 352.
129
12
Metal Pigmented Coatings
The volume of coatings for the decoration and protection of plastic substrates (excluding
automotive OEMs) has been estimated at 52 million litres in Europe in 1997, with a
growth rate of 5-10% per annum [1]. Automotive plastics OEMs add perhaps another
30-50 million litres. The major players are Akzo Nobel, BASF, Du Pont, Herberts, NPA,
PPG Industries, Sonneborn & Rieck, Verilac and Weilburger, with applications in
automotive, teletronics and building products. This chapter considers metal pigmented
coatings incorporating polymeric components as well as coatings specifically on polymer
substrates.
West [2] has produced a useful summary of the problems involved in painting on various
polymers for automotive applications, especially those connected with on-line painting.
Factors affecting adhesion to elastomer modified PP are discussed. Adhesion of paints to
plastics was also the theme of a workshop in the USA [3].
A successful coating is heavily dependent on the formulation of the coating vehicle, be it

ink or paint, as well as its application to the substrate. Although metal flake pigmentation
influences film properties, formulations developed for organic and inorganic pigmented
coatings can usually be readily modified to accommodate the unique physical and chemical
characteristics of metal pigments.
12.1 Substrate preparation
Another key requirement for a durable coating is good surface preparation to provide
satisfactory adhesion of the coating when dry. Adhesion is particularly problematic on
low energy polymer substrates, such as polyolefins, but several techniques exist to activate
them to receive and bind the coating. These include flame treatment which is popular in
Europe, corona discharge and also chemical treatments involving permanganates and
chromates. However, these latter materials, widely used in the USA, are coming under
environmental pressure.
Adhesion to metal substrates can be improved by degreasing with solvent or by laying

down a primer coat, as in the case of automotive coatings.
131
12.2 Coating formulation and properties
12.2.1 Pigment particle size
The relationship between pigment particle size and film thickness has an influence on
surface texture and gloss of the coating. Flakes whose diameters are larger than the dry
film thickness orient poorly, especially if their concentration is too high. In the extreme
they can protrude through the film surface, causing a noticeable reduction of gloss and
DOI. The problem is exacerbated by ‘seeds’, i.e., three-dimensional aggregates of flakes,
a phenomenon described by Knowles [4] and shown in Figure 12.1.
Figure 12.1 The origin of metal flake pigment seeds in a coating
In some ink processes, the very much larger dimensions of metal flake pigments restrict
the range that can be accommodated. In gravure for example, particles with any dimension
larger than about 25 µm will block the cells of the print cylinder, thereby reducing
definition. Metal flake pigments offered for ink applications, with the exception of the
screen process, tend to have fairly tight particle size distributions, with median diameters
around 8-15 µm and few coarse flakes. Grades up to 100 µm can be used in screen
printing, given an appropriate choice of screen mesh size.
12.2.2 Concentration
The much greater density and particle size of metal pigments compared to organic and
inorganic pigments dictate much higher loadings to achieve sufficient opacity. Whilst
automotive paints can have aluminium flake concentrations of 4-6% of formulation,
typical aluminium pigment loadings in inks are around 15-20%. Gold bronze inks can
require loadings of 40% or more and pure silver, at the high end of the density spectrum,
even higher loadings.
132
12.2.3 Leafing and non-leafing
Of the several properties of metal pigments which only assume relevance in coating
applications, leafing and non-leafing are arguably the most important. The terms describe
the orientation of metal flake pigment particles in a liquid coating system. This in turn
determines their appearance and applications. Information about manufacturing processes
for these pigment types can be found in Chapter 3 and a description of their properties in
section 4.3.4.
An integral part of formulations incorporating metal flakes is careful selection of the

vehicle. This is generally dictated by the end use of the coating system. Exterior versus
interior use, chemical and moisture resistance and drying speed are a few of the factors
to be considered. Formulation with leafing flake pigments demands that components are
used that will not adversely affect the ability of the flakes to leaf. In practice this means
relatively non-polar, low acid number species.
Use of leafing pigments somewhat limits solvent choice. Aliphatic and aromatic hydrocarbons
are preferred. It is important to avoid low molecular weight, polar types if leafing stability is
to be maintained. Polar solvents, such as lower acetates, ketones and to a lesser extent alcohols
will remove the thin fatty acid coating from the flakes and with it the ability of the flake to
leaf. If toluene or xylene is permitted in the formulation, leafing will be improved. The same
result is achieved by increasing the surface tension of the solvent.
Non-leafing flake pastes are rather less stringent in their compatibilities. As leafing ability
is not an issue, the choice of solvent is more likely to be limited by compatibility with the
resinous or polymeric film forming component.
12.3 Dispersion and incorporation
A clear understanding of dispersion and incorporation techniques is fundamental to

achieving optimum visual quality from a metal pigmented coating. Any attempt to apply
the principles used for organic and inorganic pigments will be disastrous.
Non-metallic pigment particles for example are sub-micron in size and often difficult to
deform during dispersion. Indeed some high energy dispersion equipment such as ball
mills, sand mills or high-speed dispersers are necessary to separate aggregates into primary
pigment particles and develop full colour strength.
Because metal pigments are fragile, the use of high energy dispersion techniques should
be avoided. Ball milling or sand milling completely destroys the integrity of the flake,
resulting in a much finer particle size, darker, non-metallic finish. High-speed dispersion
133
equipment, such as sawtooth bladed or rotor/stator dissolvers should also be avoided.

When running at high speed they will deform the flakes by fracturing, folding and bending.
When this occurs, the resulting coating will be more grey, exhibit less hiding and may
also generate seeds by cold welding. The colour loss is due to a change of orientation of
flake in the film. Loss of hiding and grittiness are related to flake deformation and the
resulting change in the flake surface area.
The recommended procedure for dispersion of a metal flake paste is to add it to a mixing
vessel fitted with a slow speed, paddle bladed agitator capable of moving the whole
mass. To the paste is added one to two times its weight of vehicle or preferably solvent.
Where possible a soaking period of a few hours is beneficial to the dispersion process.
This is especially true for leafing pastes and smaller flake sizes. Slow speed mixing will
then reduce this mixture to a thick creamy consistency. At this point most of the flakes
will be separated from one another by a layer of solvent or vehicle. When this consistency
has been achieved with no soft agglomerates present, further reduction with solvent or
vehicle can take place. Using this technique will greatly reduce dispersion difficulties and
minimise related problems.
12.4 Application to the substrate
Though some modification of conditions may be required, metal pigmented coatings can
be applied by almost all the techniques employed for metal free compositions. Sprayed
coatings may require a gun with a larger nozzle diameter and printing equipment needs
to take account of large flakes as noted in section 12.2.1.
12.5 Solvent-based systems
As metal pigments are routinely manufactured by a solvent process, their incorporation

in solvent-based coating systems is fairly straightforward. The main issue to consider is
whether the non-metal components are compatible with the constituents of the coating
system. For traditional solvent-based pastes, this means aliphatic, aromatic or mixed
aliphatic/aromatic hydrocarbons.
To reduce the odour in printed films and speed up drying, metal pastes are widely supplied
in faster, i.e., more volatile solvents. The penalty is the tendency of such pastes to dry
out and aggregate more rapidly than conventional types.
The granular form overcomes these difficulties, as well as offering easy handling.
Aluminium and gold bronze granules are available with aldehyde, ketone or acrylic
134
carriers (see also sections 5.5 and 13.2.1). These versatile products are suitable for a
wide range of solvent-based paints and inks. In the case of gold bronze, stability is
enhanced by using resins of low acid number. This restricts carrier choice to the aldehyde
and ketone types.
Ferguson [5] has produced an account of the manufacture and use of metal pigments in
paints, including details of test methods.
12.6 Water-based systems
Water-based media present considerable challenges to the application of both aluminium

and to a lesser extent, gold bronze and zinc pigments. The main problem to be overcome
is the tendency for chemical reaction. Aluminium in contact with water is afforded some
limited protection from the inert oxide coating and traces of fatty acid lubricants left
from the manufacturing process. Also, in general, the purer the metal, the more resistant
it is. After a few hours at ambient temperature however, hydrogen gas is generated
according to the equations:
2Al + 3H2O = Al2O3 + 3H2
and 2Al + 6H2O = 2Al(OH)3 + 3H2
Apart from being highly flammable, hydrogen causes a build up of pressure in the container
of paint or ink, creating a secondary hazard.
Aluminium pigment manufacturers have developed a simple test for gas generation. The
apparatus is shown in Figure 12.2. A 200 g sample of the coating containing the aluminium
flake pigment is placed in an Erlenmeyer flask, ensuring that none coats the neck. The
flask, with the stopper securely inserted, is placed in a bath maintained at 50 °C. The
water level in the burette is adjusted to the 100 ml mark and the temperature allowed to
equilibrate for at least an hour. At the end of this time, the water level in the burette is
noted. This is the zero point from which subsequent measurements are made. The test is
normally conducted for at least one week, recording the water level daily. It is important
to control the ambient air temperature to avoid volume measurement errors.
Gas generation of less than 10 ml in this period is generally considered a satisfactory

result for an automotive coating. Industrial finishes can tolerate higher levels. For each
test material, it is good practice to simultaneously run a control sample of known
gassing characteristics.
135
Figure 12.2 Gas generation testing apparatus
A considerable effort has been made by all the major metal pigment manufacturers to
find means of inhibiting or passivating metal pigments, especially aluminium, against
aqueous attack. A full survey of the dozens of literature references and patents in this
field is outside the scope of this book. Instead a brief summary is presented of all the
major techniques. These can be divided into organic inhibitors, inorganic or organometallic
treatments and encapsulation by resins or polymers.
Brown and Rolles [6, 7] discovered that merely mixing a few percent of nitro derivatives
of aliphatic or aromatic hydrocarbons or 3- or 5-nitro salicylic acid into an aluminium
paste increased its water resistance.
Toyo Aluminium [8] claimed enhanced aqueous performance by replacing the

conventional lubricant in the wet milling process by dimer acids, derived for example
from oleic or linoleic acids.
Inorganic treatments create a deposit of one or more inorganic salts by chemical reaction
from solution. Oxides of chromium, precipitated from ammonium dichromate, are
particularly effective [9, 10, 11, 12]. Such treatments are coming under increasing
environmental scrutiny, due to the difficulty in removing traces of Cr6+. The EC Waste
Packaging Directive, 94/62/EC [13], requires that hexavalent chromium levels in packaging
do not exceed 100 ppm from 2001. Eckart-Werke [14] in Germany continues to offer
chromium oxide inhibited aluminium flake pigments under the Hydrolux trade name.
136
Other inorganic or organometallic passivation processes involving molybdenum [15,

16], phosphorus [17, 18, 19, 20, 21, 22, 23, 24], silicon [25], titanium [26], cerium [27,
28] and vanadium [29, 30] have all been the subject of patent applications. Of these,
silicon and phosphorus are most used commercially.
A passivation mechanism involving metal pigment treatment with chromium, vanadium

or phosphorus compounds in the gas phase is the subject of a patent to Schmid of BASF
[31]. Indeed BASF was a pioneer of gas phase reactions on metal flakes maintained in
motion by means of a fluidised bed.
Encapsulation processes involve numerous compounds, oligomers and polymers, precipitated

from solution or created at the flake surface, for example by polymerisation. Banba [32]
describes an encapsulant for aluminium flake containing vinyl and epoxy functionality. Eckart-
Werke [33] claimed a siloxane, covalently bonded to the surface of aluminium flake, and a
three-dimensionally cross-linked synthetic resin coating covalently bonded to the siloxane. A
nitro substituted polymeric coating for aluminium flake is employed by Carpenter [34],
whilst Iri [35] disclosed a reaction of isocyanate and phosphorus compounds for the protection
of aluminium and gold bronze. A stable, high solids metal flake pigment dispersion is provided
by Chang [36] by neutralising a phosphated acrylic polymer.
In addition to the above, there are a few techniques for surface modification of the
aluminium flake which attempt to capitalise on the limited degree of protection afforded
by the natural oxide surface and traces of lubricant remaining from the production process.
Preparing an alloy of aluminium with other metals as a means of improving water

resistance has also been examined. Uchimura at Toyo [37] applied for a patent for an
alloy of aluminium, zinc and silicon, with minor amounts of indium or tin.
Much recent work on the mechanisms of aluminium flake stabilisation has been published
by Müller in Germany. The rate of the corrosion reaction was followed by measuring the
volume of hydrogen evolved.
In studies of mono, di, and polysaccharides and related hydroxycarboxylic acid

compounds, strongly reducing enediols, such as ascorbic acid or glycolaldehyde were
found to be the most effective gassing inhibitors [38]. They also retained good colour in
coatings, unlike phenolic based inhibitors. Ortho substituted phenol derivatives, especially
salicyl alcohol, are nevertheless effective in water-butyl glycol mixtures at pH 10. In
contrast, ortho substituted anilines offered no passivation [39].
Esters of gallic acid increased in passivation activity with increasing chain length [40].
Hydrogen evolution of styrene-maleic acid copolymer inhibitors could be correlated with
the acid number, lower acid numbers and higher molecular weight being most effective
137
[41]. Such copolymers were very much more effective than high molecular weight
polyacrylic acids. As expected from other studies, analysis revealed some formation of
partially soluble aluminium salts of the polymers [42].
Inhibition is enhanced in alkaline media but overall the effect of the pH of the system is
variable [43]. For low molecular weight (<60,000) styrene maleic acid copolymers, stability
is greater at pH 8 than at pH 10. At higher molecular weights, (>100,000) the effect is
reversed [44]. The isoelectric point (IEP) of aluminium oxide (~pH 9) is significant in
controlling the corrosion inhibiting effect of polyacrylic acid in alkaline media. Above
the IEP (pH 10) high and low molecular weight polyacrylic acids inhibited corrosion, the
effectiveness decreasing with increasing molecular weight. Below the IEP (pH 8), low
molecular weight material showed inhibition, but less effectively than at pH 10. Again
effectiveness decreased with increasing molecular weight. High molecular weight polymer
at pH 8 actually stimulated corrosion [45].
Some other classes of resin also show some corrosion inhibiting ability. Alkyd resins
showed good inhibition at pH 10. There is some effect from epoxy resins, and oil free
saturated polyesters were found to be the poorest of the resin classes examined [46].
The solvency of the inhibitor is important. Water soluble and ionomer dispersions tend
to inhibit corrosion better than emulsions. Certain functional groups, notably carboxy,
phenolic hydroxy and longer chain unsaturated alkyl groups, are also more effective
[47]. The passivation activity of phenolic resins is rationalised by improved adhesion to
the metal surface through formation of a surface-chelate complex [48].
A common feature of all inhibiting agents for aluminium is specificity. The inhibited
metal flake product which is highly resistant to gassing in one commercial paint or ink
medium may fail rapidly in another. At the time of writing, there is no 100% reliable
inhibited aluminium pigment on the market. This reflects the difficulty of entirely inhibiting
every flake surface. Although the evidence is circumstantial, the gassing reaction appears
to be capable of being initiated by very few partially coated or uncoated flakes. The
oxidation reaction is so exothermic that adjacent flakes are attacked. If the heat cannot
be easily dissipated, as for example when product is tightly packed in a sealed drum,
catastrophic failure can occur. Unless fitted with a vent plug, the drum will then bulge or
even rupture due to the pressure of the generated hydrogen gas. For this reason, aluminium
flakes intended for water-based applications are best not carried in water.
The recent introduction of dry granular product forms to the market overcomes this
problem. Carriers include non-ionic surfactants, intended for inks, and polypropylene
glycol, used for paints. Of other commercially available product forms, pastes in water
compatible solvents, such as alcohols, are the most prominent (see also Chapter 5). The
popular isopropyl alcohol appears to offer some inhibition of gassing, but for total
reliability in aluminium pastes, some extra passivation of the metal is desirable.
138
Passivation of gold bronze is a less important issue due to the inherently lower chemical
reactivity of its copper and zinc constituents. This is reflected in the lack of both patents
and literature on the subject. Coating with silica is widely practised as a means of
improving tarnish resistance in general.
Combining metal powder, particularly zinc, with a polymerisable monomer and spray
drying gives a pigment with greater resistance in aqueous lacquers [49].
Inhibition of hydrogen evolution in an aqueous alkaline, zinc pigmented paint medium

was also investigated by Müller. Propyl, octyl and dodecyl gallate were shown to be
good inhibitors, as were oligomeric phenolic resins, the latter through chelation to zinc(II)
[50]. In contrast, citric acid accelerated hydrogen generation in alkaline media. Some
metal salts are effective as inhibitors, the most notable being cerium(III) chelates of citric
acid. In this case, however, the pronounced inhibiting effect could be ascribed to the
cerium rather than the charge of the chelates [51].
12.7 UV/EB cured coatings
UV curing has emerged as a coating technique in the last 20-30 years. It currently represents
only 1% of the total European coatings market and 3% of the inks market [52]. Electron
beam (EB) curing is a higher energy technique, still in its commercial infancy. A
comprehensive introduction to radiation curing technology in general is provided by
Holman and Oldring [53].
The key advantage of both techniques is that they are VOC free, i.e., all the coating
applied to the substrate is retained after cure. No heat is required, making them useful
techniques for plastic substrates. Curing, which is virtually instantaneous, is effected by
a polymerisation of liquid monomers, initiated by an artificial UV light source. Such
radiation curing systems are environmentally friendly, but the monomers are expensive
and there are concerns over the perceived toxicity of some of the active components.
It is a popular misconception that metal pigments cannot be used in UV systems due to

inhibition of through-curing. What is true is that unprotected metal flake surfaces,
especially aluminium, catalyse cure in the absence of any source of UV energy. For this
reason, metal pigmented coatings are offered as either ‘one pack’ or ‘two pack’ systems.
For the former, the metal flakes are prevented from causing premature cure by resin or
inorganic compound encapsulation. For the latter, unprotected flakes are used, but they
are supplied separately from the monomer and photoinitiator system. The two components
are brought together immediately before use. At ambient temperatures, the ready-to-use
coating will remain usable for 6-24 hours, depending on metal purity, concentration and
139
flake size. High loadings of more active aluminium metal, in fine particle sizes,
corresponding to high surface area for reaction, have the shortest pot life. In contrast,
inhibited one pack types can provide usable coatings that can be stored for many months,
even years, providing light is excluded from the pack. Indeed to prevent premature curing,
all active UV formulations must be stored in opaque, preferably plastic, containers.
Metal pigment product forms available in the market and appropriate for UV/EB cured
coatings, are dry flakes and also stiff pastes in which the carrier is an inert diluent
component of the formulation. A fatty alcohol is used by at least one manufacturer.
Granular forms may also be used, providing the carrier will dissolve in the other
components and does not interfere with application properties.
In practice it is difficult to attain the visual quality of conventional liquid coatings from
a UV curing system. The reasons for this are not fully understood, but are at least partly
due to higher application viscosity and lack of flake orientation. As there is no loss of
volatiles, there is no mechanism to align flakes parallel to the surface to increase reflectivity
as would occur in a conventional liquid coating. For these reasons, high quality,
particularly reflective flake pigments must be used. This further reduces the competitiveness
of UV systems versus their liquid counterparts. Overall, however, the attractions of the
technology outweigh the disadvantages, as evidenced by the continuing growth of the
metallics UV market.
References
1. The Coatings Agenda Europe, 1997, 81.
2. E. J. West, Proceedings of a Symposium on Coatings for Plastics, Harrogate, UK,

1986, Paper No.9.
3. Adhesion of Paints to Plastics Workshop, Presented at Adhesion and Coupling

Agent Technology 97, Boston, USA, 1997, Intertech Conferences.
4. R. Knowles, Polymers Paint Colour Journal, 1991, 181, 4297, 714.
5. R. L. Ferguson, Paint and Coating Test Manual (Gardner-Sward Handbook 14th

Edn.), Ed., J. V. Koleske, ASTM, 1995, 223.
6. M. H. Brown, inventor; Aluminium Company of America, assignee, US Patent

2,848,344, 1953.
7. M. H. Brown and R. Rolles, inventors; Aluminium Company of America,

140
8. E. Uchimura and Y. Hashizume, inventors; Toyo Aluminium KK, assignee, GB

Patent 2,043,092, 1980.
9. R. L. Hawkins, Jr., G. Mills and E. G. Bobalek, inventors; The Empire Varnish

Company, assignee, US Patent 2,904,523, 1955.
10. J. A. DeRidder, inventor; Diamond Shamrock Corporation, assignee, US Patent

3,940,280, 1976.
11. T. Higashiyama and T. Nishikawa, inventors; Diamond Shamrock Corporation,

12. T. Kondis, inventor; Silberline Manufacturing Co., Inc., assignee, US Patent

4,693,754, 1987.
13. Coatings COMET, 1998, 6, 1, 63.
14. R. Besold, W. Reisser and E. Roth, Pitture e Vernici, 1991, 67, 10, 9.
15. S. Setoguchi, H. Katoh and T. Matsufuji, inventors; Toyo Aluminium KK,

16. T. Yamamoto, M. Uenishi, H. Katoh and S. Setoguchi, inventors; Toyo

Aluminium KK, assignee, US Patent 5,494,512, 1996.
17. S. Ishijima, Y. Hayashi and T. Kiritani, inventors; Asahi Kasei Kogyo KK,
assignee, GB Patent 2,053,258 B, 1979.
18. T. Kondis, inventor; Silberline Manufacturing Co., Inc., assignee, US Patent

4,808,231, 1989.
19. T. Kawabe, T. Bamba, T. Matsufuji, H. Ueshimo, Y. Hashizume, E. Uchimura, M.

Harasada, M. Aoki and T. Kimura, inventors; Toyo Aluminium KK, assignee, US
Patent 4,869,754, 1989.
20. R. Schmid, N. Mronga, H. Keller and J. A. G. Gomez, inventors; BASF AG,

21. C. Keemer, W. G. Jenkins, H. T. Lamboin and J. B. Scheller, inventors; Silberline

Manufacturing Co., Inc., assignee, US Patent 5,215,579, 1993.
22. W. G. Jenkins, C. Keemer, H. T. Lambourn and M. Curcio, inventors; Silberline

141
23. W. G. Jenkins, C. Keemer, H. T. Lambourn and M. Gurcio, inventors; Silberline

24. C. B. Keemer, W. G. Jenkins, H. T. Lambourn and J. B. Scheller, inventors;

25. R. Schmid, N. Mronga, H. Keller and J. A. G. Gomez, inventors; BASF AG,

26. W. Ostertag and N. Mronga, inventors; BASF AG, assignee, US Patent

4,978,394, 1990.
27. J. S. DePue, C. W. Carpenter and L. G. Bemer, inventors; BASF Corporation,

28. J. S. DePue, C. W. Carpenter and L. G. Bemer, inventors; BASF Corporation,

29. C. B. Keemer, W. G. Jenkins, H. T. Lambourn and J. B. Scheller, inventors;

30. T. Kondis, inventor; Tom Kondis, assignee, US Patent 4,693,754, 1987.
31. R. Schmid, N. Mronga and J. A. G. Gomez, inventors; BASF AG, assignee, US

Patent 5,352,286, 1994.
32. T. Banba, inventor; Toyo Aluminium KK, assignee, US Patent 4,434,009, 1984.
33. W. Reisser and G. Sommer, inventors; Eckart-Werke, assignee, US Patent

5,332,767, 1994.
34. C. W. Carpenter and J. M. De Haan, inventors; BASF Corporation, assignee, US

Patent 5,389,139, 1995.
35. K. Iri and M. Suzuki, inventors; Asahi Kasei Metals Ltd., assignee, US Patent
5,272,223, 1993.
36. D. C. K. Chang, inventor; E. I. Du Pont de Nemours & Co., assignee, US Patent

5,104,922, 1992.
37. E. Uchimura, inventor; Toyo Aluminium KK, assignee, British Patent

2,147,310, 1984.
38. B. Müller and M. Kurfess, Werkstoffe und Korrosion, 1993, 44, 9, 373.
142
39. B. Müller, British Corrosion Journal, 1996, 31, 4, 315.
40. B. Müller, M. Müller and I. Lohrke, Farbe Lack, 1994, 100, 7, 528.
41. B. Müller, Journal of Coatings Technology, 1995, 67, 846, 59.
42. B. Müller and T. Schmelich, Corrosion Science, 1995, 37, 6, 877.
43. B. Müller and U. Davidowski, Coating, 1995, 28, 9, 345.
44. B. Müller and A. Holland, Materials and Corrosion, 1997, 48, 2, 95.
45. B. Müller and U. Dawidowski, Materials and Corrosion, 1996, 47, 3, 154.
46. B. Müller and A. Holland, Surface Coatings International, 1997, 80, 7, 321.
47. B. Müller, T. Schmelich and M. Gampper, Farbe Lack, 1995, 101, 2, 101.
48. B. Müller, Adhasion Kleben & Dichten, 1996, 40, 12, 32.
49. E. Weiderhold, inventor; no assignee, GB Patent 1,115,338, 1965.
50. B. Müller and I. Förster, Corrosion, 1996, 52, 10, 786.
51. B. Müller, W. Kläger and G. Kubitzki, Corrosion Science, 1997, 39, 8, 1481.
52. J. Kerr and B. Seath, Proceedings of Radcure Coatings and Inks: Application and
Performance, Harogate, UK, 1996, Paper No.5.
53. UV and EB Curing Formulation for Printing Inks, Coatings and Paints, Eds., R.
Holman and P. Oldring, SITA Technology, London, 1988.
143
13
Applications of Metal Pigmented Coatings
The main application areas for metal pigmented coatings are described here.
Representative starting-point formulations are provided for the most common coating
types. They are intended as general guidance and are not optimised for any given
application. Polymers feature as substrates, binder components, or sometimes both.
13.1 Painting
Coating polymer substrates is the alternative to the mass pigmentation options described
in Chapter 11. The strengths and weaknesses of the two techniques are covered in
Chapter 6.
World Paint File 1998-2002 [1] provides an overview of production and consumption
trends and applications, plus market forecasts from 30 leading global paint makers. The
market penetration of conventional solvent-based, water-based, powder coat and radiation
cured coatings in Europe is described in Coatings Agenda [2]. Water-based coatings are
estimated to have 11.6% of the market share in Europe, almost the same as in the USA
and Japan. Conventional and high solids solvent-based paints together account for almost
three-quarters of consumption. Thus, penetration of the aqueous coatings market has
not been as rapid as anticipated in the early 1990s.
Paint application areas for metal pigments, specifically on polymer substrates, include
automotive trim components, teletronics and domestic appliance housings; indeed many
of the same applications being explored by mass pigmentation. Both solvent-based and
water-based formulations are used, though the latter must take account of the water
sensitivity of some metal pigments, as discussed in section 12.6. Other coating applications
make use of the protective and anticorrosion properties of some of the metals.
Efficient pre-dispersion of the metal flake, described in section 12.3, is a prerequisite for
a high quality finish. This is irrespective of the application or the metal pigment delivery
form. Ferguson [3] gives formulation guidelines for both leafing and non-leafing
aluminium pigments in paints and inks.
In considering the application of coatings to polymer substrates, adhesion is a key concern.

PP is the polymer of choice for many high volume applications involving metallic paints.
145
To achieve satisfactory adhesion onto such low energy surfaces, the surface must be
activated, for example by corona discharge. In this respect, the subsequent application
of a metallic coating is no different to that of a coating free of metal pigment.
Silanes, titanates and more recently zirconates have been employed to aid adhesion. Du
Pont [4] have patented an alkyl titanate for the purpose.
13.1.1 Solvent-based paints
Metal flake pigment in the traditional hydrocarbon solvent paste form is generally suitable
for solvent-based paints, especially where aromatic solvent has enhanced the solvency of
the paste. It is this form that is widely used in automotive formulations. A basecoat
formulation suitable for both OEM and refinish is shown in Table 13.1. It is applied to
an approximately 15 µm thickness and overcoated with a clear film some 40 µm thick.
For general industrial coatings where a single coat suffices, Table 13.2 shows a typical
formulation, again using a medium-fine aluminium paste.
Hammer finishes are an other important outlet for aluminium flakes. Their function is
protective as well as decorative. A silicone additive generally provides the distinctive
mottled effect (see Table 13.3). Applications include metal fences and railings and to
provide an antique gold effect, for example on gas and electric fires.
Fine and medium-fine grades of both aluminium and gold bronze are used in aerosol
paints. A starting point formulation for the latter is reproduced in Table 13.4.
A simple formulation to provide paint suitable for application by brush, for example in
modelling paints and general gilding simulation work, is provided in Table 13.5.
The advantages of a dry, granular form of metal pigment, so familiar to ink makers, are
now being recognised by paint makers. Formulations are adjusted for the generally higher
metal content of granules and for the presence of carrier that will replace an equal weight
of resin in the formulation.
146
Table 13.1 Silver metallic basecoat formulation for OEM or refinish

Polyester resin 17.4%
Melamine resin 13.7%
CAB (cellulose acetate butyrate) resin, 31.5%
20% solution in n-butyl acetate
Polyethylene wax, 10% dispersion in 5:4:1 xylene:n-butyl acetate:isobutanol 25.2%
Aluminium flake pigment paste (NV (non-volatile content) = 65%; 12.2%
D50 = 15 µm), dispersed 1:1 in 2:1 butyl acetate:xylene
The resin solutions and wax dispersion are combined in a high-speed disperser and filtered to
remove any gelled particles. The metal dispersion is mixed in with gentle agitation and the system
diluted to a spray viscosity of 15 s, DIN 4, using 2:1 butyl acetate:xylene. The paint should be
filtered again before use.
Table 13.2 One coat silver industrial stoving paint

Short-oil, non-drying alkyd (70% in xylene) 50.0%
Melamine formaldehyde resin (65% in n-butanol) 15.0%
Xylene 13.0%
n-Butanol 3.0%
2-Butoxyethanol 5.0%
Aluminium flake pigment paste (NV = 64%; D50 = 16 µm), 14.0%
dispersed 1:1 in xylene
Resins and solvents are combined to form a smooth dispersion, to which the aluminium
flake dispersion is added with gentle paddle agitation. The paint is thinned to 20 s in a
Ford No.4 cup with a blend of 4:1 xylene:n-butanol before use.
Table 13.3 Silver industrial hammer finish paint

Aluminium flake pigment paste (NV = 65%; D50 = 30 µm), 20.0%
dispersed 1:1 in xylene
Styrenated alkyd resin (60% in xylene) 79.7%
Silicone oil 0.2%
Cobalt drier 0.1%
The aluminium flake dispersion is added to the resin solution with gentle paddle agitation.
Silicone oil and cobalt drier are stirred in and the paint thinned with ethyl acetate, butyl
acetate, xylene, or a mixture of these, to 20-30 s spraying viscosity in a Ford No.4 cup.
147
Table 13.4 Gold bronze aerosol paint

Acrylic resin (65% in xylene) 6.5%
Toluene 10.5%
Xylene 18.0%
Acetone 50.0%
Rich pale, extra fine lining paste (NV = 85% in white spirit; D50 = 6 µm), 15.0%
dispersed at 2:1 in xylene
The bronze pigment premix is gently stirred into a dispersion of the remaining components.
Table 13.5 Gold bronze brushing paint

Polyurethane alkyd varnish (65% in xylene) 70.0%
Rich, fine lining paste (NV = 85% in white spirit; D50 = 11 µm) 30.0%
The gold bronze pigment paste is gently combined with the varnish and white spirit
added to application viscosity, whilst under agitation.
13.1.2 Water-based paints
Paint manufacturers have been active in the passivation of metal flake pigments. A patent
to Nippon Paint [5] discloses surface treatment of aluminium, copper or zinc by aqueous
phosphorus or vanadium ions. A related patent [6] claims a phosphated aluminium flake
pigment and derived water-based paint for automotive finishes.
Frangou and Backhouse [7, 8, 9, 10] at ICI researched vinyl and addition polymer resins
containing phosphorus, optionally as a metal salt. These are used to passivate aluminium
flake pigment in aqueous automotive basecoats. Resin formulations are tailored to improve
adhesion between basecoat and clearcoat.
The Eastman Kodak Company [11] patented an aqueous metallic coating containing a
cellulose mixed ester and a compatible amine neutralised acrylic resin. Cellulose esters
impart improved metallic orientation, solvent release and high gloss. The acrylic resin
contributes strength and hardness in the final film.
Anderson at BASF [12, 13] described a two pack system in which unpassivated
aluminium flake was retained in solvent and added to the water-based resin system
immediately before use. The vehicle is a water reducible acrylic latex, with non-ionic,
acid or urethane functionality, plus a rheology control agent. The resulting paint is
intended for automotive use.
148
Anionic PU and acrylic resins, formulated with aluminium pigment inhibited by a

phosphate ester, have also been patented by BASF [14] for automotive use.
A stable, water-borne, high solids, metal flake pigment paint, incorporating a neutralised
phosphated acrylic film former, was patented by Chang of Du Pont [15]. An alkylated
melamine formaldehyde polymer provides cross-linking.
Outside the patent literature, the large paint companies tend to guard their formulations,
making it difficult to provide specific guidance. Nevertheless, there are a few ground
rules. A pH range from 5-9 is desirable, with 7.5-8.5 preferred. Gassing can be expected
to become more of a problem in aluminium flake pigmented systems the further the pH
moves away from this range. Wherever possible, pH should be adjusted prior to the
addition of the metal pigment.
Unlike solvent-based coatings, water-based formulations tend to be very system specific.

There is no substitute for thorough compatibility and stability testing on a small scale.
Many of the resin systems in use require neutralisation in situ. It has been found that
complex amines which are used to control the pH and also to take the resins into solution,
such as dimethylethanolamine (DMEA), trimethylethanolamine (TMEA), 2-
dimethylamino-2-methyl-1-propanol and the well known 2-amino-2-methyl-1-propanol
(AMP-95) are less aggressive to the metals than triethylamine or the cheaper ammonia
solution. Chlorinated polyolefins are reputed to improve the orientation of flakes in
basecoat-clear systems [16]. This allows thinner basecoats to be used, yet with greater
opacity. Film forming resins include acrylics, polyesters, and polyurethanes.
A useful water-based automotive paint test system, based on an inhibited grade of

aluminium flake pigment, is provided in Table 13.6. Acceptable stability is typically a
release of <10 ml of hydrogen in the gas test apparatus of Figure 12.2 after 7 days at
50 °C or sometimes 4 weeks at 40 °C.
149
Table 13.6 Water-based silver automotive paint test system

Premix
Inhibited aluminium flake pigment paste (NV = 65%; D50 = 12 µm) 6.9%
Ethylene glycol monobutyl ether 6.0%
Trimethyl pentane diol mono propionate 0.3%
Vehicle
Acrylic resin (50% NV in water) 66.7%
Dipropylene glycol methyl ether 3.3%
Deionised water 16.5%
Rheology modifier 0.3%
Aluminium and ethylene glycol ether are gently blended to a creamy paste, to which the
surfactant is added. In a separate vessel, resin, water and dipropylene glycol ether are
combined and the aluminium premix added with low shear agitation. Finally, the
rheology modifier is added, again under slow agitation.
As an example of a general purpose, water dilutable coating, Table 13.7 shows the use of
an inhibited aluminium flake pigment paste, incorporated in a water reducible alkyd
resin system.
Table 13.7 Water reducible, general purpose silver industrial paint

Premix
Vehicle
Water reducible alkyd 27.6%
Manganese aqueous curing agent, 8% 0.4%
Cobalt aqueous curing agent, 5% 0.7%
Water 54.5%
25% aqueous ammonia solution 1.4%
The vehicle components are blended together in turn, finally adjusting the pH to 8.3
with the ammonia solution. The aluminium flake, soaked and well dispersed in the
2-butoxyethanol, is gently stirred into the prepared vehicle.
150
A silver, water-based acrylic formulation, equally suitable for industrial coatings on metal
and plastic, is described in Table 13.8. When spray applied, this coating has a fast touch-
dry time.
Table 13.8 Fast drying, water-based acrylic, general industrial paint

Premix
Diethylene glycol monobutyl ether 3.2%
Vehicle
Aqueous acrylic resin solution (NV = 55%) 70.0%
Manganese aqueous curing agent, 8% 0.4%
Water 3.8%
Dibutyl phthalate 1.4%
The vehicle components are blended together in turn, with a final adjustment of the
pH to 8.3 with the ammonia solution. A well dispersed aluminium flake premix in
2-butoxyethanol alone is diluted with the diethylene glycol monobutyl ether under
gentle agitation. The completed premix is gently stirred into the prepared vehicle and
the following components added under slow agitation.
Rheology modifier 0.1%
Modified polydimethylsiloxane (50% in 2-butoxyethanol) 0.3%
Heat resistant, water dilutable aluminium pigment formulations are used in coatings on
automobile exhaust manifolds, exhaust pipes and the like. A simple formulation is given
in Table 13.9. The coating can be applied by brush, or thinned if necessary for spray
application. Curing is typically carried out at around 210 °C. The cured coating can
withstand temperatures in excess of 600 °C without losing adhesion.
Table 13.9 Heat resistant, water dilutable silver paint

Silicone resin emulsion (NV = 55%) 75.0%
Inhibited aluminium pigment paste (NV = 64% in water; D50 = 19 µm) 25.0%
The aluminium paste is gently stirred directly into the vehicle.
151
Table 13.10 shows a gold metallic water-based paint, suitable for spraying or use in an
aerosol. In the latter case, a propellant, such as dimethyl ether, is required in a ratio of 3
parts paint to 2 parts ether. The formulation shows some stability under ambient
conditions. If the paint is to be used in an aerosol, tests should be carried out to verify its
stability in the presence of the propellant.
Table 13.10 Water-based gold-bronze aerosol paint

Acrylic resin emulsion (NV = 50%) 33.4%
Isopropyl alcohol 16.2%
Propylene glycol monomethyl ether 8.3%
Antifoam 0.8%
2-amino-2-methyl-1-propanol (95% in water) 4.7%
Wetting agent solution 3.3%
Extra fine lining gold bronze powder (D50 = 9 µm) 10.3%
The resin is diluted with the water and the amine added. The remaining components
are mixed in with slow agitation, leaving the metal flake addition to last. The final
pH should be adjusted to between 7.5 and 8.5 if necessary.
13.1.3 In-mould coating
This technique is the coating equivalent of the mass pigmentation in-mould decoration
method described in section 10.6. In this case, a pigmented system is applied to one face
of the mould tool by spraying, optionally by robot. A liquid, thermally cross-linkable
polymer-based coating system is normally chosen to eliminate any problems from solvent
release [17]. Polymer is then injected to bond to the pigmented layer. Thereafter the
completed part is ejected.
Although a more expensive technique than direct mass pigmentation, it provides the
visual quality and uniformity of a painted finish without any of the application and
drying problems of a separate painting operation. It is particularly useful for metal flake
pigments as troublesome flow and weld lines are eliminated.
152
13.1.4 Miscellaneous paints
Both leafing and non-leafing grades of nickel flake are used in decorative coating systems.
They produce an attractive, bright finish with a warm hue, somewhat reminiscent of
metallic silver or pewter. They can be incorporated into solvent-based paint and powder
coatings systems and also into water-based coatings, since nickel shows excellent resistance
to attack in aqueous media.
The largest application of nickel flake pigment is in the manufacture of electrically conductive
coatings. These have become very important over the past twenty years in the electronics
industry, for shielding purposes where they are used to achieve compliance to electromagnetic
compatibility legislation. A special grade of nickel flake that is selectively treated to give a
surface that maximises its electrical properties is produced specifically for this purpose and
described as a conductive grade (see sections 15.3 and 15.4).
Stainless steel flakes are widely employed in decorative and functional coating applications.
They are somewhat darker than aluminium, with a bluish overtone. A wide size range is
available, larger flake sizes giving a brighter appearance than the fine. Finer grades are
used to produce coatings that have an appearance similar to that of pewter. The major
advantage of these flakes is undoubtedly their resistance to corrosive attack. The UNS-S
31603 alloy composition confers excellent properties in a whole range of corrosive
environments. This enables finishes containing stainless steel flakes to be used, for example,
in external atmospheric exposure applications without any further protective top coat
system. Other significant applications include the production of aerosol coatings.
13.2 Printing
In general, flexible packaging is the largest outlet for inks containing metal pigments.
High quality, usually silver dollar type aluminium and some coated gold bronze pigments
are used for spot colour, highlights and borders in high quality packaging, gift wrap and
in prestige publications such as company reports. State of the art aluminium pigments
are also beginning to compete with aluminium foil and golds prepared by coating
aluminium foil with yellow lacquer.
The ultimate in colouristic quality is found by using aluminium flake prepared by vacuum
deposition, whose preparation is described in section 3.7. Properly applied, their uniformity
of reflection approaches that of vacuum deposited film. Lower price, cornflake grades of
aluminium flake are extensively used in commodity packaging, especially foodstuff wrappers.
For inks applied to polymeric substrates, the same concerns about adhesion that are
expressed for paints, continue to apply.
153
13.2.1 Solvent-based inks
Metal pigments of choice for this application are pastes and granules. Dry flakes are still
used, especially gold bronze, but the same drawbacks of poor wetting and contamination
of the environment apply.
Traditional solvent pastes, i.e., those containing high boiling hydrocarbon solvents are
unsuitable for solvent-based liquid inks. Their drying rate is too slow for modern, high-
speed presses and they tend to leave residual odour in the printed stock.
The response of pigment manufacturers has been to offer paste forms in the faster, i.e.,
more volatile solvents, widely used in the industry. Thus aluminium and gold bronze
flakes are commercially available in esters such as ethyl or isopropyl acetate, or alcohols
such as isopropanol. As it is difficult to get adequate brightness from non-leafing bronze
pigments made by milling, leafing grades are de-leafed as required.
The greatest disadvantage of pastes supplied in fast solvents is that the solvents tend to
evaporate in the can. This leads to flake aggregation (seeds) and loss of hiding and surface
smoothness in application. For this reason, containers must be securely lidded when not
in use. The disadvantages of pastes are overcome by granular forms.
The most popular granular grades for solvent-based inks use a synthetic aldehyde or
sometimes a ketone resin. These resins have very wide solvent and binder compatibility.
They are also film formers in their own right and so form a part of the dried ink film.
Granules are more expensive to produce since they are derived from pastes. The inclusion
of carrier resin that would otherwise have to be added by the ink maker is a cost-mitigating
factor that is often overlooked.
Tables 13.11 and 13.12 show solvent ink formulations for gravure and flexographic
printing. For the former, pigments with median particle sizes below 14 µm are preferred.
To print such inks satisfactorily onto polyolefin film, the film surface must be activated,
for example by corona discharge, as described for paints.
13.2.2 Paste inks
Metal pigments intended for litho printing are supplied in paste form, often in a high
boiling petroleum distillate, known as High Boiling Petroleum Fraction (HBPF), with a
typical boiling point of 160-180 °C. This is the same solvent that is commonly used in
such inks, thereby guaranteeing compatibility. Table 13.13 shows one such formulation.
154
Table 13.11 Solvent-based aluminium ink for gravure printing

Premix
Aluminium flake pigment granule (D50 = 12 µm; 80% in aldehyde resin) 18.0%
Ethyl acetate 18.0%
Vehicle
Acrylic resin (100%) 19.0%
Isopropyl acetate 40.0%
Methoxy propanol 5.0%
The vehicle components are homogenised by high-speed stirring and the premix
thereafter added under slow speed mixing.
Table 13.12 Solvent-based gold bronze ink for flexographic printing

Gold bronze flake powder (D50 = 12 µm) 35.0%
Polyvinylbutyral resin 12.0%
Isopropanol 52.8%
Adhesion promoter 0.2%
The bronze powder is gently added to the remaining components which have been
pre-dispersed by high speed stirring. Isopropanol is used to reduce to a printing
viscosity of around 25-30 seconds (Zahn No. 2. cup)
Table 13.13 Silver ink for lithographic printing

Aluminium flake, (D50 = 10 µm), supplied at 80% in HBPF 25%
Hydrocarbon resin solution 72%
Wax dispersion 3%
The components are combined by low energy agitation to a homogeneous, stiff mix.
155
13.2.3 Water-based inks
The same general product forms, powder, paste and granules, can be used in aqueous
inks. In addition, ink concentrates are offered. These consist of a high loading of metal
flake, with sufficient resin and solvent or water to prevent aggregation.
The wetting problems of dry powders are exacerbated by the high surface tension of
water. Use of surfactants to wet out metal flake powders must be carried out sparingly,
as excessive amounts can later lead to foaming of the inks and poor adhesion of the
subsequent film to the substrate.
Isopropyl alcohol carried pastes and the more modern granular forms with low foaming,
non-ionic surfactant carriers are widely used. Metal pigment/resin dispersions are often
acrylic, for compatibility with the acrylic resins widely used in metallic water-based inks.
Passivated aluminiums may be required for derived inks to be adequately gas stable in
some applications. In practice the stability of gold bronze limits the range of acceptable
binder systems. Cartons, labels, gift wrap and cigarette, cosmetic and confectionery
packaging are the main applications.
Table 13.14 illustrates a general purpose ink, based on a leafing aluminium flake granule.
A corresponding granule containing non-leafing flake can be substituted, as can a paste
of non-leafing flake in isopropanol. Alcohol pastes are best wetted and dispersed in part
of the organic solvent component, as loss of leafing is not an issue. The presence of some
solvent in the formulation improves print quality.
Table 13.14 General purpose, water-based, leafing aluminium ink

Premix
Inhibited aluminium flake granule (D50 = 15 µm; 80% in non-ionic surfactant) 18.5%
Vehicle
Pure acrylic solution (35% in water) 50.0%
Isopropanol 2.0%
Propylene glycol monomethyl ether 7.5%
The granule is allowed to soak in the water and subsequently mixed to a smooth, creamy
paste by low energy agitation. The components of the vehicle are combined and the
premix gently stirred in. Let down by 25-30% with water is required for press readiness.
156
Table 13.15 Non-leafing aluminium-based silver gravure ink

Inhibited aluminium flake (D50 = 14 µm; 38% with 17% acrylic resin 35.0%
in water)
Antifoam 0.1%
Wax dispersion 0.2%
The components are combined with gentle agitation. The desirable final pH is within
the range 7.5-8.5.
Table 13.16 Rich gold bronze gravure ink

Stabilised rich gold bronze (D50 = 7 µm; 73% in water) 54.0%
Antifoam 0.2%
Preparation is as in Table 13.15.
Silver and bronze rotogravure formulations are given in Tables 13.15 and 13.16,
respectively. The silver uses an acrylic dispersion, the gold a stabilised bronze flake in
water. The difference in pigment content is an illustration of the density difference between
gold bronze and aluminium. Aluminium is present as 13.3% of the formulation, whilst
gold bronze comprises 39.4%. The difference is further emphasised by the fact that the
coarser aluminium flake has less hiding power.
13.2.4 Laminates
The preparation of decorative surfaces, such as kitchen worktops, is achieved by printing

down a design that is subsequently laminated to layers of thermoplastic or thermosetting
sheet. Alternatively, the printed substrate is overcoated by thermosetting polymer, applied
by knife or curtain coating and cured. Only the printing process selected limits the range
of metal pigments that can be used in this application.
13.2.5 Security Inks
Metal pigments, especially novel effect types, play a valuable role in security printing.
Here cost is subsidiary to protection from forgery. Metal pigments are difficult to forge
157
without the production expertise of the few specialist manufacturers. Even under a low
resolution microscope, it is easy to compare flake particle size, surface finish, flake
roundness and the smoothness of edges.
An example of the novelty required is provided by Thomas de la Rue & Company [18].
A coating containing combinations of luminescent pigments and 10-20 µm diameter
aluminium or nickel flakes is disclosed for application to credit cards, cheques and the
like. Although silver in daylight, such coatings appear coloured under UV light.
13.2.6 Bronze replacement
For coatings in general, and inks in particular, there is interest in replacing gold bronze
because of increasing health and environmental concerns over its copper component.
The growing interest in water-based formulations for environmental reasons also creates
difficulties. Unless surface treated, which increases their cost, gold bronze pigments tend
to tarnish in water-based media.
It has long been known that gold effects could be produced from mixtures of aluminium
flake pigments and organic pigments or dyes. Transparent yellow, orange and red colorants
are mixed for green and red-shade golds, with brown giving ‘antique’ golds. Because of
their ‘flop’ effect, such mixtures are not able to accurately reproduce the visual effect of
gold bronze. The origin of flop, defined as the change of colour depth with angle of
viewing, is described in section 4.3.3.
In practice, due to the flop effect, gold bronze formulations can only be accurately matched
at a given angle of viewing. This is not necessarily a disadvantage in new formulations as
it may not be necessary to provide an exact match.
Aluminium based formulations can compete on cost because of the much lower density
of aluminium compared to gold bronze. The lower cost associated with the lower
concentration required to provide a given opacity per square metre helps to offset the
usually higher cost of the organic pigment component of the formulation. Table 13.17
shows the use of mixtures of organic red and yellow tinted, solvent-based aluminium
inks to provide a wide range of gold shades. A corresponding water-based system is
illustrated in Table 13.18. The formulation shown provides a mid-shade gold, but the
ratio of yellow to red can be manipulated to give a wide shade range.
158
Table 13.17 Solvent-based gold inks prepared from aluminium pigment

Ink bases Ink A Ink B
C.I. Yellow 13 pigment powder 12.0%
C.I. Red 48.2 pigment powder 12.0%
Nitrocellulose 400 5.0% 5.0%
Ketone resin 8.0% 8.0%
Ethoxypropanol 10.0% 10.0%
Ethyl acetate 13.0% 13.0%
Ethanol 52.0% 52.0%
The components are ball milled or bead milled to provide a well dispersed coloured
concentrate.
Vehicle
Nitrocellulose 400 9.0%
Ketone resin 8.0%
Ethoxypropanol 10.0%
Ethyl acetate 15.0%
Ethanol 55.0%
Silicone oil 2.0%
PE wax dispersion 1.0%
Gold ink
Aluminium pigment granule (D50 = 12 µm; 80% 35.0%
in aldehyde resin)
Ink base A + B 30.0%
Vehicle 35.0%
The granule is soaked directly in the vehicle and later gently dispersed by low shear
agitation. A blend of ink bases is mixed in to give the desired shade.
159
Table 13.18 Water-based gold inks prepared from aluminium pigment

Inhibited aluminium pigment paste (D50 = 16 µm; 65% in isopropanol) 24.6%
Pure acrylic solution (35% in water) 53.7%
C.I. Yellow 13 (40% water-based, surfactant dispersion) 8.0%
C.I. Red 53.1 (40% water-based, surfactant dispersion) 1.0%
Antifoam 0.3%
The aluminium pigment is mixed to a paste-like consistency with the water and let down
into a prepared combination of the remaining components.
A key disadvantage of aluminium-based gold formulations is the potential for pigment

separation. This is best illustrated on corrugated board packaging (see Figure 13.1).
Although homogeneous when applied, the organic pigment or dyestuff component of
the ink is carried to the more absorbent areas between the corrugations. Little is left at
the paper junctions where the glue has reduced the absorbency. The less mobile aluminium
flake tends to remain where it is deposited. In an extreme case, the visual result is stripes,
alternately silver and excessively pigmented metallic gold.
To overcome this deficiency and also to accurately reproduce the visual effect of gold
bronze with increased durability, industrial researchers looked for ways to surface colour
aluminium flakes. The discovery that many surface coloration techniques increased the
resistance of the underlying aluminium to aqueous attack proved a useful bonus in water-
based applications. Cost, however, is a deterrent to commercialisation.
Figure 13.1 Organic pigment migration in corrugated packaging.
160
13.3 UV cured coatings
Coatings cured by UV light are an alternative to water-based systems where low or zero
VOC are required.
Most UV cured metallic formulations are inks. Applications are mainly in packaging,
where freedom from solvent taint is required. Advantages of UV curing, which help to
offset its generally higher cost, include dry handling direct from the press, plus the absence
of set off and odour or taint. Superior abrasion resistance is an advantage in the printing of
vinyl floorcoverings and leathercloth, because tougher, thicker films are produced.
Starting point formulations for UV cured inks are provided by Holman and Oldring [19]
and by Kerr [20]. Aluminium flake pigment concentrations are 10-20% by weight of
formulation, for flexographic and screen inks. A higher concentration, some 15-25%, is
required for lithographic ink. The exact percentage is dependent on particle size, lower
concentrations being appropriate for finer grades.
Table 13.19 contains a typical starting point formulation for a stable, one pack aluminised
UV curing ink for flexographic application to polyolefin surfaces. The aluminium must
be inhibited by surface treatment to prevent premature cure.
Table 13.19 One-pack UV curing flexographic ink for polyolefin substrates

Inhibited aluminium pigment (D50 = 12 µm; 80% in long chain 20.0%
aliphatic alcohol)
Polyurethane acrylate prepolymer 60.0%
Acrylic monomers 10.0%
Photoinitiators and synergists 6.0%
Silane adhesion promoter 1.5%
Additives (e.g., waxes, flow modifiers) 2.5%
The pigment is wetted in the monomers and gently mixed into a blend of the remaining
components.
For flexible PVC sheet and leathercloth applications, urethane acrylates with flexible
backbones are used in conjunction with mono and difunctional monomers. Medium
particle size grades of aluminium pigment give the greater brightness and degree of sparkle
required (see Table 13.20).
161
Table 13.20 One-pack UV curing coating for PVC and

leathercloth applications
Inhibited aluminium pigment (D50 = 22 µm; 80% in long chain 20.0%
aliphatic alcohol)
Urethane acrylate prepolymer 46.0%
n-vinyl pyrrolidone 15.5%
Alkyl diglycol acrylate 12.0%
Alkyl diol diacrylate 4.0%
Photoinitiators 2.5%
The pigment is wetted out in the pyrrolidone and added with low shear agitation to a
blend of the remaining components.
13.4 PVC Plastisols
Leathercloth and other fabric coatings, along with T-shirt and sweatshirt decoration and
the like, are market areas for metal pigmented PVC plastisols. These mixtures of PVC
polymer, finely dispersed in plasticiser, can be printed or spread by knife and cured to
tough, flexible films by exposure to around 160 °C for a few minutes. They are of virtually
100% NV, with high viscosity for a high film build. Application of a printed design is
usually by the silk screen process, which accommodates the larger metal flakes well. A
basic formulation appears in Table 13.21. The viscosity reducer increases ink penetration,
especially into fibrous substrates, with a corresponding improvement in bond strength.
Table 13.21 Aluminium pigmented plastisol coating

Aluminium flake pigment (D50 = 30 µm; 80% in dodecyl phthalate) 24.0%
PVC plastisol base 72.0%
Viscosity reducer 4.0%
The aluminium pigment is gently blended into the plastisol and the viscosity reducer
added last. The amount shown may not always be required.
13.5 Anticorrosive and barrier coatings
Aluminium and stainless steel flakes and zinc dust (see section 2.6) are used extensively
in so-called barrier coatings for anticorrosion applications. Applications are often in
162
harsh environments, such as chemical plant, external storage tanks, bridges and roof
coatings. Such solvent-based paints are mainly applied to steel, rather than polymer
substrates, but are often formulated with polymeric binders. Much work on the
effectiveness of both metal and non-metal flake pigments has been carried out by Hare
(see section 15.13).
A typical starting point formulation for a general purpose barrier coating is shown in
Table 13.22.
Table 13.22 Non-toxic, aluminised, silicone-alkyd barrier paint

Calcium borosilicate 5.0%
Leafing aluminium pigment paste (D50 = 9 µm; 68% in white spirit) 14.6%
Organo-montmorillonite suspending agent 0.1%
Silicone resin modified long soya oil alkyd, 60% NV in white spirit. 31.3%
White spirit 48.0%
Zirconium/cobalt drier 1.0%
The aluminium paste is soaked in its own weight of the white spirit. After gentle agitation
to a smooth dispersion, it is stirred into a dispersion of the remaining components.
The Aluminum Association [21] in the USA has produced a short guide to aluminium
pigmented maintenance coatings, including formulation guidelines and seven
representative formulations.
13.6 Other applications
The application of metal pigments in wax crayons is not so much a coating as a means of
making a coating. Thus glitter flakes are incorporated with a colorant, an emollient and
a waxy material such as a plasticiser or fatty acid in a patent to Binney and Smith [22].
There is a small market for filler pastes with a metallic appearance. Aluminium and
stainless steel flakes are the pigments of choice, incorporated in polyester or epoxy resins.
The main application is repair of accident damaged vehicles.
High purity aluminium powder is combined with free radical initiated acrylic monomer
to provide an adhesive in a patent to Loctite [23].
163
References
1. Market Trade International, World Paint File 1998-2002, DMG Business Media,
Redhill, UK, 1998.
2. The Coatings Agenda Europe, Campden Publishing Limited, London, UK, 1998, 49.
3. R. L. Ferguson, Pigment Handbook, Vol.1, Ed., P. A. Lewis, Wiley-Interscience,

New York, 1988, 785-801.
4. E.I. Du Pont de Nemours Inc., assignee, US Patent 2,943,955,
5. T. Okai, Y. Okamura, M. Oda, T. Yamamoto and T. Kuwajima, inventors;

Nippon Paint Co., Ltd., assignee, US Patent 4,885,032, 1989.
6. T. Kuwajima, S. Nagahata and S. Konishi, inventors; Nippon Paint Co., Ltd.,

7. A. Frangai, inventor; ICI plc, assignee, British Patent 2,182,939, 1986.
8. Z. Vachlas and S. J. Thorne, inventors; Imperical Chemical Industries plc,

assignee, European Patent 0,238,222, 1987.
9. A. J. Backhouse, A. Frangou and S. J. Thorne, inventors; Imperical Chemical

Industries plc, assignee, European Patent 0,170,474, 1985.
10. A. Frangou, inventor; Imperial Chemical Industries plc, assignee, US Patent

4,675,358, 1987.
11. K. R. Walker, inventor; Eastman Kodak Company, assignee, US Patent

5,286,768, 1994.
12. J. L. Anderson, Jr., H. J. Finkenauer, D. L. Newton and J. P. Jones, inventors;

BASF Corporation, assignee, US Patent 5,168,105, 1992.
13. J. L. Anderson, Jr., H. J. Finkenauer, D. L. Newton and J. P. Jones, inventors;

BASF Corporation, assignee, US Patent 5,204,401, 1993.
14. C. W. Fowler, M. C. Knight and A. J. Nichols, inventors; BASF Corporation,

assignee, European Patent 0,394,737 B2, 1990.
15. D. C. K. Chang, inventor; E.I. Du Pont de Nemours and Company, assignee, US

Patent 5,104,922, 1992.
164
16. R. A. Cowles, inventor; Inmont Corporation, assignee, US Patent 4,539,360, 1983.
17. Matsushita Electrical Works, assignee, Japanese Patent 63/239052.
18. J. Beck and A. Nutton, inventors; Thomas de la Rue & Company Ltd., assignee,
European Patent 0,253,543, 1987.
19. R. Holman and P. Oldring, UV and EB Curing formulations for Printing Inks,
Coatings and Paints, SITA technology, London, 1988, 182-187.
20. S. Kerr, European Chemical & Polymer Engineer, 1998, December, 34.
21. Aluminium Pigmented Coatings for Industrial Maintenance Applications, The

Aluminum Association, Washington, D.C., USA, 1996.
22. M. S. Craig, inventor; Binney & Smith Inc., assignee, US Patent 5,261,952, 1993.
23. D. J. Dunn, P. P. Vano, J. P. Moran, Jr., M. Holmes and E. Frauenglas, inventors;

Loctite Corporation, assignee, US Patent 4,722,960, 1988.
165
14
Powder Coatings
Powder coating, sometimes known as dry paint, is both an environmentally friendly or

‘green’ technology and one of the least expensive finishing techniques on the market.
Globally it has grown eleven-fold since the early 1970s and growth continues at around
11% p.a. By 1995, world production was estimated at around 400,000 tonnes, or
about 15% of the industrial coatings market [1]. It has been projected to reach 836,000
tonnes by the year 2000 [2]. Within this figure, the part of the market using metallic,
sparkle or hammer finishes is estimated at a minimum of 40,000 tonnes, offering a
total market potential of at least 1000 tonnes of aluminium flake pigment, of which
about half is in Europe.
The Powder Coating Institute in the USA has provided a very comprehensive overview
of powder coatings and their manufacture and application [3]. World markets and coating
types favoured in each geographical area are described by Dreher [4].
In its most basic form, the manufacturing process consists of compounding polymer
resins with a curing agent, other additives and colorants and reducing the resultant mass
to fine powder particles. Application is by coating a substrate with the powder, by dipping
or more commonly, electrostatic spraying. The coating is then heated above its melt
point to cause flow out to a continuous film. The curing agent acts by a chemical
mechanism that is irreversible, thereby providing a very durable finish.
Powder coating is energy efficient because it is VOC free. Equally there are no aqueous
coating residues requiring increasingly expensive disposal. Curing can be carried out in
static air, so the considerable cost of heating high airflow drying tunnels, characteristic
of liquid coatings, is avoided. Labour costs can be lower because the process lends itself
better to automation and can be operated by a less skilled work force. Application skill
is not so critical because the coatings do not sag or run, resulting in fewer rejects. Finally,
the absence of flammable solvents helps to reduce fire insurance premiums.
The typical payback period for conversion of a ‘wet paint’ line to a powder coating
system is 6-18 months. Since overspray powder, i.e., the proportion that misses the target,
can be recycled and reused, material utilisation can exceed 97% of input. This is far
greater than for wet paint. Powder coating can be expected to become more cost
competitive as legislative and cost constraints on emission of volatiles tighten.
167
In film performance terms, powder coating provides a thicker film that also has a higher
cross-link density than its liquid counterparts. This provides better impact, abrasion,
corrosion and humidity resistance. The last of these is particularly relevant to aluminium
flake pigmented systems.
The disadvantages of the technique are mostly related to the quality of surface finish.
Metal flake pigments have a major influence on this. In practice it is difficult to approach
the brightness achievable from the same grade of metal pigment in a liquid coating for
reasons covered in section 14.3.
14.1 Material types and properties
Powder coating is by no means a new technology. Indeed its origins can be traced back
to the fluidised bed applied, thermoplastic dip coatings of the early 1950s. The use of
thermoplastic polymers such as vinyl, polyamide and especially polyolefins has declined
in favour of thermosets, initially epoxy types. Poor UV resistance and chalking caused
these in turn to be overtaken by epoxy-polyesters around the mid 1970s. This type remains
the mainstay of the European market today. Polyester-triglycidyl isocyanurate (TGIC), is
currently in second place, but will lose ground due to health concerns. A UK Health and
Safety Executive guidance note [5] describes the known health effects, maximum exposure
limits and sampling and analysis methods. On 31st May 1998 the European Union
assigned TGIC a Category 2 mutagenic classification, which requires the ‘T’ (toxic) symbol
and corresponding risk phrases [6]. Implications of the legislation and alternative cross-
linkers are considered by Goemans [7]. The main contender as a TGIC replacement is
hydroxy alkyl amide (HAA). Other candidates are described by Osmond and Steele [8].
Polyester-urethane has a very low European market share, and acrylic types are under
1%, mainly due to their higher cost. Some work had been done on acrylic and melamine
compounds in the early seventies with no success. A revival in acrylic technology has
recently taken place for niche applications where a higher cost can be tolerated. Metal
flake pigments can be made compatible with all these polymer types.
Preferences outside Europe are rather different. Polyester and polyester/urethanes hold
the majority of the North America market, with the latter even more popular in Japan
where it has a claimed market share of 34%.
14.2 Manufacture
There are four routes to the manufacture of metal pigmented powder coatings. The
oldest of these is the physical blending of dry metal flakes with micronised powder resin
168
Powder Coatings
particles prior to spraying. The hazards and technical limitations of this method prompted
development of the so-called ‘bonded’ route, pioneered by Alcoa [9], in which metal
flakes are attached to the resin particles. The high costs and limited palette associated
with bonded powders were in turn a driving force for the challenges of the extrusion
route, also referred to as co-extrusion. Here resin, metal flake and other colorants and
additives are mixed together, extruded and subsequently micronised.
Most recently, individual flakes have been encapsulated with resins capable of simulating
the density and charging characteristics of the micronised resin powders into which they
are subsequently mixed. This brings the technology full circle, since it is merely a more
sophisticated form of dry blending. A useful review of all aspects of metal pigments in
powder coatings has been provided by Besold [10].
14.2.1 Dry blend
Dry blend describes the mixing of pre-compounded micronised powder coating resin
with dry metal flake. Its main advantages are low cost and the retention of flake integrity
due to the low energy involved in blending the pigment with the resin. The method was
fraught with problems in its early days as the flake was uncoated. In the case of aluminium
there was a very high risk of fire or explosion.
The flake also has completely different charging characteristics to those of the powder,
making the coating uneven. Particularly prevalent is a fault known as ‘picture framing’,
which describes the much brighter edges of a coated article compared to the remaining
area. This is caused by the preferential deposition of loosely adherent flakes.
The technique is unsuitable for application by tribo (see section 14.3) and there is poor
penetration into recessed areas. This has been attributed to the Faraday Cage effect [11].
As the densities of the two components are also widely different, the overspray has a
different composition to that of the starting material, so cannot be readily recycled.
Despite these disadvantages this method of coloration is inexpensive, so it is still widely
used, although now declining.
14.2.2 Bonding
The bonded powder process was developed as a response to the safety and application
drawbacks of the dry blending of uncoated metal flakes. As the name implies, dry
metal flake powder is physically attached to powder coating resin that has already
been micronised [12]. The technique is preferred in Europe due to the powder
169
producers’ awareness of the explosion hazards of dry flakes. Colouristic properties

are good and both leafing and non-leafing finishes are possible. Another advantage
is that overspray will have a composition that is not significantly different from that
of the starting material.
The main disadvantage is high cost. This is derived at least in part from an historic lack
of competition, since the technology has limited licences. Also, in order to make a
homogeneous product, all the powder must be bonded. This is akin to using coloured
compound compared to masterbatch. For this reason too, the bonding route is less versatile
in the available range of visual effects. Care in preparation and application is needed if
abrasion is not to detach flakes from the resin surfaces. Should this occur to any extent,
the application characteristics will move towards those of dry blend, described above.
An early patent for this technique was filed by Rolles [13]. A brush polishing device for
combining the metal flakes with thermoplastic or thermosetting polymer particles at an
elevated temperature is described. The polymer either forms a continuous film on the
flake surfaces or the flakes coat the polymer particles. In either case the integrity of the
fused mass is maintained by cooling. Screens can be used to remove any aggregates
formed. Examples show the utility of the process with various metals such as aluminium,
zinc and gold bronze.
Richart and Daly [14] patented a flake pigmented coating powder prepared by mixing a
thermosetting resin, such as a polyester based system, with a metallic flake such as leafing
or non-leafing aluminium. The temperature is maintained between the softening point
and the melting point of the resin, with sufficient mechanical shear to prevent agglomerates
from forming. The mixing time is adjusted until at least 75% of the flakes are embedded
in the resin particles.
A similar process, using leafing aluminium flake pastes, ball milled with resin powder,
was patented by the H.B. Fuller company [15]. The milled material is screened to
remove aggregates and post-treated with a fluidising agent such as fumed silica, to
maintain flow properties.
Spray drying also achieves the objectives of the bonding process. Thus in 1976, Camelon
and Gibeau [16] at Ford Motor Company patented powder paint consisting of
aluminium flakes individually coated with a continuous film of thermoplastic polymer
in a spray dryer. A useful feature is the possibility of using the same polymer as flake
encapsulant as that used as the principal film former in the final powder coating
formulation.
170
Powder Coatings
14.2.3 Co-extrusion
For metal-free powder coatings, the process of choice remains extrusion, introduced in
commercial volume in the late 1960s. Harris [17] provides a review of production
machinery. Manufacture routinely consists of four stages. In the first, resin, colorants,
and any additives such as levelling agents, are intimately mixed. The particle size of the
resin is influential in the efficiency of dispersion, coarse particles some millimetres in size
giving a scouring action that prevents pigment and additive agglomeration. An enclosed,
high speed, vertical axis mixer is normally used, often with second impeller mounted at
right angles to act as a vortex breaker.
The homogeneous premix is continuously fed into an extruder. Extruded melt is cooled
from around 120 °C to ambient temperature using a mill with chilled nip rolls to produce
a band of material around a metre wide and 3 mm thick. This friable material is flaked
off the rolls by doctor blades and broken down into pieces around 1 cm square. In the
third stage of production, these are subjected to micronising by milling before final
screening to produce the desired particle size, generally in the range 10-80 µm.
Metal flake pigments incorporated by the co-extrusion route must be specially designed
to withstand the high degree of attrition inherent in each stage of production. Traditional
extrusion techniques have also had to be modified to avoid a detrimental effect on flake
aesthetics. Metal flake pigment may be added to the premix with the other ingredients,
but flake damage can be minimised by homogenising the other components first. Modern
granular forms of metal pigment are predispersed and therefore require only brief further
compounding. Their carriers are compatible with all the commonly used resin systems
and the carrier itself becomes an integral part of the coating.
Those metal flake pigment grades developed specifically for the extrusion route are thicker,
in order to be more degradation resistant. They also contain fewer fine particles that can
contribute to a dark appearance. Figure 14.1 shows a typical low aspect ratio flake for
this application. If conventional flakes must be used, it is customary to use a rather
larger flake size than is required in the finished product. In this way, after incorporation,
the flake size is brought into the desired range.
One advantage of this route is that, like bonded material, the powder is homogeneously
pigmented. The overspray will therefore have virtually the same composition as the starting
powder and so can be readily recycled. Another benefit is that such powder coating
formulations are suitable for both electrostatic and tribo application. Penetration into
cavities is excellent and finishes are free of ‘picture frame’ edge effects.
171
Figure 14.1 Typical low aspect ratio aluminium flake pigment for powder coatings
prepared by the extrusion route. [1 cm = approx. 60 µm]
14.2.4 Coated flakes
The original dry blend method was recognised to have the advantage of simplicity, versatility
and low cost, all very attractive attributes if the hazards and limited aesthetics could be
overcome. The modern response of metal pigment manufacturers has been to coat or
encapsulate each metal flake with a resinous or inorganic coating. Several examples can be
found in the patent literature [18, 19, 20, 21, 22, 23] and both types are commercially
available. In practice it is difficult to ensure uniform coating of single flakes, particularly
with resinous polymers. As a result, encapsulated grades tend to be more aggregated and
provide less opacity than the powders or pastes on which they are based.
Comparisons of dry blending with the bonding and extrusion processes are provided by
Kerr [1] and by Birch [24]. This comprehensive review covers powder recovery, metallic
effect, curing gun blockages and reduction of picture framing effects. Some improvements
in bonded coatings, including resin and pigment development are also described.
14.2.5 Other technologies
A hybrid of dry powder and bonding is provided by so-called dedusted flakes, such as
the DF range of Silberline Inc. Here, dry aluminium flakes are restrained by entanglement
172
Powder Coatings
with PTFE microfibres. Environmental contamination and explosion hazards are reduced.
Very low concentrations of PTFE, typically 0.1%, are required. The treatment is sufficient
to prevent significant dusting in transit, but the free flake form is regenerated during
mixing with powder resin prior to spraying. As the resulting mix retains the limitations
of dry flakes, the technique has been developed to allow dedusting of resin coated flakes,
now marketed as the LE range. Resin coating alone does not prevent dusting but improves
the compatibility on application, i.e., reducing picture framing, etc.
Another variant and one of the most promising for the future is the use of water to carry
the powder. Thus Williams and Gessner at BASF [25] applied for patent protection for a
process in which conventionally produced powder is combined with water, surfactants
and rheology control agents. Such powder slurries are suggested for formulating primers
and coloured basecoats with metallic effects, applied by spraying and subsequently cured
at elevated temperature. A wide range of powdered polymers can be used, but acrylic
resins are preferred. Like water-based coatings, formulations involving aluminium flake
pigments will require the metal to be passivated against aqueous attack if long-term
storage stability is a prerequisite.
14.3 Formulation, application techniques and markets
Aluminium, gold bronze, zinc and stainless steel flake are all offered for powder coating,
the first two for their aesthetic effects, zinc and stainless steel in small quantities for their
anticorrosion properties. The thick film build of powder coating compared to liquid
coatings allows obliteration of the substrate by as little as 2% w/w on formulation of a
fine particle size metal pigment. Coarser grades may require up to 5%. Another useful
advantage of high film build is that coarser grades of flake, which would protrude through
a conventional liquid coating, can be used. Disadvantages include cost.
The main application methods are fluidised bed or electrostatic spraying. In the former,
the article to be coated is heated above the softening point of the powder resin, then
dipped in a bath of the powder, held in an agitated state by air injected from below. The
coating that forms on the part by this dip coating method is subsequently hardened by
curing in an oven. The coating is prevented from running off the part by adhesion and
controlled viscosity. The technique is useful for limited production runs, but is not as
easy to automate as spraying.
Electrostatic spraying requires that the article to be coated is well earthed. Coating is
achieved by applying an electrostatic charge to the pigmented powder, which is then
attracted to the part. When a sufficient thickness of coating powder has been attached,
the part is cured in an oven. In practice, the operation is generally continuous, the parts
173
being carried on a moving coating line past the spray heads and into a curing tunnel.
Electrostatic charging may be by an induced or corona mechanism, or by tribo, in which
the charge is created by frictional contact of powder particles in the gun.
Metal flake pigments that are neither coated nor physically attached to the powder, tend
to cause electrical short circuiting of the spray gun. The charging characteristics of metal
flakes are in any case very different to powder, so the quality of finish tends to be at the
margins of acceptance. For these reasons, co-extrusion and bonding are the currently
preferred techniques.
In comparison with the metallic effect obtained from liquid coatings, powder coatings
have some deficiencies. In particular, orientation and therefore brightness are adversely
affected by the high melt viscosity and the short residence time in the liquid state. There
is also no appreciable film shrinkage. Consequently the solvent loss from liquid coatings,
responsible for forcing an alignment of flakes parallel to the substrate thus increasing
brightness, is absent. Lower melt viscosity binders and longer cure times will help, but
there are then limitations of sag and low productivity.
On the positive side, powder coatings can provide thicker coatings capable of
accommodating larger flakes. They also offer better chemical, weather and abrasion
resistance than the corresponding liquid coatings. For outdoor applications, especially
for leafing effects, a clear powder topcoat is often applied to give further protection.
The main markets for metal pigmented powder coatings are domestic appliances, metal
furniture, tools, automotive components and general exterior and architectural extrusions,
especially window frames. All the metallic effects available from liquid coatings are also
available from powder coatings, including sparkle and hammer finishes, metallic, coloured
metallic, tinted lacquers, fluorescent and pearlescent effects. For technical and commercial
reasons the last three of these have made little impact.
A sizeable fashion driven market exists for sparkle finish in bicycles, metal furniture,
garden implements and to a lesser extent, automotive components. Hammer finishes
appear in the domestic sector, particularly on gas and electric fires, to give an antique
appearance. Straightforward metallic effects are prominent in vehicle wheel trims where
the high film thickness gives enhanced stone chip resistance. Clear powder coats are
increasingly applied over conventional metallic pigmented basecoats in automotive
applications.
Gold bronze flakes must be protected to provide sufficient colour stability in powder
coating applications. Silica coated grades such as the Resist range of Eckart-Werke,
Schlenk’s ‘Constant’ or Wolstenholme International’s Tarnish Resistant have been
commercially available for many years.
174
Powder Coatings
Zinc flake is used for its protective properties. It enhances the already good barrier
properties of powder coating films, even at relatively low concentrations. In this respect
the flake is superior to the more common powder form and delivers reasonable cathodic
protection [26]. Further advantages are film flexibility, resistance to blistering and easy
overpainting. Against this must be set the necessity for rather high loadings, around 10-
15%, partly due to the metal’s higher density.
One substantial application of stainless steel flakes is in the manufacture of decorative

organic powder coating systems, particularly those intended for use in demanding
environments. They are used extensively in both epoxy and polyurethane resin systems
as coatings for structural steelwork in food processing plants. Their resistance to chemical
attack in aqueous media also makes them eminently suited for use in water-based resin
systems, including water carried powder coat (see section 14.2.5).
14.4 Safety and handling
Powder coatings pose a lower safety risk than liquid coatings. A resin dust in the
atmosphere requires 50-100 times more ignition energy than a solvent/air mixture [27].
Nevertheless, the high surface area of fine resin particles requires precautions to prevent
dust explosions. Dusts can also be a mild respiratory irritant. Electrical grounding and
avoidance of dust clouds are the main considerations. Safety aspects are fortunately well
understood in the industry.
Reference has already been made to the hazards of dry metal flake in the electrically
charged environment of a powder spray gun. The energy for ignition is known as the
MIE or minimum explosive energy, measured in millijoules (mJ). Data quoted by Besold
[26] show that aluminium flake poses the greatest hazard, having an MIE comparable to
that of the resin powder itself. The value is claimed to be independent of whether the
pigment is dry blended, extruded or bonded. The MIE value for zinc is some 20 times
higher than that for aluminium. Gold bronze, whilst flammable in fine particle sizes, is
not considered an explosion hazard.
The Paintmakers Association of Great Britain publishes a code of safe practice for the
application of powder coatings by electrostatic spraying [28]. Current health and safety
concerns relating to powder coatings in general are described by Cooke [29].
175
References
1. J. D. Kerr, Product Finishing, 1995, September.
2. Coatings COMET, World Outlook, 1997, 7, 2, iii-xiv.
3. Powder Coating, The Complete Finisher’s Handbook, Ed., N. P. Liberto, The

Powder Coating Institute, Alexandria, VA, USA, 1994.
4. B. Dreher, Polymers Paint Colour Journal, 1993, 183, 4326, 166.
5. EIS 15, Control of Exposure to TGIC in Coating Powders, UK Health and Safety
Executive.
6. Coatings COMET, 1996, 4, 7, 66.
7. C. Goemans et al., Polymers Paint Colour Journal, 1998, 188, 4405, 19.
8. M. F. Osmond and G. D. Steele, Polymers Paint Colour Journal, 1992, 182,

4303, 182.
9. R. Rolles, J. E. Williams, Jr., and T. J. Kondis, inventors; Aluminium Company of

America, assignees, US Patent 4,138,511, 1976.
10. R. Besold, et al., 13th International Conference, Paint Research Association, UK,
1993, Paper No.18.
11. Powder Coating, The Complete Finisher’s Handbook, Ed., N. P. Liberto, The
Powder Coating Institute, Alexandria, VA, USA, 1994, 99.
12. H. Groebl, Farbe und Lack, 1974, 80, 10, 930.
13. R. Rolles, J. E. Williams, Jr., and T. J. Kondis, inventors; Aluminium Company of

America, assignee, US Patent 4,138,511, 1976.
14. D. S. Richart and A. T. Daly, inventors; Morton International Inc., assignee, US

Patent 5,187,220, 1993.
15. S. V. Bigalk and S. C. Hart, inventors; H.B. Fuller Licensing & Financing, Inc.,
16. M. J. Camelon and R. C. Gibeau, inventors; Ford Motor Company, assignee, US

Patent 3,932,320, 1976.
176
Powder Coatings
17. S. T. Harris, Polymers Paint Colour Journal, 1992, 182, 4303, 186.
18. C. A. Ponyik, Jr., inventor; Mobil Oil Corporation, assignee, US Patent

3,575,900, 1969.
19. T. Banba, inventor; Toyo, Aluminium Kabushiki Kaisha, assignee, US Patent

4,434,009, 1984.
20. K. Higashi, Y. Imasato and K. Iri, inventors; Asahi Kasei Metals Ltd., assignee,
21. W. Reisser and G. Sommers, inventors; Eckart-Werke Standard Bronzpulver-

Werke Carl Eckart GmbH & Co., assignee, US Patent 5,332,767, 1994.
22. R. Schmid, N. Mronga, J. A. G. Gomez, R. Rieger and R. Schlegal, inventors;

BASF AG, assignee US Patent 5,505,991, 1996.
23. Asahi Kasei Metals, assignee, PCT 9,638,506,
24. J. Birch, European Coatings Journal, 1997, No.7-8, 709.
25. C. F. Williams and M. A. Gessner, inventors; BASF Corporation, assignee,

European Patent 0,652,264 A2, 1994.
26. R. Besold, Farbe und Lack, 1983, 89, 3, 166.
27. Safe Powder Coating, 4th Edn., CEP, 1990.
28. Application of Powder Coatings by Electrostatic Spraying, Paintmakers

Association of Great Britain Ltd, London, 1983.
29. M. Cooke, Surface Coatings International, 1998, 81, 2, 86.
177
15
Non-colouristic Applications
Though metal flakes are best known for their role as pigments in paints, ink and plastics,
there are many existing and potential applications in which these pigmentary properties
are of lesser or even no relevance. In such applications, the properties of the metal
itself are often more important than the shape or size of the flakes.
The non-pigmentary applications relevant to polymers are discussed in the following

sections. Some have already yielded commercially viable products. Others can be
regarded as subjects for research and development. In total however, the contents of
the section should dispel the impression that metal flakes are only useful for their
pigmentary properties.
15.1 Mechanical reinforcement
The influence of metal pigments on the mechanical properties of polymers is discussed

in section 7.5. Developments in mechanical reinforcement are concentrated on modifying
the surface of the metal flake to improve the bonding between the flake surface and the
polymer matrix. Lack of bonding in the gaps between flakes and matrix at a fracture
surface was shown in Figure 7.1. Suitable bonding or crosslinking agents (used to
create a bond between the metal surface and the matrix) include multi-functional organic
titanates, zirconates and silanes.
Applications are those in which a metallic appearance is required, combined with

mechanical properties closer to those of the pure metals, i.e., ‘metal replacement’
applications. Weight saving, as in automotive parts, is a secondary attraction.
There is a compelling commercial justification for surface treated pigments in mass

pigmented polymers. Polyolefins have attractive properties such as good chemical
resistance and low cost. If their relatively poor mechanical properties can be raised
towards the level of the engineering polymers such as ABS, PC and the like, the
pigment cost is offset against the more expensive polymer that would otherwise have
to be used.
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15.2 Microwave heating
Interest in metal flakes for microwave heating comes from the observation that they
heat up in a microwave beam when incorporated in high melting polymers such as
polyethylene terephthalate (PET) [1]. PET is temperature stable and used in food contact
applications.
Microwave packages can be divided into two groups, passive and active containers.
Passive containers simply hold the food and cannot provide any additional heating.
These containers are made from microwave transparent materials that allow energy to
pass through with little or no resistance, thus allowing energy absorption by the food
mass. Passive containers are commonly made from glass, polymer compounds, or coated
fibreboard.
Food containers formed from high temperature polymers such as PET are unable to
heat the outside surfaces of foods contained in them. As a result, the browning and
crisping of bread, pastry, pizzas, french fries, batter coated and related foodstuffs, that
would occur naturally in a conventional oven, does not take place. Worse, such foods
can become soggy and unappetising.
Active containers not only hold the food for heating purposes but are also designed to
interact with microwave energy. This implies that part or all of the container absorbs
or reflects microwave radiation, thereby heating that part of the food in immediate
contact. The shape, dimensions and construction materials contribute to the efficiency
of cooking. To achieve significant browning and crisping, the food surface must be
heated above 190 °C. This can be achieved by the use of susceptors.
The development of the microwave susceptor or receptor, was to overcome this

deficiency and revolutionise this part of the fast food market. Rapid developments in
the early 1980s led to inexpensive, one trip ‘pad susceptors’, formed from aluminium,
vacuum deposited onto polymer film, itself usually laminated to a paperboard backing.
Seiferth [2] describes ‘a laminate for use in a disposable container, adapted to heat the
surface of a quantity of food when exposed to microwave radiation’. The laminate
consists of a continuous vacuum deposited layer of aluminium less than 70 nm thick,
a heat resistant polymer film and a structural support of paper stock. The extreme
thinness of the metal film confers the microwave activity, since it was observed that
thicker films have no heating potential.
The logical development was to move to a flake metal pigment. If the coating is applied
by a printing process, the position and degree of heating within a single sheet of
composite material can be controlled to a greater degree than is possible with a pad
susceptor. This is of potential interest to manufacturers of lidding films, the flexible
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polymer film used to cover and seal the tray. In such cases the film acts to reduce or
prevent direct microwave irradiation of the food, thus giving additional control of
heating rate.
Huang and Plorde [3] at Du Pont patented a composite consisting of a polymeric

substrate such as PET film, coated by a mixture of an electrically conductive metal or
metal alloy in flake form in a thermoplastic dielectric matrix. Circular flakes with flat
surfaces and smooth edges were found to give the most efficient heating performance.
A particle size range of 10-35 µm is generally preferred, incorporated in a coating

system to give a 50-70% concentration in a dry film weight of 40-70 g/m2. The coating
system itself is advantageously formulated with a polyester resin for good compatibility
with a PET substrate. Formulations of this type are capable of attaining surface
temperatures of over 200 °C in a 2450 MHz, 650 watt microwave oven in periods as
short as one to two minutes.
Paleari [4] developed a multilayer sheet having a sealing layer, an inner layer and an
outer, abuse resistant layer. The film included 0.05-2.5% by weight, based on total
film weight, of fine aluminium powder, dispersed between two of the layer components.
The composition, which has a metallic appearance, is thermoformable into complex
shapes and has some gas barrier properties.
A greater measure of temperature control could be obtained because a pigmented system

could be printed down in grids or other patterns in which temperature was controlled
by flake concentration per unit area. Carbon black will absorb microwave radiation in
a similar fashion, but is difficult to control. Mixtures of aluminium and carbon black
with metal flakes have proved effective [1].
A microwave interactive double bag, especially suitable for popcorn was patented by
Hartman [5]. The active component is a printed coating of aluminium flake, clay and
a binder.
The two main drawbacks of continuous film pad susceptors are that they are limited
to flat sheets and only function in one heating cycle. The heat generated destroys the
continuity of the metal film. Once crazed in this way, they cease to operate. Thus they
are regarded as ‘one trip’ disposable packaging, suitable for pies, pizzas, french fries
and popcorn.
Incorporating metal flake by mass pigmentation provided a route to the reusable or

‘rotable’ container. A low cost alternative to the present ceramic browning dishes also
became possible, making the microwave frying pan an economically attainable goal.
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Substantial R&D effort has been expended to establish the optimum metal type, flake
size and loading [6, 7]. Metal concentration per unit area of a tray controls the temperature.
At all metal concentrations, a steady state is reached at which heat is radiated from the
surface at the same rate as incident microwave radiation is absorbed and converted into
heat energy. Matching the metal content of a tray to the anticipated food load is required
for generation of the required 190-230 °C browning temperature in an average microwave
oven. Using aluminium flakes, a loading between about 10% and 22% w/w with the
polymer is required in a 0.5-0.7 mm thick PET tray, used in a 650-700 watt oven operating
at 2450 MHz.
The heating rate is relatively insensitive to flake size. Large flakes appear to function
slightly better than smaller particle sizes. A useful advantage is the ability to generate a
different temperature in different areas of a container by varying the thickness of the
moulding and with it, the flake concentration per unit area. This is particularly useful
for the so-called TV dinner. This is a multi compartment meal, usually composed of
meat, a vegetable and potato or rice. Injection moulding allows areas of differing thickness
within a single tray. When aluminium pigmented, such trays offer differential heating
rates to accommodate the differing heat capacities of various foods. All the components
of the TV dinner can then be brought to the same temperature at the same time.
In trials of an empty container, the hottest areas were surprisingly not at the corners,
which are reputed to concentrate microwave energy, but at the centre of the panels. Even
at loadings of over 20% w/w aluminium in PET trays, no arcing occurred. The tray was
also little affected by its position in the oven and retained its structural integrity well
throughout trials, including multiple dishwasher cycles.
A practical example of microwave heating using an aluminium flake pigmented PET

tray is to poach or fry eggs since they are notoriously difficult to cook in a microwave
oven. The technique used is to exclude microwave energy from the egg itself and to cook
it by the thermal energy emitted by the tray and its similarly pigmented cover. Cooking
time is around 1.5 minutes at a medium-high power setting. The result is comparable to
frying an egg in a conventional frying pan.
Products are commercially available in which aluminium flake is formulated with a carrier
resin, approved for direct food contact. The composition is offered in granular form at
the highest metal/carrier ratio that can be sustained to retain adequate dispersibility in
polyesters such as PET at the high loadings required.
It is possible that the demonstrated microwave heating ability of metal flake filled polymers
may have other less obvious uses in the area of selective heating. For example, a metal
flake pigmented plastic sleeve could be softened using microwave radiation to bond two
plastic pipes together without heating or deforming the pipes themselves.
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15.3 Electrical conductivity
Although advances have been made in inherently electrically conductive polymers, a

review is outside the scope of this book. In a non-conductive polymer matrix, the filler
provides conductivity, whether it be conductive carbon black or a metal. For metal
pigments, the key requirement apart from high conductivity in the bulk metal is a high
aspect ratio. In this respect, metal fibres can be more effective than flakes.
15.3.1 Product forms
It is widely assumed that since bulk metals conduct electricity, so also must derived flake
pigments. Whilst true for most metals, it is not so for aluminium. Given its widespread
use and apparent lack of chemical activity, it is surprising to find aluminium so high in
the electrochemical series. Indeed it lies just below the more obviously reactive elemental
metals potassium, sodium, calcium and magnesium.
The reason for this inert behaviour lies in the nature of the metal surface. All aluminium
in ambient conditions is coated by a film of aluminium oxide, estimated at only 3-5 nm
in thickness. This tenacious coating helps to protect the underlying metal from chemical
attack, but is itself a limited conductor of electricity. Various ingenious attempts have
been made to render aluminium flake conductive, often for suppression of electromagnetic
interference (see section 15.4) or merely for antistatic performance (see section 3.3.4).
Sternfield reviewed such aluminium pigments, including 1-1.4 mm long, 25-40 µm thick,
quench cooled flakes manufactured by Transmet Corporation [8]. Typical formulations
required 18-22% concentration by volume to change conductivity suddenly from low to
high. The Thermofil company in the USA has developed an aluminium pigmented,
conductive Nylon 66 blend [9].
Charles claimed certain organo aluminates, titanates and zirconates as agents capable of
enhancing the electrical conductivity of metal particulates [10]. The electrical resistivity
of a mixture of sub 45 µm particulate aluminium, a phosphorus-containing titanate and
a polyethylene glycol was 26 ohm/cm, compared to 31,850 ohm/cm when the titanate
was omitted. Similar results were claimed for copper, nickel, tin and zinc.
Deguchi [11] disclosed an electrically conductive thermoplastic resin composition. It

comprises a thermoplastic and 8-15% by volume of a dispersed phase consisting of at
least 2% by volume of metallic fibres of diameter 10-150 µm and length 0.5-10 mm and
at least 2% by volume of carbon fibres. The metal fibres may be of steel, gold bronze,
copper, aluminium and their alloys.
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Figure 15.1 Use of conductive ink in a calculator keypad

Reproduced with permission of Chris Williams
The noble metals, silver and gold, in particulate or flake form are used in electrically
conductive inks for polymeric or resinous printed circuit boards. For example, McGowan
of the then Ciba-Geigy Corporation [12], disclosed such a coating containing fine, particulate
silver and glass frit. Silver flakes also find a use in the defrosting elements of car windscreens.
Fine particle size conductive metals, such as nickel and silver, are used in inks for touch
keys in calculators, TV and video controllers and the like (see Figure 15.1).
Such conductive coatings are generally produced in solvent based resin systems, however
nickel flakes are also suitable for conductive water-based systems due to their good
resistance to corrosive attack.
15.4 EMI shielding
This section follows logically from the last, as EMI shielding requires a degree of
electrical conductivity.
Wherever an electrical current flows, an electric field exists. Electronic devices are capable
of both emitting and receiving extraneous electromagnetic radiation. This generates
electro-magnetic interference, more usually referred to as EMI.
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15.4.1 Origin and measurement
There are numerous sources of EMI. These include natural atmospheric noise, electric
storms, fluorescent lights, vehicle ignition systems, unsuppressed motor commutators,
high voltage overhead power lines and unwanted radio transmissions. The effects
generated by these emissions range from the annoying, such as poor radio or TV reception,
to the disruptive, for example the wiping of a computer’s memory, to the dangerous,
where emergency services or air traffic systems are disrupted. In the modern world of
instant electronic communication, increased use of limited bandwidth airways has only
exacerbated the problem. The very rapidly rising number of mobile telephones increasingly
need to be protected against absorption of spurious radiation. Coincidentally, they may
need to be protected from radiating interference from their own circuits.
15.4.2 Legislative requirements
The need for government regulation of electromagnetic emissions has been recognised
for some time, but its introduction in Europe has been delayed. Almost twenty years
ago, the United States Federal Communication Committee (FCC) [13] issued regulations
limiting the field strength of emitters to between 30 MHz and 1 GHz. In Europe the long
awaited EEC Electromagnetic Compatibility Directive 89/336/EEC [14], as amended by
92/31/EEC finally came into force on 1st January 1996. The directive requires almost all
items of electrical equipment sold in the European Community to ‘be so constructed that
they do not cause excessive electromagnetic interference and are not unduly affected by
electromagnetic interference.’
These requirements are met by what is now generally described as EMI shielding or
simply EMS (Electro-Magnetic Shielding).
15.4.3 Shielding principles and techniques
Several textbooks collectively provide a comprehensive introduction to the subject.

‘Grounding and Shielding Techniques in Instrumentation’ [15] introduces the properties
of electrical fields before moving on to describe the applications of electrostatics to the
practical problem of shielding instruments. ‘Noise Reduction in Electronic Systems’ [16]
considers cabling, grounding, filtering and shielding techniques. It includes a useful section
on electrostatic discharge and in an appendix, a very practical noise reduction checklist.
‘Controlling Radiated Emissions by Design’ [17] contains a chapter devoted to box
shielding, including the shielding effectiveness of materials such as conductive plastics.
The strength of this text is that it teaches the principles of cost-effective EMS design,
starting with how to determine box attenuation requirements.
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Ideally, shielding should completely enclose all sensitive components, forming a so-called
Faraday Cage of highly conducting material. The obvious route of using fabricated metal
cages tends to be expensive and is undesirable in weight-critical applications such as
mobile phones. Designers prefer plastics, which as well as being lightweight, are more
easily formed into complex shapes. They also offer corrosion resistance, durability and a
good surface finish without the need for machining.
15.4.4 Shielding of polymers
Unfortunately, unlike metals, polymers are virtually transparent to electromagnetic

radiation. They must therefore be shielded. There are several techniques available to
achieve this. Early solutions involved metal foil, later adapted for attachment directly to
the polymer during injection moulding. Alternatively, the surface of the article may be
prepared to take an electrocoat. Zinc arc spraying is another method in which zinc wire
is continuously fed through an electric arc. The melted zinc is then sprayed onto the
substrate by compressed air.
The most widely used pigment is conductive carbon black. In the finest particle sizes
it has very high surface area to establish a conductive path. It is also relatively
inexpensive. Its main disadvantage is its colour. Carbon black is therefore unsuitable
for transparent or coloured finishes. A further problem is its strong absorption in the
IR region of the electromagnetic spectrum. On exposure to sunlight, heating of the
coated or mass pigmented article can occur, which can affect the performance of
enclosed electronic circuits.
Shielding methods relevant to metal pigments are coating and mass pigmentation. Coating
the plastic component with a conductive paint became the favoured route in the 1970s
and remains widely used today. Conductive paints containing fine nickel, copper, silver-
coated nickel or even pure silver flakes are applied by spraying using conventional spray
painting equipment.
The mass pigmentation route uses conductive carbon black, as powder or fibre, or metal
fibres or flakes, especially those derived from stainless steel.
Table 15.1 shows the signal attenuation effectiveness of these various techniques.
Several coating and mass pigmentation techniques for EMI shielding involving metal
flakes have been proposed. The Novamet Specialty Products Corporation and TBA
Industrial Products Ltd., are firmly associated with such products.
186
Table 15.1 Effectiveness of various shielding techniques

Shielding system Shielding effectiveness (dB)
In-mould foiling 40-90
Metal flake 40-60
Metallised fibre 40-80
Nickel paint 30-80
Vacuum metallising 50-90
Zinc arc spraying 30-60
15.4.5 Coating techniques
The earliest air drying acrylic paints had values around 1 ohm/cm2, but advances in flake
orientation and drying characteristics have reduced this to below 0.5 ohm/cm2.
Hart has recently provided a summary of the requirements and advantages of the coating
route, especially in relation to the Compatibility Directive [18].
Metal loadings of over 40% w/w are required in dry film for the highest degree of shielding
effectiveness. This places considerable demands on the formulation of the coating,
especially to avoid settling of relatively heavy metal particles in low viscosity media.
Low shear incorporation is necessary to avoid folded and broken flakes that can adversely
affect the smoothness of the dry film. A continuous, uniform film is important. Any
flakes protruding through the film surface can be removed by abrasion, with a
corresponding reduction in shielding efficiency. There is little requirement for a good
appearance since the coating is normally applied to the inside of the enclosure.
The range of suitable metal ‘pigments’ is limited by the requirement for high electrical
conductivity, corrosion resistance and high aspect ratio. In practice, copper and nickel are
the most widely used. Although it has the better conductivity, copper tends to tarnish
thereby reducing its effectiveness. In recent years more resistant forms have been formulated.
Nickel has excellent corrosion resistance. Its magnetic properties are also an advantage
in attenuating low impedance waves. The variety of geometries available increases the
metal’s versatility. The dendritic (see figure 15.2) and flake forms (see figure 15.3) are
more effective than the spherical type illustrated in figure 3.6. (see figure 15.4) Though
popular for its cost-effectiveness amongst coating techniques, there are concerns over
nickel’s toxicity, especially as it tends to be supplied as a dry powder (see Chapter 16).
187
Figure 15.2 Electron micrograph of dendritic nickel powder [1 cm = approx. 7 µm]

Figure 15.3 Electron micrograph of conductive nickel flake [1 cm = approx. 3 µm]

188
Figure 15.4 The effect of pigment loading on the resistivity of various conductive
nickel systems.
The corrosion resistance of nickel makes it suitable for water-based coatings, giving very
good overall performance. Stainless steel flake is an alternative, since like nickel it is
corrosion resistant (see Figure 3.7).
Nickel-coated graphite is an angular particulate (see Figure 15.5). It provides particularly

good electrical properties when incorporated into silicone resins used to produce gaskets
for shielding applications. These grades are available containing 25%, 62% and 75%
nickel, the two higher nickel content materials being preferred for electrical conductivity.
Nickel-coated mica at 10-15% loading has also been found to give good shielding
effectiveness [19]. Where better impact strength is required, blends with stainless steel
fibres are suggested.
For the greatest attenuation (reduction in electromagnetic transmission = shielding

effectiveness) in the most demanding applications, silver flake is used despite its high
cost. A less expensive compromise, that still retains the conductivity of silver is silver-
coated nickel flake.
Friedli and Lau at the Dow Chemical Company [20] patented an aqueous coating
composition for EMI and radiofrequency (RF) shielding. Flakes or powders of nickel,
189
Figure 15.5 Electron micrograph of conductive nickel-coated graphite

[1 cm = approx. 40 µm].
copper, aluminium or combinations of these are combined with a zwitterionic, bisphenol-

A based monomer, a polyacrylamide, a non-ionic surfactant and water. Other envisaged
applications include conductive tapes, adhesives and inks for printed circuits.
Related work by the Honda Motor Company is described by Monte [21]. Surface
oxide-free zinc, prepared by friction milling, when formulated in an acrylic coating
and applied and cured on ABS, offers an electromagnetic compatibility comparable to
that of a molten zinc coating.
Where the weight of an enclosure is important, a coating has the advantage over mass
pigmentation that it concentrates the flakes in a relatively thin film. It also allows flow
and weld lines to be avoided where the aesthetic appearance of the part is important.
Coating however, unlike mass pigmentation, is a multistage process. It tends to be labour
intensive and processing time is extended. Spray equipment, now increasingly required
to have provision for volatiles capture, is expensive and does not always adequately coat
parts with complicated geometry. Furthermore, the coating may peel or wear, thus
destroying the conductivity essential for effective EMI shielding. For these reasons, mass
pigmentation has been investigated as an alternative. At the time of writing however,
commercial acceptance of mass pigmentation has been limited.
190
15.4.6 Mass pigmentation techniques
A text on the electrical properties of metal-filled polymer composites is provided by Bigg

[22] of Battelle Columbus Laboratories. Very large aluminium flakes with an aspect
ratio of 16.7:1 were found to become conductive at 10% by volume when compression
moulded. Considerable flake damage was reported when the same formulation was
injection moulded. This increases the critical concentration for EMI performance.
Chen [23] investigated PP compounded with carbon black and aluminium flake, not
only for EMI performance, but also for processability and mechanical properties retention.
The conductivity threshold was about 5 vol.% (20 wt.%) for conductive carbon black,
but 5-10 vol.% (20-40 wt.%) for aluminium flake. At the maxima within these ranges,
shielding effectiveness reached 30 and 35 dB, respectively. This performance is comparable
with that of 1 mm copper sheet or of a continuous nickel coating. Chen found that in
general, conductive fillers with a high aspect ratio have greater statistical likelihood of
forming the necessary conductive paths in the polymer matrix.
Kanda of Showa [24] disclosed an EMI shielding material comprising a thermoplastic

resin, an aluminium particle, preferably a very large flake, and electrically conductive carbon
black. A wide range of polymers with 0.1–5 mm aluminium flake and a carbon black
having a specific surface area of 20-1800 m2/g is claimed. The aluminium flake and carbon
black are mixed in approximately equal parts to provide 10-60% of the composition by
volume. Attenuations measured for the examples range from 25 to 43 dB.
Also at Showa [25], an olefin-based rubber was combined with aluminium or alloy in
powder, fibre or flake form, a vulcanising agent and the carbon black. Attenuation was
in the range 35-50 dB.
A key disadvantage of mass pigmentation is the high concentration of metal flake or

fibre required. As well as increasing the cost of the moulding, such loadings also
compromise its mechanical properties. Although more effective, high aspect ratio flakes
are also more prone to damage during incorporation than those of low aspect ratio.
Inclusion of low concentrations of silane, titanate or zirconate coupling agents enhances

EMI shielding efficiency in filled systems, according to Monte [26]. This is achieved by
lowering melt viscosity during processing. This deagglomerates the conducting particles,
improving their dispersion and increasing the adhesion between filler and matrix. In
turn this limits the loss of mechanical properties.
The main use of spherical nickel and silver-coated nickel powders is to produce composites
for electromagnetic shielding applications. Because of their controlled size range they
can be incorporated into media such as silicone elastomers or epoxy resins that are used
to make conductive gaskets or adhesives. They are not normally used in coatings because
191
the filamentary (thread-like) powder and flake forms are more effective, providing higher
levels of conductivity at lower pigment loadings than the spherical product.
Nickel-coated carbon fibre is suitable for incorporation into thermoplastic materials for
a wide range of electrically conductive applications, including EMI shielding.
A potential disadvantage of the mass pigmentation method is that surface finish may be
adversely affected, especially if large fibres or flakes are used. It may then be necessary to
paint the resulting mouldings to mask the defects and provide an aesthetically pleasing
moulding. If this is the case, it may well be more cost-effective to revert to applying an
EMI coating to the inside of the component. Alternatively co-injection moulding can be
used to apply a thin skin of aesthetically acceptable polymer simultaneously over a core
containing the conductive pigment.
15.5 Light exclusion

Carbon black remains the most cost-effective means of rendering a polymer opaque to
light. Where a more aesthetically pleasing effect is also required, such as in the packaging
of light sensitive foods, the high covering power of fine grades of aluminium flake pigments
makes them a good choice.
A recent development combining the aesthetic attractions of aluminium and gold bronze
pigments with the functional attribute of high opacity is known as ‘scratch cards’. These
are cards issued as lottery tickets, promotional or contest forms or the like. A winning
ticket is identified when the opaque coating covering printed information is removed by
scratching it off with a fingernail or coin. Opacity and inter-coat adhesion are essential
to dependably conceal this underlying information until the coating is removed.
Construction of the card is complex to prevent tampering (see Figure 15.6). To a base of
paper stock, a thin film of metal foil may be attached for added security. The design is
printed down next. This is the layer ultimately revealed by the act of scratching off the
overlying coatings. A clear overlacquer or lamination follows, then the all-important
metal pigmented obliterating patches. Finally, optional additional personalisation may
be printed onto the obliterating layer.
The obliterating layer is typically formed from a fine particle size, high opacity aluminium
or gold bronze flake pigment in resin and solvent. Alternatively it may be water-based,
using a polymer latex.
Carrick [27] describes a scratch-off coating composition comprising an aqueous acrylic

polymer resin, a pigment such as aluminium flake and a powdered filler such as calcium
carbonate.
192
Figure 15.6 Structure of a lottery scratch card

Reproduced with kind permission of Chris Williams
15.6 Heat and light reflection
The reflective nature of aluminium flakes also makes them a good choice for light and
heat reflective polymer film.
Reflectivity is enhanced by the orientation of flakes which takes place during mono- or
bi-axial stretching of the film. A typical application is crop ripening films, usually made
of polyolefins (see section 11.3).
A potential, but unproved application is use of metal flake coated PET film to replace
the vacuum aluminised PET film that is bonded to plasterboard to enhance thermal
reflectance and control vapour permeability. Very high quality leafing aluminium flakes
are required to approach the degree of reflectivity provided by vacuum deposition.
The most commercially developed application in this category is reflectors for vehicle
light cluster coatings. Again the highest reflectance aluminium flakes are necessary.
An unusual patent application by the 3M Company [28] describes light reflective articles
in which metal flake is used to enhance the reflectivity of transparent spheres. A coating
containing, for example, aluminium flakes in a transparent resin system is applied to a
substrate. It is then overcoated with spheres, such as glass beads. When partly pressed
into the surface, the metal flakes take the shape of the sphere’s surface, enhancing
reflectivity. The technique is used for reflective road and pavement markings.
193
Aluminium flake is also used to control the opacity of transparent polymers by imparting
opacity. When incorporated in PC sheet used as a glass substitute, the flakes regulate
solar transmission in proportion to their concentration. Flakes in the 30-70 µm diameter
range that are free of fines are the most effective. They reduce solar transmission without
preventing visibility.
A further specialised use of aluminium flake is to enhance the insulation value of foamed
PE pipe insulation. The flake particle size appears to control the nucleation of the PE.
This determines the cell size, on which the insulation value depends. As aesthetic properties
are of secondary interest, low cost, fine particle size grades are generally used.
Aluminium flake is also used in a novel process to prevent photographic or electrostatic

copying of documents by light reflection [29]. An orange, red or brown coating on white
paper, overlaid with a pattern of aluminium ink, prevents photocopying. The coating
‘blinds’ the copier and a black image is obtained. The invention is intended to maintain
the security of sensitive documents.
15.7 Thermal conductivity
The excellent thermal conductivity of metal flakes is demonstrated by the observation

that even at the relatively low concentration used for purely decorative effects in polymers,
it is often possible to reduce the temperature of the processing equipment by several
degrees. The improvement in thermal conductivity of polymer pigmented by large metal
flakes can be quite marked.
Cullen of Transmet Corporation [30] in the USA claimed that composites formulated
with up to 40 per cent by weight of high aspect ratio aluminium flakes have a heat
transfer effectiveness of 80 to 95% of that of the pure metal.
Spherical metal powders will increase heat transfer through polymers, but because of
their low aspect ratios and high density, high loadings, often over 50 weight percent,
have to be used. At such concentrations, mechanical integrity is poor and injection
moulding becomes difficult. Flakes are therefore preferred to atomised powder not only
due to their higher aspect ratio, but also their greater surface area for heat transfer.
Potential applications of metal filled polymers include any injection-moulded components

that have complex shapes, expensive to manufacture by casting or machining of the pure
metal. A good example is semiconductor heat sinks for the electronics industry, but car
engine components are also of interest, particularly since weight-saving is an incidental
bonus. Account must be taken of the effect on the mechanical strength of the polymer at
194
such high metal loadings. Nevertheless, metal filled plastics combine the conductivity of
metal with the low cost and easy processing of plastics.
The thermal conductivity of a material is the rate of heat flow in a temperature gradient.
Put more simply, it is the speed at which heat can move through a material. In the following
formula, thermal conductivity (K) is given by:
K = QD/A(T1-T2)
where: Q is the rate of heat flow

D is the sample thickness
A is the area
(T1-T2) is the temperature gradient, T1 being the temperature of the warm
surface and T2 the temperature of the cold surface.
Measurement of thermal conductivity is described in ASTM C-177 [31]. In this test two
flat plates of material of uniform thickness are placed one on each side of a heater. This
assembly is then placed between two cooling blocks, and surrounded by insulation.
Temperature measurements are made at the interface between the material and the cooling
block. The temperatures, and the thickness and area of the material are known, as is the
output of the heater, which is determined electrically. From these measurements, the
thermal conductivity can be calculated.
Using ASTM C-177, it is possible to measure thermal conductivities of both pigmented

and unpigmented polymers, and rank them. The Transmet workers were also able to
show inherent differences in thermal conductivity of polymers alone, PVC being superior
to polyolefins, which in turn were more conductive than ABS or PS.
To dramatically increase thermal conductivity, a metal with as high an aspect ratio as possible
must be incorporated into the base polymer. The Transmet work was directed to rapidly
quenched aluminium flakes. Such flakes are manufactured by a melt spinning process. The
very rapid cooling stage limits oxidation, allowing the metal to retain more electrical as well
as thermal conductivity. For commercially useful thermal conductivity, a loading of 18 to 22
volume% (approx 40 weight%) is necessary. Loadings of 35 volume% were achieved and in
some cases higher loadings were possible. Moulding could still take place on any injection
moulding machine.
195
15.8 Lubrication and wear reduction
The current use of copper and aluminium flakes in high temperatures greases suggests
that they may also be incorporated in polymers to extend the life of plastic bushes and
bearings. To prevent flakes from abrading from the polymer surface, it may be necessary
to bond them into the polymer matrix using coupling agents such as titanates, zirconates
or silanes. The heat dissipation property of metal flake is a further advantage in extending
bearing life. Activity in this area is at the research stage.
Nickel flakes are used in a number of specialised applications such as anti-seize additives
for high temperature lubricants and in others that rely on magnetic properties of the metal.
Stainless steel powders are produced primarily for powder metallurgical and thermal
spray applications and for use in controlled porosity filtration systems. They are
incorporated into GRP mouldings to increase the wear resistance of the surface layer.
15.9 Gas and moisture barrier
Formulations providing gas and moisture barrier properties have some features in common
with mechanical reinforcement. The absence of bonding between conventional flakes and the
polymer matrix leaves capillary channels that promote rapid migration of gases and moisture.
Although the presence of metal flakes may increase the path length for migration from
one side of a pigmented polymer film to the other, the net result, even at metal loadings
up to 10% w/w, is little change in barrier properties. Eliminating capillary channels by
the use of surface treated metal flakes bonded into the polymer matrix, combined with
good orientation of the flake by film stretching during manufacture, have shown improved
barrier properties in recent tests. The cost-in-use of these pigmented films, compared to
existing barrier films such as vacuum deposited metallised film and films co-extruded
with barrier polymer layers, is the subject of current research and commercial interest.
15.10 UV protection
Aluminium reflects approximately 90-95% of incident UV light [32]. This has implications
for the protection of UV sensitive polymers such as polyolefins from embrittlement in
exterior applications. The crop ripening films described in section 11.3 are a good example.
Unpublished work carried out by Silberline in the USA compared 1%, 3% and 6%
loadings of a fine particle size aluminium pigment in high density PE with the performance
196
of unpigmented polymer. All samples were exposed for up to 1200 hours in an Atlas
Weatherometer.
Even a 1% loading provided a modest improvement in tensile strength retention. At 3%,

the useful life of the polymer was extended by a factor of 3. When the loading was
increased to 6%, over 80% of the tensile yield and break strengths were retained after
1200 hours exposure. In comparison, the unpigmented polymer lost over 50% of both
properties after less than 600 hours.
15.11 Laser marking
As well as the familiar cutting applications, modern industrial lasers have recently found
use in marking a very wide range of materials, including polymers. The main advantages
are speed, precision, cost-effectiveness and access without mechanical contact. The
technique is very flexible, easily automated and environmentally friendly since there are
no solvent emissions. Moreover, since the laser beam writes into, rather than onto, the
surface, the marking is fade and abrasion resistant, effectively providing a permanently
readable surface.
A typical installation has a CO2 or higher intensity neodymium doped, yttrium aluminium
garnet (Nd:YAG) laser whose beam is directed onto the workpiece by galvanometer
mirrors. A computer controls the marking process to produce a wide range of characters,
symbols, logos and graphics. CAD and graphics files may be directly imported from
other applications. Marking speeds up to several metres per second are achievable with
an accuracy of 0.1 mm.
There are three marking mechanisms, depending on the nature of the polymer. All are
equally durable. The first method uses a laser to heat the material, creating a colour
change at the surface, in a process called annealing marking. Surface contours are retained.
Alternatively, material can be physically removed to achieve laser engraving. This is
useful where infill coloration is subsequently applied.
Laser marking of polymers is technically more challenging than that of most other
substrates. The third technique, pigment marking, specifically refers to the incorporation
of special pigments, such as mica flakes into mass pigmented polymers to create a colour
change under a laser beam. For example, white polyolefins can be coloured black by
carbonising the polymer. The mica is believed to absorb the laser energy at its surface,
which in turn causes carbonising of the local polymer. By a similar mechanism, black
pigmented polymer can be marked white by foaming the polymer.
197
Figure 15.7 The effectiveness of aluminium flake in laser marking. Unpigmented PP,
left, exhibits less definition than 2% mica pigmented PP, centre. 2% SILVET LR 30
aluminium flake filled PP, right, shows the highest definition
The main challenges in laser marking of polymers are definition quality and coloration
strength. The visual contrast between image and non-image areas of unpigmented
polymers is generally insufficient, which explains the interest in colour enhancing pigments
such as mica.
Most recently, work on aluminium flakes via the pigment marking process has yielded
very encouraging results, prompting Silberline to release a range of aluminium pigments
in granular form [33]. These ‘LR’ or laser receptive grades provide a higher degree of
both fine coloration and definition than mica types, as shown in Figure 15.7.
15.12 Magnetic applications
The magnetic properties of iron particles, in powder or flake form, are applied as moulded
alternatives to permanent magnets. High loadings are required, incorporated in polymers
by mass pigmentation. Although lacking aesthetic properties, the resulting mouldings can
have complex shapes, difficult or impossible to produce in a conventional permanent magnet.
One of the more prominent applications is in elastomeric door sealing strips for refrigerators.
Patterns in coatings can be achieved by applying liquid coating systems, pigmented by

magnetically susceptible flakes, to substrates under a magnetic field. The flakes orient
along lines of magnetic force to create a decorative effect.
198
15.13 Corrosion resistance
Zinc powder and flake, and aluminium, nickel and stainless steel flakes are used in a
variety of anticorrosive and other protective coatings [34].
Hare [35], in several papers, has evaluated both elemental metal pigments and pigments
free of elemental metals, such as micaceous iron oxide, in barrier coatings. Binder selection
is generally confined to those polymers with inherently low moisture and oxygen
transmission rates and high dielectric constants. A polymer bearing carboxyl, hydroxy
and backbone ester groups does not usually perform as well as a polymer having a
carbon-carbon, carbon-oxygen or aromatic backbone. On the other hand, some polarity
improves adhesion. Vinyl and coal tar systems make excellent vehicles, followed by epoxies
and urethanes. Section 13.5 contains a typical starting point formulation.
In pigmentation trials involving extended outdoor exposure, leafing aluminium flake

was found to be particularly effective [36]. The metal appears to provide some UV
protection to the binder. Formulations are also relatively insensitive to flake particle size
or leafing value. Aluminium gives uniformly excellent protection and good aesthetics,
regardless of vehicle type or test environment. Hare [37] found that comparative tests
with glass flake and mica gave very poor results. Stainless steel and micaceous iron
oxide, though better, showed neither the degree of performance nor the universality of
aluminium. The only weakness of aluminium was its sensitivity to extremes of pH.
15.14 Flame retardation
Inclusion of aluminium flake pigment in certain polymers has been shown to generate
some flame retarding activity. Unfortunately, loadings above normal commercial colouring
concentrations are necessary, typically from 5% w/w on polymer upwards. There is
some evidence that finer grades are more efficient than coarse types. Irrespective of flake
size however, the effect is insufficiently marked to allow a recognised flame retarding
agent to be omitted from formulations in which it is otherwise required.
The most amenable polymers are polyolefins, ABS, polystyrene and polycarbonate.
Polyamide of the common polymers shows least activity. Apart from a slowing of the rate
of burn, structural integrity is better maintained and dripping of burning polymer reduced.
A possible explanation is that aluminium oxide generated during combustion coats and
helps to protect unburned material. Aluminium oxide is a component of commercial flame
retarding agents. Unburned aluminium may conduct away the heat of combustion, which
is higher than it otherwise would be, because oxidation of aluminium is very exothermic.
199
15.15 Radiation absorption
Another specialised non-colouristic application involves the use of lead particles in

polymers intended for high energy radiation shields. A typical example is the moulded
lead aprons worn by radiographers for protection from the cumulative effects of continued
daily exposure to X-rays in the course of their work.
References
1. K. A. Pollart and T. P. Lafferty, inventors; James River Corporation of Virginia,

2. O. E. Seiferth, inventor; James River Corporation, assignee, US Patent 4,641,005,

1987.
3. H-F Huang and D. E. Plorde, inventors; E.I. Du Pont de Nemours, assignee,

4. M. Paleari, inventor; W. R. Grace & Co.-Conn, assignee, Canadian Patent

2,149,097, 1995.
5. R. R. Hartman, B. D. Berger and K. J. DeHaan, inventors; James River

Corporation of Virginia, assignee, US Patent 4,982,064, 1991.
6. K. Goddard, Food Manufacture, 1990, September, 49.
7. The Influence of Microwave Radiation on Aluminium Flake Pigments, Product

Information, Silberline Ltd., UK, 1991.
8. A. Sternfield, Modern Plastics International, 1982, 12, 7, 48.
9. Survey of commercially available polymers in Modern Plastics, Mid-November

1994, B-169.
10. H. Charles, inventor; no assignee, US Patent 4,374,760, 1983.
11. R. Deguchi, inventor; Ube Industries Ltd., assignee, US Patent 4,569,786, 1986.
12. E. McGowan, Jr., inventor; Ciba-Geigy Corporation, assignee, US Patent

4,369,063, 1983.
13. United States Federal Communication Committee Rules and Regulations, July
1981, 11, Part 15, Docket No. 20780.
200
14. EC Directive 89/336/EEC, relating to electromagnetic compatibility, 1992.
15. R. Morrison, Grounding and Shielding Techniques in Instrumentation, 3rd

Revised Edition, John Wiley and Sons Inc., Chichester, 1986.
16. H. W. Ott, Noise Reduction in Electronic Systems, 2nd Revised Edition, John
Wiley and Sons Inc., Chichester, 1988.
17. M. Mardiguian, Controlling Radiated Emissions by Design: EMI/RFI Reduction,

Van Nostrand Reinhold, New York, 1992.
18. A. C. Hart, Polymers Paint Colour Journal, 1996, 186, 4378, S3.
19. S. Naik, M. Carmel and M. Fenton, Proceedings of the SPI 41st Annual
Conference, The Reinforced Plastics/Composites Institute, Atlanta, USA, 1986,
Paper No.15E.
20. H. R. Friedli and P. Y. Lau, inventors; The Dow Chemical Company, assignee, US
patent 4,556,506, 1985.
21. S. J. Monte, Ken-React Reference Manual, Kenrich Petrochemicals Inc., 2nd

Revised Edition, 1993, 63-5.
22. D. M. Bigg in Metal-Filled Polymers, Ed., S. K. Bhattacharya, Marcel Dekker

Inc., New York, 1986, 165-217.
23. D. K. Chen, C. H. M. Ma and A. T. Hu, Proceedings of the 36th International

SAMPE Symposium, San Diego, USA, 1991, 1474.
24. M. Kanda, T. Hatakeyama and Y. Morito, inventors; Showa Denko KK, assignee,
US Patent 4,508,640, 1985.
25. M. Maeda, N. Watanabe and K. Fujitani, inventors; Showa Denko KK, assignee,
US Patent 4,557,859, 1985.
26. S. J. Monte, Ken-React Reference Manual, Kenrich Petrochemicals Inc., 2nd

Revised Edition, 1993, 65.
27. B. W. Carrick, inventor; GTECH Corporation, assignee, US Patent 5,215,576,

1993.
28. K. Hachey, inventor; Minnesota Mining and Manufacturing Co., assignee,

European Patent 0,683,403 A2.
201
29. K. Nagafuchi, inventor, Kisokaseisangyou, Co., Ltd., assignee, US Patent

5,114,782, 1990.
30. D. L. Cullen, M. S. Zawojski and A. L. Holbrook, Plastics Engineering, 1988,

44, 1, 37.
31. ASTM C 177-97

Test Method for Steady-State Heat Flux Measurements and Thermal
Transmission Properties by Means of the Guarded-Hot-Plate Apparatus.
32. J. H. Tundermann and J. H. Harrington, inventors; The International Nickel

Company, assignee, US Patent 3,941,584, 1976.
33. ‘SILVET LR’ aluminium flake pigments, Product Information, Silberline Ltd.,
UK, 1998.
34. T. Higashiyama and M. Nakazato, inventors; Nippon Dacro Shamrock Co.,

assignee, European Patent 0,468,883, B1, 1996.
35. C. H. Hare, Journal of Protective Coatings and Linings, 1989, February, 59.
36. C. H. Hare, Modern Paint and Coatings, 1985.
37. C. H. Hare and M. G. Fernald, Modern Paint and Coatings, 1984, 136.
202
16
Health, Safety and Handling
This chapter contains health, safety and environmental information on the common
metal pigments from a UK perspective. It includes specific guidance on correct handling,
storage, disposal and fire fighting techniques. Under each of these headings, information
common to all metal pigments precedes any guidance for particular metal types. Much
useful information is contained in a reference work by Lewis [1]. Health aspects of
aluminium and gold bronze pigments, not well covered in the period up to about 1980,
are well summarised by Wendon [2].
Several metals appear in the Approved Supply List, part of the European Commission (EC)
Directive 67/548, known as the Substances Directive. Its text has been incorporated into
the national law of the member states and revised and extended on numerous occasions.
The most recent UK enactment is the Chemicals Hazard Information and Packaging for
Supply or ‘CHIP’ 98. This provides a method for classifying the risk posed by a chemical
substance and expressing it via a group of numbered Risk, or ‘R’ Phrases of prescribed
text. The Risk Phrases are complemented by Safety, ‘S’ Phrases, which describe how to
respond to the stated hazard. In addition, substances and preparations are classified by the
hazards they present, such as flammable, harmful or toxic. Table 16.1 contains the hazard
classification, R and S phrases for the common metal pigments in dry flake form, together
with their European Inventory of Existing Chemical Substances (EINECS) and Chemical
Abstracts Service (CAS) identification numbers. Stainless steel is not included due to its
minimal hazard and variability of composition.
CHIP also contains rules governing the risk and safety classifications of preparations,
defined as compositions containing two or more substances. It is impractical to list
classifications of the very large number of preparations based on metal pigments.
Traditional aluminium pastes however, consisting of around 60-75% metal, with a balance
of high boiling aliphatic and/or aromatic hydrocarbons, are generally classified as
flammable. Only fine grades of copper and gold bronze are so classed. The remaining
metal pigments are not regarded as flammable.
Due to their physical form and absence of solvent, commercially available plasticiser
dispersions and metal pigment granules do not usually present a hazard and are therefore
not classified under CHIP. There is then no obligation to provide a Material Safety Data
Sheet under the Data Sheets Directive, 91/155/EC [3].
203
Table 16.1 Hazard classifications of metals in flake form

used as pigments
Metal Hazard R S EINECS CAS No.
Aluminium F 10 7/8,43 231-072-3 7429-90-5
Gold bronze F* (10) (7,43) None 12597-71-6
Copper F* (10) (7,43) 231-159-6 7440-50-8
Iron NC** - - 231-096-4 7439-89-6
Nickel Xn 40,43 (Z)22,36 231-111-4 7440-02-0
Zinc NC** 231-117-3 7440-66-6
* Flammable below about 10 µm ** NC = Not classified
Another important piece of legislation is the UK Control of Substances Hazardous to

Health Regulations 1999, (COSHH) [4] which update the 1994 Regulations in line with
the directive 96/55/EC [5] on the marketing and use of dangerous substances and
preparations. COSHH requires risk assessments to be prepared, which relate to the actual
use of the products. All metal pigments present a low degree of risk, provided they are
handled correctly. This chiefly means taking precautions to minimise dust formation and
maintaining good housekeeping practices (see section 16.2).
16.1 Health
Health aspects of metal pigments arise from two sources; those concerned with particle
geometry and those related to the toxicology of the metals themselves.
Particle geometry is relevant because the flake form, even of the heavier metals, is easily
carried in air currents. The smaller the particle size and the lower the density, the greater
the potential for dusting. Dry flake products present the greatest problem in this respect.
Pastes that have dried out will tend to aggregate, but inevitably some particles will also
break free. Both product types can therefore have the properties of nuisance dusts, with
assigned occupational exposure standards, (OES) defined in EH40 [6]. OES values for
aluminium particulates are 10 mg/m3 for inhalable dust and 4 mg/m3 for respirable dust.
These limits do not apply to exposure to aluminium coated with mineral oil.
Particles with a largest dimension of less than about 5 µm pass the hairs which line the
nose and are drawn into the lungs. The hazards here depend on the metal’s toxicology
and its ability to pass into the body tissues rather than being excreted.
204
The hydrocarbon solvents traditionally used as carriers for metal pigment pastes defat
the skin and with repeated contact can cause irritation and dermatitis. Habitual skin
contact should therefore be avoided.
Fatty acid lubricants are nowadays generally obtained from vegetable sources. When used
in products intended for food contact, this eliminates any possibility that the brain disease
CJD could be contracted. Traditionally these lubricants were derived from animal sources.
Plasticiser pastes are solvent-free, but phthalate esters, used for many years as inexpensive
carriers of low level of acute toxicity, are coming under scrutiny. Di-2-ethyl hexyl phthalate,
more commonly known as DOP (dioctyl phthalate), is a confirmed carcinogen in animals
[7]. A link with male testicular cancer and female breast cancer, as well as declining
sperm counts, is suspected [8]. Products containing DOP, emanating from the USA, are
required to display a carcinogen warning label. In Europe, DOP is classed as Xn (harmful)
according to the Substances Directive and is required to carry the risk phrases R62
(‘possible risk of impaired fertility’) and R63 (‘possible risk of harm to the unborn child’).
Though there is rebuttal of a cancerous link in man, phthalate substitutes are being
researched and introduced. Concurrently, a Dutch research group has produced evidence
to allay the apprehensions of the EU Scientific Committee for Toxicity, Ecotoxicity and
the Environment (CSTEE) [9, 10]. At the time of writing the future health and safety
status of DOP is unclear. It is worth noting, however that its hazard classification has
remained unchanged in CHIP 98.
Solid carriers such as low molecular weight polyolefins, used for granular product forms,
are generally unclassified for any health or safety risk. Granular products, being non-
dusting and virtually solvent-free are in any case unlikely to be accidentally ingested.
Indeed some are food contact approved, as are many mineral oil carriers. They therefore
present no significant health concerns.
16.1.1 Aluminium
Although found in the body, aluminium is not thought essential to any bodily function.
It has also long been accepted that aluminium flake does not present a health hazard in
manufacture or use.
Wendon [11] documents early studies on workers exposed to aluminium dusts during
manufacture. There was no indication that aluminium should be categorised as a health
hazard providing a conventional long chain fatty acid lubricant is used in the
manufacturing process.
205
Aluminium enters the body in food, drink and by inhalation. There is an effective
mechanism in the gut to limit absorption and in the kidneys to control excretion. In a
healthy adult, intake and excretion are in balance. Only where there is impairment of
bodily functions does the metal accumulate. Even then, cases of aluminium toxicity are
exceedingly rare [12].
Suggestions were first made of a link between aluminium and the degenerative brain
disorder Alzheimer’s disease in the mid 1970s, following the discovery of abnormally
high levels of aluminium in the brains of sufferers. The metal was also implicated in
dialysis dementia, a consequence of kidney failure and in a bone disease called
osteomalacia.
The Aluminum Association in the USA as long ago as 1955 had carried out an exhaustive
survey of over 800 sources of information on aluminium and health. The review was
updated in 1974 and again in 1981. Thereafter, a team at the University of Cincinnati
took up the monitoring process. Research programmes were put in place by the Aluminum
Association to establish where and how aluminium enters the body, how much is absorbed
and where it accumulates.
The state of knowledge was summarised for the layman by Epstein [13], who concluded
that the cause of Alzheimer’s disease had not been established. Neither was the biological
significance of aluminium in the brain understood. Absorption by the body is poor
and ordinary environmental exposure to aluminium is safe. Indeed a patent application
has recently been made for the use of iron oxide coated aluminium flake as a food
colorant [14].
16.1.2 Gold bronze and copper
Gold bronze is apparently non-toxic to man [15]. Both its copper and zinc constituents
are essential trace elements in the diet and a slight deficiency is not uncommon.
Due to its high copper content, inhalation of large quantities of gold bronze flake will
produce metal fume fever, which causes an influenza-like illness. The effect is transient,
typically lasting only 24 hours. There are no known adverse long-term effects of exposure.
It is not persistent in the lungs and is believed to be absorbed into the body in soluble
form. For this reason it does not lead to lung diseases such as pneumoconiosis that are
characteristic of some mineral dusts.
Concerns over the safety of gold bronze in packaging inks have been largely allayed by
Warnes [16].
206
The health and safety status of gold bronze is less of an issue than its environmental
impact. Its substantial copper content is often closely regulated in aqueous effluent by
environmental agencies.
As well as producing metal fume fever, copper also causes irritation of the upper respiratory
tract, a metallic taste and discolouration of hair and skin. The body is able to eliminate
any excess copper that is absorbed. Nevertheless, the 8 hour Time Weighted Average
(TWA) exposure limit for copper dust under the UK EH40 legislation is a very low 1 mg/
m3. The intraperitoneal LD50 in mice is also low at 3.5 mg/kg [17]. The relative absence
of health effects for gold bronze, which as noted previously is predominantly copper,
may be attributed to the protective effects of the milling lubricant.
16.1.3 Other metal pigments
The International Agency for Research on Cancer, IARC, classifies nickel as a carcinogen.
It is a poison by intratracheal, intraperitoneal, subcutaneous and intravenous routes
[18]. EC Directive 67/548 also classifies nickel as a carcinogen in Class 3, which requires
the hazardous designation Xn. The metal has a Maximum Exposure Standard or MES
with an 8 hr Time Weighted Average (TWA) of 0.1 mg/m3 [19]. This section of EH40
now contains the former schedule 1 of COSHH, the Control of Substances Hazardous
to Health Regulations, 1994, amended in 1996, 1997 and 1999 [20]. Skin contact should
be avoided. A form of dermatitis known as ‘nickel itch’ may be contracted and nickel
has also been found in the hair of workers exposed to the oxidised dust.
Iron and zinc are not inherently toxic materials [21, 22]. Iron dust can cause conjunctivitis.
When oxidised by heating, zinc causes a disease called ‘brass founders’ ague’ or ‘brass
chills’. It is not persistent. Type 316 stainless steel is classified in the same way as nickel,
because of its 12-14% concentration of the metal.
Silver and gold have no harmful effects other than the transient eye irritation to be
expected of flake particulates.
16.2 Safety
Safety precautions should address avoidance of both fire and personal contact, the
latter particularly by inhalation. The degree of fire risk is broadly proportional to the
position of the metal in the electrochemical series; in effect how prone to oxidation it
is. Thus, dry aluminium flake is regarded as a potent fire and explosion hazard, whilst
silver is non-flammable.
207
Classification of the flammability of metal pigments for transport is according to tests

prescribed in the UN Recommendations on the Transport of Dangerous Goods [23]. The
procedure involves spreading a carefully formed track of the product on an inert surface,
igniting one end of the track and determining the distance covered by the flame front in
two minutes (or 20 minutes in the case of metallic powders). If the distance is less than 20
cm, the material is declared non-flammable. Above this figure, a more stringent set of tests
must be followed, potentially requiring the product to carry a flammable designation.
Safety precautions should be directed at preventing contact of the metal pigment product
with any part of the body. In accordance with good industrial practice, basic personal
protective equipment comprising PVC gloves, eye protection and impervious clothing
should be worn. A mask suitable for nuisance particulates should be worn if conditions
are dusty. In warm conditions in confined spaces, the handling of large quantities of
solvent pastes may require a suitable respirator.
In the case of metal pigment compositions, account must be taken of the other components,
for example the flammability of the solvent components of pastes.
Contacting metal pigments with certain other commonly used materials can give unwanted
chemical reactions, or even pose an explosion hazard. Table 16.2 provides a list of materials
that should not be stored with, or allowed to come into contact with, the various metal
pigments in unpassivated form.
Table 16.2 Materials that should not be contacted with metal pigments
Metal Materials to avoid
Aluminium Acids, alkalis, chlorinated hydrocarbons, oxidising agents, iron oxide.
Gold Bronze Acids, acetylene, chlorates, bromates, iodates and oxidising agents.
Copper Acetylene, oxidising agents and halogens.
Nickel Acids.
Iron Strong oxidising agents and acids.
Zinc Acids, nitrates, chlorates, sulphur.
16.2.1 Aluminium
There is a tendency to underestimate the potential of aluminium to burn, probably because

in the bulk form and due to its thin, protective oxide coating, it appears inert. Powders
208
and solvent-based pastes are classified as flammable under the UN recommendations

mentioned previously [23]. In the case of pastes, it is common for the solvent component
to burn to the track length required by the UN test without ignition of the metal. Metal
ignition, where it occurs, is characterised by an intense white light.
Depending on the nature of the carrier, some granular products are non-flammable. This
is probably because the mainly hydrocarbon carrier burns to a rigid carbon residue that
coats the metal flakes, thereby preventing their ignition.
When airborne in finely divided powder or especially in flake form, the high surface area
of typically a few m2 per gram, provides enormous explosive potential, generating a rate
of pressure rise of over 20,000 psi/s. The quantity suspended in the atmosphere required
for this to occur is small, at around 10 g/m3, as is the few mJ required to initiate an
explosion. Such a low energy level can be generated by many apparently mundane sources,
for example loose electrical wiring, electric motor commutators or poorly lubricated,
overheating bearings; even static caused by pouring non-earthed powders. An atmosphere
containing as little as 9% oxygen in nitrogen will support combustion.
Aluminium flake in any non-passivated product form should not be allowed to come
into contact with water, especially at elevated temperature. The reaction between the
two generates extremely flammable hydrogen gas. For this reason an aluminium fire
should never be tackled with water (see section 16.6).
Contact with oxidising agents and halogens should be avoided. Iron oxide is another
substance that should be prevented from coming into contact with aluminium flake, since
a highly exothermic chemical reaction known as the thermite reaction may occur [24].
16.2.2 Gold bronze
Gold bronze powder is combustible but not explosive. Grades with median particle
diameters below about 30 µm are classed as flammable for supply and carry the CHIP
risk phrase R10. They are also flammable for transport. Coarser grades are generally
regarded as non-flammable for both transport and supply. Because much gold bronze is
still sold in the dry flake powder form, dusting should be avoided by use of good handling
techniques. Airborne material has the properties of a nuisance dust. There is no OES,
but an 8 h TWA exposure limit of 10 mg/m 3 is recommended [Manufacturer’s
recommendation; Wolstenholme International Ltd.]. The material is stable under normal
conditions, but contact with acetylene, chlorates, bromates, iodates and oxidising agents,
which could induce a violent reaction, should be avoided.
The solvents influence the safety classifications of paste forms in much the same way as
for aluminium pastes.
209
16.2.3 Other metal pigments

Copper flake can react potentially explosively with acetylenic compounds, oxidising
agents and halogens. Copper dust has an OES (8 h TWA) of only 1 mg/m3. Iron, stainless
steel and zinc pose no significant safety hazard.
Due to its classification as a carcinogen, measures must be taken to limit inhalation of
nickel flake dusts. It is also important to keep nickel out of wounds.
16.3 Health and safety in use

When incorporated in polymers, whether by mass pigmentation or as part of a coating,
the explosion hazards posed by dry metal pigments in particulate form are eliminated.
Health and safety issues then refocus on the properties of the metals themselves and on
the carriers, both liquid and solid, used to convey them into application media.
One of the most frequently asked questions on the health and safety of metal pigments
relates to food contact acceptability. The US FDA sets down in numbered paragraphs,
conditions and concentrations under which substances, but not preparations, are to be
regarded as safe in contact with food. Aluminium, for example, is approved as a pigment
and colorant in Title 21, Paragraph 26, Page 154 of Section 175.300 of the US Code of
Federal Regulations. In the UK the relevant legislation is the Statutory Instrument 1998
No. 1376, the Plastic Materials and Articles in Contact with Food Regulations. Gold
bronze is not approved for direct food contact applications.
Directive 95/45/EC [25], which came into force in the member states in July 1996, builds
on 89/107/EC [26] and 94/34/EC [27] to define the purity of colorants used in foodstuffs
for human consumption. Aluminium (E173), silver (E174) and gold (E175) pigments are
listed. Also listed in this Directive are the red, yellow and black oxides of iron used as
coloured coatings on metal flake surfaces.
A further EC Directive, 94/62/EC [28], on recovery, recycling and re-use of packaging
and packaging waste also impacts on metal pigments. Article 11 requires that the sum of
the concentrations of lead, cadmium, mercury and hexavalent chromium shall not exceed
600 ppm, 250 ppm and 100 ppm by 30 June of the years 1998, 1999 and 2001,
respectively. In practice, the high purity metals used in modern pigments comfortably
comply with this legislation, even at loadings well above commercial limits.
Another key piece of European legislation, applicable to both mass pigmented polymers
and coatings, is EN71 Part 3, (1994) [29], produced by the European Committee for
Standardisation. These so-called ‘Toy Regulations’ specify limiting concentrations of
certain elements, mostly heavy metals, extractable from toys. It is important to note that
the Standard does not specify limits for the elements themselves, but deals with
210
extractability or migration of these impurities from the finished toy material. Adoption
of the Standard, which supersedes that of 1988, is mandatory in all CEN member states.
As with the Packaging Directive mentioned previously, the purity of metal pigments is
generally sufficiently high for compliance, even above normal commercial loadings.
16.3.1 Mass pigmentation
Metal pigments incorporated by mass pigmentation present no safety concerns related

to their physical form. Of more interest is conversion temperature since it is this
parameter that differentiates mass pigmented systems from coatings. Carriers that are
of little safety concern at ambient temperatures can become a risk at processing
temperatures. It is therefore important not to exceed the temperature ceiling defined
by the manufacturer.
Precautions should also be taken to avoid hot melt coming into contact with the skin.
Heat resistant gloves or gauntlets should be worn.
16.3.2 Coatings
Hazards associated with metal pigments in coating media are more associated with the
carriers for the metal than the metals themselves. These are typically low flash point ink
solvents, capable of providing the necessary fast solvent release. Volatile organic solvents
in general are coming under increasing scrutiny. In 1996 the EC proposed a Council
Directive on ‘Limitation of emissions of volatile organic compounds (VOC) due to the
use of organic solvents in certain industrial activities’. A VOC is defined as ‘any organic
compound having at 293.15K a vapour pressure of 0.01 kPa or more, or having a
corresponding volatility under the particular conditions of use’. The ramifications of
this proposed legislation are explored by Kershaw [30].
At the time of writing there is no convergence. Each EU country applies its national
legislation. In the UK, the 1990 Environmental Protection Act, amended in 1995,
introduced a broad control of air, water and land pollution. Guidance notes on compliance
include PG6/10, describing operating limits for coatings manufacture, and PG6/23, relating
to coatings on metal and plastics in enclosed conditions, such as a spray shop. The VOC
limit for primers and undercoats is 250 g/l and 420 g/l for topcoats.
A related, and potentially more far reaching EC directive, is the Integrated Pollution
Prevention Control (IPPC) Directive, 96/61/EC [31]. It must be transposed into UK
legislation by October 1999. When fully effective in 2007 it will control the release of
solvent to air, water and land by large users.
211
16.4 Environment
Environmental considerations applicable to metal pigments relate both to the metals

themselves and to their carriers. All metal flakes are persistent and will accumulate.
The more chemically active will slowly convert to soluble or insoluble compounds.
Although persistent in the environment, aluminium- and copper-based flakes degrade
into non-bioavailable forms.
Traditional solvent pastes generally contain sufficient hydrocarbon solvents to classify

them as flammable for transport and as marine pollutants. Many are required to carry
the relatively new EC risk phrase R65 - ‘hazardous for the environment’.
No metal pigment in any delivery form should be allowed to enter drains or

watercourses.
Although naturally present in the environment, high concentrations of copper and zinc
may have an effect on aquatic organisms. Copper is regarded as an environmentally
hazardous substance, with the UN classification 3077. It must be so labelled for carriage.
Copper is designated a marine pollutant or ‘marpol’ by the International Maritime
Organisation (IMO). Some aluminium pastes can also carry the marpol designation,
but by virtue of their solvent content, rather than due to the metal itself.
Aqueous copper-based effluents can normally be discharged into sewers. Consented

limits vary according to local circumstances and relevant legislation. Values are around
10 mg/l, approximately the same as for nickel and zinc.
16.5 Handling, storage and disposal
Dry flake products should be handled gently, using a non-sparking scoop for transfer.
Pastes and granules are less prone to dusting, but it is good practice to treat them in the
same way. All containers should be kept closed and tightly sealed when not in use. For
pastes, apart from avoiding solvent loss to atmosphere and possible dust creation, the
application qualities of the product are preserved.
Metal pigments should be stored in their original containers in a cool, dry place, away
from sources of ignition and the materials listed in Table 16.2. Unless for storing UV
products (see section 16.5.3), glass and plastic containers should be avoided as they may
build a static charge.
Empty containers should be cleaned and recycled or re-used. Scrapped metal pigment
should be disposed of in accordance with local regulations. The less chemically active
212
metals may be melted and re-used. Due to the high oxide content, it is not possible to
recover aluminium flake other than by the same electrolytic process used in its production
from bauxite. If aluminium waste cannot be re-milled to pigment, it is generally landfilled.
Good housekeeping practices should be followed. These include collecting up spillages

promptly and not allowing dust to collect on hot electrical equipment, or roof beams or
in extraction trunking.
16.5.1 Aluminium
In the special case of fine aluminium powder, transfer scoops and containers should be
earthed to avoid the possibility of static discharge. Powder and paste should not be
stored in areas containing flammable liquids or other combustible materials due to
differences in fire fighting methods.
Dry aluminium flake should not be allowed to come into contact with rust, as for
example provided by rusty containers or implements. Contact only requires an energy
source to cause the extremely exothermic thermite reaction.
Good housekeeping is particularly important to prevent accumulation of powder, which

if disturbed could provide the fuel for a powder explosion. For this reason, the use of
local exhaust ventilation (LEV) trunking is discouraged. So also is vacuum cleaning of
spillages.
16.5.2 Other metals
The other common metal pigments pose no significant handling problems in the forms
in which they are commercially supplied. The same avoidance of dust and personal contact,
combined with good housekeeping, apply.
16.5.3 UV grades
Some metal flakes, especially aluminium, are capable of curing UV monomers in the
absence of light. For this reason, unpassivated metal flake and the UV system should be
stored separately, only being combined before use. For maximum shelf life, storage of
active UV curing coating systems should always be in opaque, preferably plastic packaging.
If metal containers must be used, they should be well coated with an inert resin.
213
16.6 Fire fighting
Only the metals high in the electrochemical series burn. All but aluminium can theoretically
be extinguished by water, but dry powder or foam extinguishers are preferred. Particle
size influences flammability, the finest particles, with the largest collective surface area
being the most likely to burn.
16.6.1 Aluminium
Aluminium fires are particularly dangerous. At high temperatures aluminium will combine
chemically with water, halogens, nitrogen and carbon dioxide. For this reason an
aluminium metal fire is almost impossible to extinguish. Fire fighting therefore consists
of trying to prevent metal ignition by controlling the fire in the incipient stages.
If dry powder catches fire, it is best left undisturbed. Any attempt to use an extinguisher
is likely to create a dust cloud, due to the pressure of the propellant. If the fire is small
and confined to a relatively flat area, it may be gently ringed with dry sand and left
undisturbed to burn out.
Alternatively, a dry powder extinguisher may be directed over the fire, allowing powder
to gently rain down on the burning mass. Better still, long handled scoops may be used
to carefully add dry powder extinguishing agent, taking care not to disturb the burning
material. If the fire is ringed in this way, combustion will generate a crust that will
eventually bring the fire under control. This can take several days in the case of a large
fire. Caution is required during this time, as the fire can continue to burn under the crust
of material, without obvious external indication.
Aluminium paste fires start with combustion of the solvents. In most cases the solvent
component will burn out without reaching a sufficient temperature to trigger a metal
fire. Indeed, it is rare in practice to achieve metal ignition. An aluminium fire, should it
occur however, is easily recognised by the spread of an intense, white-hot glow.
Under no circumstances should water be used on any form of aluminium fire. There will be
two consequences. The water will vapourise almost instantaneously, the expansion throwing
the flakes into the air. Secondly, hydrogen gas will be generated by reaction with the metal,
providing more highly combustible fuel. The result is a violent explosion. Foam and
halogenated fire extinguishers are also unsuitable, again because of the possibility of reaction.
Finally it is worth remembering that local fire department personnel may not be trained
for the special response needed for an aluminium fire. The site fire team should therefore
guide them.
214
16.6.2 Other metals
Coarse grades of gold bronze powder are poorly supportive of combustion. They are
unlikely to catch fire, but if ignited, can be extinguished by excluding oxygen. Irrespective
of particle size, sand is the most effective extinguishing agent. Water and foam may be
used, but at low pressure.
Zinc is classed as flammable. Fires involving zinc and also the similarly combustible
nickel should be tackled with dry chemical extinguishers, not water.
Iron and stainless steel are all either poorly combustible or non-flammable, unless of
extremely fine particle size. Fires can be tackled by normal wet methods. Silver and gold
are not flammable, irrespective of particle size.
References
1. R. J. Lewis Sr., Sax’s Dangerous Properties of Materials, 9th Edn., Van Nostrand
Reinhold, New York, 1996.

Publications Limited, Ayr, Scotland, 1983, 83-90.
3. EC Directive 91/155/EC, for the system of specific information relating to

dangerous preparations in implementation of Article 10 of Directive 88/379/EEC,
1991.
4. UK Control of Hazardous to Health (Amendment) Regulations 1999 (COSHH).
5. EC Directive 96/55/EC, on the approximation of the laws, regulations and

administrative provisions of the member states relating to restrictions on the
marketing and use of certain dangerous substances and preparations (chlorinated
solvents), 1996.
6. EH40 Occupational Exposure Limits 1998, UK Health & Safety Executive,

Sudbury, UK, 1, 3-18.
Reinhold, New York, 1996, 1391-2.
8. Plastics & Rubber Weekly, 1995, 1596, 1.
215

Publications Ltd., Ayr, Scotland, 1983, 85-86.
12. J. T. Hughes, Aluminium and Your Health, Rimes House, Cirencester, UK, 1992.
13. S. G. Epstein, Aluminum and Health, 4th Edn., The Aluminum Association Inc.,
Washington, DC, USA, 1996.
14. Gerhard Ruth GmbH, assignee, German Patent Application 4,215,367, reported
in Chemical Abstracts, 120, (3) : 29819F.

Publications Ltd., Ayr, Scotland, 1983, 89.
16. P. Warnes, Polymers Paint Colour Journal, 1995, 185, 4364, S1.
Reinhold, New York, 1996, 913.
19. EH40 Occupational Exposure Limits 1998, UK Health & Safety Executive,
Sudbury UK, 2, 21.
20. Control of Substances Hazardous to Health (COSHH), 1994, amended 1996,

1997 and 1998.
Reinhold, New York, 1996, 1943
23. UN Recommendations on the Transport of Dangerous Goods, Manual of Tests

and Criteria, Part III, Subsection 33.
24. G. G. Hawley, Condensed Chemical Dictionary, 10th Edn., Van Nostrand

216
25. Official Journal of the European Communities, Vol. 38, L226, 22 September
1995, 1.
26. EC Directive 89/107/EEC, concerning food additives authorised for use in

foodstuffs intended for human consumption, 1988.
27. EC Directive 94/34/EEC, amendment of 89/107/EEC concerning food additives

authorised for use in foodstuffs intended for human consumption, 1994.
28. EC Directive 94/62/EC, on packaging and packaging waste, 1994.
29. Safety of Toys, Migration of Certain Elements, EN71 Part 3, 1994.
30. Y. Kershaw, European Coatings Journal, 1998, No.4, 230.
31. EC Directive, 96/61/EC, concerning integrated pollution prevention and

control, 1996.
217
Author Index
A Chan, C. H. 87
Chang, D. C. K. 137, 149
Akay, M. 88
Charles, H. 183
Allan, P. S. 98
Chen, D. K. 191
Anderson, J. L. 148
Chida, K. 29
Clegg, N. E. 27
B Cooke, M. 175
Backhouse, A. J. 148 Cullen, D. L. 194
Banba, T. 137
Barkley, D. 88 D
Barrick, P. L. 85
Daly, A. T. 170
Bernhardt, A. 93
Deguchi, R. 183
Bertacchi, G. 93
Dreher, B. 167
Besold, R. 169, 175
Bessemer, H. 4
Bevis, M. J. 98 E
Bigg, D. M. 191 Edwards, J. D. 11, 41
Birch, J. 172
Bittler, K. 27
F
Blechschmidt, D. 128
Bock, G. 27 Fawcett, S. L. 125
Booz, A. D. 13 Ferguson, R. L. 135, 145
Boswell, P. 23 Fetz, A. 26
Bradley, D. 92 Frangou, A. 148
Brown, M. H. 136 Friedli, H. R. 189
Bryce, D. H. 93 Fritz, H. E. 116
Fritzsche, T. 126
C
G
Camelon, M. J. 170
Carpenter, C. W. 137 Gardner, G. 97
Carrick, B. W. 192 Gazonnet, J. P. 97
Catoen, B. 92 Gessner, M. A. 173
221
Introduction to Rubber Technology
Gibeau, R. C. 170 K
Gilmore, G. D. 86
Kanda, M. 191
Goemans, C. 168
Kazmer, D. O. 97
Gray, H. R. 24
Keemer, C. B. 29
Green, W. I. 26
Kern, G. M. 45, 57
Greening, W. G. 27
Kerr, J. D. 172
Grossman, E. M. 95
Kerr, S. 92, 107, 161
Kershaw, Y. 211
H Kim, J. K. 88
Hagerman, E. M. 85 Kim, S. G. 85
Hall, E. J. 14, 19 Knittel, R. 115
Hamada, H. 86 Knowles, R. I. 132
Harakawa, Y. 26 Knox, J. 26
Hare, C. 163 Kondis, T. J. 13
Hare, C. H. 199 Kramer, E. 13
Harrington, J. H. 21 Kuvshinikov, P. J. 87
Harris, S. T. 171
Hart, A. C. 187 L
Hartman, R. R. 181
Lalande, F. 88
Hashemi, S. 89
Lau, P. Y. 189
Hashizume, Y. 29
Lautenbach, S. 87
Hatch, B. 93
Levine, S. 24
Henninger, F. 125
Lewis, R. J. 203
Herten, J. F. 87
Lim, J. K. 88
Heuzey, M-C. 81
Hieda, T. 19
Hobbs, S. Y. 85 M
Holman, R. 139, 161 Malguarnera, S. C. 82, 84, 85
Huang, H-F. 181 Malloy, R. 97
Mandle, H. H. 13
I McAdow, W. R. 24
McGowan, E. 184
Imasoto, Y. 19, 48
McKay, A. 22
Iri, K. 137
McKay, C. 22
Mekhilef, N. 87
J Merhar, C. F. 86
Janicki, S. L. 86 Miekka, R. G. 24
Jong, W. R. 87 Miller, B. 88
Monte, S. J. 190, 191
222
Author Index
Mosle, H. G. 86, 108 Schmid, R. 27, 137

Mronga, N. 27 Seo, K. S. 85
M¸ller, B. 137, 139 Souma, T. 28
Muller, F. 29 Spencer, R. S. 86
Murphy, W. G. 27 Steele, C. D. 168
Suzuki, M. 29, 48
N
T
Nadkarni, S. K. 27
Thamm, R. C. 88, 91
O Tundermann, J. H. 21
Oldring, P. 139, 161

U
Osmond, M. F. 168
Ostertag, W. 27 Uchimura, E. 137
P W
Paleari, M. 181 Wada, A. 98
Peacock, A. J. 88 Walker, W. H. 97
Pecorini, T. J. 85 Warnes, P. 206
Peters, R. B. 86 Watters, C. 92, 107
Philips, R. W. 28 Wendon, G. W. 11, 12, 203, 205
Piccarolo, S. 86 West, E. J. 131
Plorde, D. E. 181 Wheeler, I. R. 57
Wilkinson, R. 92
R Williams, C. F. 173
Wray, R. I. 11, 41
Ravella, A. 27 Wu, C. C. 87
Rawson, K. W. 98
Richart, D. S. 170
Y
Ringan, E. 22, 92, 107
Roberts, C. B. 24 Yeh, J. W. 23
Roe, D. S. 97 Yokoi, H. 86
Rolles, R. 136, 170 Yolles, S. 30
Rosato, D. V. 92, 114
S
Sanschagrin, B. 90, 111
Savadori, A. 88
223
Company Name Index
3M Company 193 F
Flex Products 28
A Ford Motor Company 170
Akzo Nobel 131 H.B. Fuller Company 170
Alcoa 13, 169
Aluminum Association in the USA 163, 206 G
Asahi Chemical Industry Company 98
General Electric (GE) 60
Atlantic Powdered Metals 19
Avery Dennison Corporation 24
H
B Hartstoff-Metall AG 13
Herberts 131
BASF 27, 28, 118, 131, 137, 148, 149, 173
Honda Motor Company 190
Battelle Columbus Laboratories 191
Husky Injection Moulding Systems 92
Binney Smith Inc. 163
C I
ICI 148
C-Mold 87, 92
Interchemical Corporation 26
Carlfors 13
International Agency for Research on
Ciba-Geigy Corporation 184
Cancer 207
Cilas 35
International Maritime Organisation
(IMO) 212
D
Datacolor 44 K
Dow Chemical Company 86, 189
Kenrich Petrochemicals Inc. 66
DSM 60
Du Pont 19, 29, 92, 131, 146, 149, 181
L
E Loctite Corporation 163
Eastman Kodak Company 148

Eckart-Werke 26, 56, 136, 137, 174
225
Introduction to Rubber Technology
M SMH AG 127
Sonneborn & Rieck 131
Macbeth 44
Malvern 35
Mercedes Benz AG 127 T
Moldflow 87, 92 TBA Industrial Products Ltd. 186
Mond Nickel Company 30 Texas Plastic Technologies 93
Thermofil 183
N Thomas de la Rue & Company 158
Toyo Aluminium 29, 136, 137
Nippon Paint 148
Transmet Corporation 125, 183, 194,
Novamet Specialty Products Corporation 195
30, 186
NPA 131
U
O United States Federal Communication
Committee 185
Optronik 44 University of Cincinnati 206
P V
Paintmakers Association of Great Britain Verilac 131
175
Pole Européen de Plasturgie 97
Powder Coating Institute 167 W
PPG Industries 131 Weilburger 131
Pratt and Whitney Co. 23 Wolstenholme International 77, 174, 209
R X
Revlon 24 X-Rite 44
Rohm and Engel 118
S
Schlenk 174
Scortec Inc. 95
Senoplast 118
Showa Denko KK 191
Silberline 22, 26, 57, 59, 92, 109, 196, 198
Silberline Inc. 172
SISE 97
226
Main Index 227
Index Terms Links

A
Absorbency 160
Acid 137
ascorbic 137
citric 139
gallic 137
hydroxycarboxylic 137
stearic 14
Acid dimer 136
Acid number 135
Acrylonitrile-butadiene-styrene 59
Acrylonitrile/styrene/acrylate 118
Additive 146
silicone 146
Adhesion 131
Adhesives 190
Aggregate 56
Aggregation (seeds) 154
Alcohols 47 138 156
Aldehyde 119
Alloy 3 137
Aluminium (see also passivation) 7 13 135 137 138 162
163 204 206 208
absorption 206
flake 191
gas generation 135
oxide 138 183 199
spherical 22
toxicity 206
Alzheimer’s disease 206
Amines 149
Antioxidants 12 77
Application characteristics 69
Applications 4
agricultural film 125
architectural 174
automotive 126 174
bags 125
bicycle components 124
coatings 145
containers 126
copy prevention 194
corrosion resistance 199
domestic 174
EMI shielding 184
enclosures (cabinets) 123
fibres 128
This page has been reformatted by Knovel to provide easier navigation.

228
Index Terms Links

Applications (Cont.)
flame retardation 199
floor coverings 123
footwear 123
furniture 174
garden 123
hammer finish 174
heat sinks 194
household 123
laser marking 197
lubrication 196
magnetic 198
mechanical reinforcement 179
microwave heating 180
non-aesthetic 4
pipe insulation 194
plasterboard 193
radiation absorption 200
sacks 125
scratch cards 193
sheet laminate 128
solar transmission 194
sports goods 124
substrate 134
textiles 128
thermal conductivity 194
toys 123
tubs 128
UV protection 196
wear reduction 196
Approved Supply List 203
Area
by BET method 42
specific surface 42
water covering 41
Aspect ratio 39 90 171 187 194 195
Attenuation 189
B
Bags
carrier 126
garbage 126
Ball mill 11
Barrier 175
gas 196
moisture 196
Barrier coatings 199
Bearings 196

229
Index Terms Links

BET method 42
Binder 4
Blow moulding 84
parison 84
parison pleating 84
Blown film 110 115
pinholing 115
Bonding 169 182
pipes 182
Brightness 63
Bronze 7
gold 4 8 12 13 19
silver 4
true 4
Building products 131
C
Carbon black 115 126 181 183 186 191
Carcinogens 205
Carriers 138
acrylics 59
aldehydes 59
coumarone-indene 59
fatty alcohol 140
glycol 59
hydrocarbons 59
ketones 59
polypropylene glycol 138
resins 59
surfactant 138
CAS see Chemical Abstracts Service
Cavity
additional 94
Cerium 137
Chemical Abstracts Service 203
Chemical resistance 43
Chemical Hazard Information & Packaging
for Supply Regulations 203
CHIP ’98 203
Chromium 137
Chromium oxides 136
Co-extrusion 115 171
Coating 63 152 157 161 162 163
168 187 193
advantages of 63
anticorrosive 162
applications 145

230
Index Terms Links

Coating (Cont.)
barrier 162
bridges 163
chemical plant 163
curtain 157
dispersion 133
EB cured 139
fabric 162
in-mould (see paintless film)
incorporation 133
knife 157
leafing 133
leathercloth 162
light cluster 193
metal on non-metallic substrates 29
non-leafing 133
one pack 139
one pack UV cured 162
oxide 135
paint 145
plastisol 162
powder (see also powder coating) 167 168
reflective 193
road markings 193
roof 163
solvent-based 134
sprayed 65
storage tanks 163
substrate preparation 131
two pack 139
UV cured 139 161
water-based 135
Coating formulation 132
Coatings 139 162 167
Cold welding 5 15
Colour 7 44 69
bleed 79
concentrate 59
depth 65
detachment 9
Fantasy 60
measurement 44
retention 115
saturation 76
shift 70
uniformity 64

231
Index Terms Links

Conductivity 183
electrical 183
thermal 93 114
Constant 174 199
Containers 180 181
active 180
cosmetic 128
passive 180
rotable 181
toiletry 128
Continuous milling 13
Copper 7 8 190 203 204 207 208
Cornflakes 38 106 153
Corona discharge 131 146
Corrosion 137
resistance 126
Cost 7 67
coatings 67
formulation 75
mass pigmentation 67
Coupling agents 191
Crayons 163
Credit cards 158
Curing 139 174
EB 139
UV 139
Cut foil glitters 25
D
Data Sheets Directive 203
Deformation 134
Degradation
plasticiser 78
resistance to 39
Degreasing 131
Delivery forms 5 55
compound 60
dry masterbatch 59
dry powder 55
liquid masterbatch 59
paste 55
plasticiser dispersion 56
granules 57
Density 3 158
Dermatitis 205 207
Di-isodecyl phthalate 57
Di-octyl phthalate 57
Dipping 64

232
Index Terms Links

Dispersibility 69
Dispersion 56
energy 133
plasticiser 56 113
resin 56
Disposal
paint residues 66
Distinctiveness of image 50
DOI see distinctiveness of image
Dosing 60 114
Dry milling 11
Drying 170
Ductility 3 86
Dusting 58 173
Dyestuffs 108
E
Effluent 207
EINECS 203
Elastomers 88 191
Electrical conductivity 183
Electro-Magnetic Shielding see EMI
shielding
Electrostatic spraying 173
Elements
metallic 3
Elongation 88
EMI shielding 184 185 187 191
design 185
effectiveness 187 191
measurement 185
origin 185
polymers 186
principles 185
Emulsions 138
Encapsulation 137
Environmental hazards (see also
Hazards) 158 203
Equipment
metering 58
Esters 47
Ethyl acetate 56
Ethylene-vinyl acetate copolymer 78
EU Scientific Committee for Toxicity,
Ecotoxicity 205

233
Index Terms Links

European Inventory of Existing
Chemical Substances 203
Explosion risk see Hazards
Explosive potential see Hazards
Extrusion
biaxial stretching 110
mandrel 84
spider’s legs 84
twin screw 114
F
Fantasy Colour 60
Faraday Cage 169
Fashion 3 126
Fastness
heat 42
light 42
Fibreglass 120
Fibres 3 183
metal 183
Films 180
crop ripening 125
lidding 180
silage wrapping 125
weed suppression 125
Fire 169
Fire extinguishing agent 214
Fire fighting 214
aluminium 214
gold bronze 215
Flakes 134 172 174 196
aluminium 196 199 206
broken 109
coated 172
coloured surface 25
concentration 106
copper 196 210
cut foil 25
dry 113
electrical charging 174
folded 109
glass 199
glitter 25 52 79 128
inertia of 91
iron 107
mica 197
morphology 3
nickel 153 184 196 210

234
Index Terms Links

Flakes (Cont.)
orientation 63 110 174
rapidly solidified 23
silver-coated nickel 30
size 106
stainless steel 153
with coloured surfaces 78
with pre-formed colorants 28
zinc 175
Flame retardation 199
Flame treatment 131
Flammability 209
Flip 45
Flop 45 64 158
Flow line 5 81
definition 81
origin 81
Fluidised bed 173
Foaming 156
Foil 4 11
Food colorant 206
Foodstuffs 180
Formaldehyde 77
Formulations 105 111 132
flake concentration in 106
deep shades 108
low shear forces in 109
metallic/organic pigment
combinations in 108
spherical pigments in 108
G
Gate 89 93
pin 89
size 93
strip 93
Gel coat 119
Glitter flakes 52
Glycol ethers 48
Gold 3 10 184
Gold bronze 4 12 13 19 175 203
204 208 209
Gold leaf 4
Granules 57 113 146
graphite conductive nickel-coated 190
handling of 75
nickel-coated 189
Greases 196

235
Index Terms Links

GRP
spraying of 120
H
Hydrolux 136
Hall process 14 22 23
Handling 212
aluminium 213
Hazards
environmental 158 203 212
explosion 5 12 169 209
explosion potential 209
fire 169
Health and safety 203 204 210
aluminium 205
coatings 211
copper 206
gold bronze 206
Hiding power 70
History 4
Household goods 123
Hydrocarbons 119
Hydrogen 135 209
I
Inhibition 136
Injection moulding
tool design 85
Inks 154 156 157 159 160 161
aluminium 155 156 157 159 160
bronze replacement 158
flexographic 155 161
gold 159 160
gold bronze 155 157
gravure 155 157
lithographic 154 155
non-leafing 157
one pack UV cured 161
paste 154
petroleum distillate 154
polyolefin substrates 161
screen 162
security 157
silver 155 157
solvent-based 154 155 159
water-based 156 160
water-based leafing 156

236
Index Terms Links

Iron 7 9 204 207 208
Iron oxide 199 206 209
micaceous 199
Iron particles 198
Isoelectric point 138
J
Jetting 84
K
Ketones 119
L
LALLS 35
Laminates (see also Simulants,
mineral) 180
Laser marking 197
Lead 200
Leafing 13 47 48 170 199
measurement of 48
surface tension in 48
value 48
Leathercloth 129 162
Legislation 185
electromagnetic emissions 185
environmental 66
health and safety 210
landfill 66
pollution prevention 211
Light
exclusion 192
scattering 47
Liquid monomers 139
Localised mould heating 98
Lubricants 5 47
M
Magix 60
Magnetism 43
Malleability 3 7
Manufacturing 11 168
Marine pollutants 212
Mass pigmentation 63 69 105
general techniques 105
interrelationship 105
optimisation 105
Masterbatch 57 59
dry 59
liquid 59
Maximum Exposure Standard 207

237
Index Terms Links

Measurement of
colour 44
leafing 48
particle size 35
specific gravity 41
Mechanical properties 71
Meld line 82
Metal fume fever 206
Metal pigmented coatings 131
Metallisation
vacuum 65
Metalure 25
Metasheen 25
Meterability 113
Methyl ethyl ketone 56
MFI 108
Mica 3
nickel-coated 189
Microwave
browning 180
heating 180
MIE see minimum explosive energy
Milling
ball 5 11
continuous 13
dry 11
Mills 133
ball 133
sand 133
Mineral oil 57
Minimum explosive energy 175
Molybdenum 137
Molybdic acid 29
Mould tool
design of 92
gates 92
runners 92
sprues 92
texturing 94
Moulding
annealing 85
blow 115
blown containers 116
blown film 115
bright surface 98
fountain flow 90
in-mould decoration 99

238
Index Terms Links

Moulding (Cont.)
induction heating of 98
injection 55
localised mould heating 98
moving boundary 97
multi-coloured 97
multiple live feed 95
paint-less film moulding (PFM) 117 127
parison 84
parison pleating 84
pinholing 115
post finishing by punching 99
reversible transient flow 97
rotational 118
stratification 110
tool design 85 111
voids in 95
Mylar 25
N
Nickel 7 8 20 187 192 204 207
carbon fibre 192
carbonyl 20
conductive flake 188
dendritic powder 188
filamentary 20 192
itch 207
silver-coated 189 191
spherical 21 191
Nitro salicylic acid 136
Non-colouristic applications 179
Non-leafing 13 47 170
Non-volatile content 18
O
Occupational exposure standards 204
Odour 134 154
Oleic acid 14
Opacity 3 45 70 192 194
Orientation 71 149 193
flake 63
sphere 78
weld line 87
Overspray 167 171
Oxidation 14
Oxidising agents 209

239
Index Terms Links

P
pH see Aluminium, gas generation
Packaging 153 156 160 181 192
corrugated board 160
disposable 181
food 192
gift wrap 153
Paints 146 147 148 150 151 152
153 163 167
aerosol 146 148 152
automotive test system 150
barrier 163
brushing 148
conductive 186
dry 167
fast drying 151
gold-bronze 148 152
hammer 146 147
heat resistant 151
industrial 150 151
industrial stoving 147
metal 7
miscellaneous 153
OEM 146 147
refinish 146 147
silver 147 150 151
solvent-based 146
water reducible 150
water-based 148
water-based acrylic 151
Parison 117
Particle size 35 111 132
distribution 35 36
measurement 35
shape 38
Passivation 56 135 139
aluminium 135
cerium 139
gallate 139
gold bronze 139
silica 139
specificity 138
Pastes 55 163
filler 163
Pewter 9 153
Phosphorus 137
Picture framing 169 171

240
Index Terms Links

Pigment 56 128 135 160
aggregates 114
characteristics 35
colour-variable 28
compatibility 77
compounding 60
concentration 71 128
concentration in coatings 132
dendritic 187
dispersion 113
disposal 212
effect 79 126
glitter flakes 52
handling 203 212
incorporation in polymers 109
inorganic 3
loading 71
mica 92
mineral simulant 128
morphology 35
nickel-coated mica 30
nickel-coated carbon fibre 30
nickel-coated graphite 30
orientation 71 89
pearlescent 3 38
pearl simulants 127
plasticiser dispersions 56
quality 110
separation 160
spherical 22 78 108 194
storage 212
water-based aluminium 56
zinc 135
Pipes
plastic 182
Plasticiser 205
Plastisols 57 129 162
Polishing 11 22
Polyacetal 77
Polybutylene terephthalate 118
Polyester-triglycidyl isocyanurate 168
Polyethylene terephthalate 24
Polymeric media 4

241
Index Terms Links

Polymers
ABS 73
cellulose acetate propionate 85
compatibility 77
decomposition 77
dynamic melt 94
EMI shielding 186
fibre reinforced 90
glass filled 87
glass reinforced plastic 119
mass pigmented 197
melt flow index 108
molecular weight 138
multiphase 87
Nylon 6 86
pellets 114
polyamide 74
polycarbonate 86
polymethyl methacrylate 86
polypropylene 72
polystyrene 73 86
PP/EPDM blends 88
PP/HDPE/EPDM blends 88
pre-drying 70
processing 112
polyvinyl chloride 74 162
PTFE 173
relaxation time 86
screening 75
shear minimisation 109
single stage 66
styrene acrylonitrile copolymer 86
styrene-maleic 137
temperature 65
thermosetting 120
transparency 107
virgin 113
viscosity 107
Pot life 140
Powder coating 167 168 171 173 175
application 173
bonding 169
dry blend 169
encapsulation 172
formulation 168 173
handling 175

242
Index Terms Links

Powder coating (Cont.)
manufacture 168
metals 173
safety 175
Printing 153
gravure 132
screen 132
Processing 70
air entrapment 85 86
chemical modification 26
co-extrusion 117 118
coloration in situ 27
conversion 113
double cone blender 69
extrusion 117
gas phase 137
Hall 14 15 22 23
in-mould decoration 118
injection moulding 114 118
laser marking 197
melt spinning 195
milling 75
multi stage 66
rapid solidification 23
rotational moulding 118
spinning disc 23
stamping 11
thermoforming 118
vacuum deposition 24
vacuum forming 118
Properties 126 132
adhesion 145
barrier 117 175
brightness 44
colour 44
corrosion resistance 126
distinctiveness of image 50
gassing 135
impact strength 71
interrelationships 76
mechanical 4 71
physical 41
sparkle 50
tensile strength 71
thermal expansion 89
visual 43
weight saving 126
Propyl acetate 56

243
Index Terms Links

Protective equipment 208
PTFE 173
Poly vinyl chloride see Polymers
R
Radiation absorption 200
Radiation sources 185
Rapidly solidified flakes 23
Receptors 180
Recycling 66 117 212
Reflection
heat 193
light 193
Resins 138 154
acrylic 134
aldehyde 134 154
alkyd 138
epoxy 138
film formers 154
ketone 134 154
phenolic 138
polyester 138
Resinous media 4
Resistance 168
abrasion 168 174
chemical 43 174 175
corrosion 7 168 187
degradation 171
heat 151
humidity 168
impact 168
stone chip 174
water 136
weather 174
Risk phrases 203
Runner
hot 93
size and location 93
Rusting 9 213
S
Safety 207
aluminium 208
gold bronze 209
Safety Phrases 203
SCOREX 97
SCORIM 95 96 97 98

244
Index Terms Links

SCORTEC 94
venting 97
Scratch cards 192 193
Screening 4 5 17
Seed 132
Sheet 161
leathercloth 161
Shelf life 18
Shielding see EMI shielding
Silanes 146
Silica
fumed 170
Silicon 137
Silver 3 7 10 19 184
Silver dollars 18 38 106
SILVET® 57 109
Simulants
mineral 128
pearl 127
Sink marks 95
Smart car 127
Solvents 133 154
acetate 133 154
alcohols 133 154
aliphatic 134
aromatic 134
ketone 133
polar 133
release 152
toluene 133
xylene 133
Sparkle 17 50
Specific gravity 7 41
Specific surface area 42
Spheres
aluminium 22
silver-coated nickel 30
Spraying 167 173
electrostatic 167 173
Stabiliser
lead 77
tin 77
Stainless steel 7 9 21 43 162 163 186
austenitic 9 43
powders 196
UNS-S 31603 9 22 153
Stamping 4 11

245
Index Terms Links

Standards
ASTM C-177 195
ASTM D480-88 48
DIN 53196 36
DIN 53217 41
DIN 55923 48
Star-Brite 25
Stearic acid 14
Stoneware 128
Storage 213
Strength
tensile 88
Substances Directive 203
Surface uniformity 41
Susceptor 180
T
Teletronics 131 145
Test methods
particle size 36
Thermal conductivity 194
Thermal expansion 75
Time Weighted Average 207
Tin 10
Tint strength 70
Titanates 146
Titanium 10 137
Toiletries 126
Toluene 47
Toxicity 204
Travel 45
Tribo 169 171 174
Tufflakes 19
U
UN Recommendations on the
Transport of Dangerous Goods 208
Urethane acrylates 161
UV protection 199
V
Vacuum deposition 24 153
Vacuum metallisation 65
Visual properties 43
VOC see volatile organic compounds
Volatile organic compounds 139 161 167 211
W
Water covering area 41
Weight saving 179

246
Index Terms Links

Weld line 5 81 82 86
crack propagation 88
definition 81
origin 81
strength 87 88
vanishing angle 87
vanishing point 86
wall slip 81
Wetting 71 79
Wetting agents 47
White spirit 56
X
X-rays 200
Z
Zinc 7 9 22 139 162 175 186
199 204 207 208
Zirconates 146

Metallic Pigments in Polymers

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Metallic Pigments in Polymers

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Metallic Pigments

Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire SY4 4NR, United Kingdom

1MP Title Page etc 1 27/11/01, 12:08 pm

Rapra Technology Limited

©1999, Rapra Technology Limited

The right of Ian Wheeler to be recognised as author of this Work

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

Typeset by Rapra Technology Limited

1MP Title Page etc 2 27/11/01, 12:08 pm

1 Introduction and History ................................................................................ 3

2 Metal Pigment Types ....................................................................................... 7

2MP CONTENTS 1 27/11/01, 12:08 pm

3.3 Wet milling .......................................................................................... 14

4 Pigment Characteristics ................................................................................. 35

2MP CONTENTS 2 27/11/01, 12:08 pm

4.2.3 Specific surface area ................................................................. 42

5 Delivery Forms .............................................................................................. 55

6 Comparison of Mass Pigmentation and Coating ........................................... 63

2MP CONTENTS 3 27/11/01, 12:08 pm

6.1.3 Flop ......................................................................................... 64

7 Mass Pigmentation Application Characteristics ............................................ 69

8 Flow and Weld Lines in Mass Pigmented Applications ................................. 81

2MP CONTENTS 4 27/11/01, 12:08 pm

8.5 Mould tool design for metal pigments ................................................. 92

9 Formulation of Mass Pigmented Polymers .................................................. 105

10 Conversion Processes .................................................................................. 113

2MP CONTENTS 5 27/11/01, 12:08 pm

10.1 Injection moulding ............................................................................. 114

11 Applications of Mass Pigmented Systems .................................................... 123

12 Metal Pigmented Coatings .......................................................................... 131

2MP CONTENTS 6 27/11/01, 12:08 pm

12.1 Substrate preparation ......................................................................... 131

13 Applications of Metal Pigmented Coatings ................................................. 145

2MP CONTENTS 7 27/11/01, 12:08 pm

14 Powder Coatings ......................................................................................... 167

15 Non-colouristic Applications ...................................................................... 179

2MP CONTENTS 8 27/11/01, 12:08 pm

15.10 UV protection ................................................................................. 196

16 Health, Safety and Handling ....................................................................... 203

2MP CONTENTS 9 27/11/01, 12:08 pm

Author Index ..................................................................................................... 221

Company Name Index ....................................................................................... 225

Main Index ........................................................................................................ 227

2MP CONTENTS 10 27/11/01, 12:08 pm

3MP PREFACE 1 27/11/01, 12:08 pm

Dr Margaret Henderson, John Maynard, Dr Geoff Ormerod and Joanne Mitchell of

3MP PREFACE 2 27/11/01, 12:08 pm

1.2 Origins and history

Table 2.1 Metal Properties

2.2 Gold bronze

2.5 Stainless steel

2.11 Other metals

3.1 Dry milling

Figure 3.1 A typical production ball mill.

3.1.2 Gold bronze

3.2 Continuous dry milling

As might be expected, the main advantages of a continuous process are in throughput

3.2.2 Gold bronze

3.3 Wet milling

Figure 3.3 Atomised aluminium powder [1 cm = approx. 40 µm]

Addition of an aromatic hydrocarbon solvent is often made at the mixing stage, to

A related development is degradation resistant flakes or ‘Tufflakes’ [Registered

3.3.2 Gold bronze