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Handbook of

Polymer Foams

Editor: David Eaves


Handbook of
Polymer Foams

Editor: David Eaves

C. Vasile

Rapra Technology Limited

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


Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
First Published in 2004 by

Rapra Technology Limited


Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

©2004, Rapra Technology Limited

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.

Every effort has been made to contact copyright holders of any material reproduced within
the text and the authors and publishers apologise if any have been overlooked.

Cover photograph reproduced with permission from EVC

ISBN: 1-85957-388-6

Typeset, printed and bound by Rapra Technology Limited


Cover printed by The Printing House, Crewe, UK
Contents

Contents
Preface .................................................................................................................. ix

1 Foam Fundamentals ........................................................................................ 1


1.1 Introduction ........................................................................................... 1
1.2 Foam Structure ...................................................................................... 1
1.3 Foam Properties ..................................................................................... 3
1.3.1 Compression Properties ............................................................. 3
1.3.2 Energy Absorption Properties .................................................... 5
1.3.3 Thermal Properties .................................................................... 6
References ....................................................................................................... 8

2 Blowing Agents ............................................................................................... 9


2.1 Introduction ........................................................................................... 9
2.2 Physical Blowing Agents ...................................................................... 10
2.2.1 Selection Criteria for Physical Blowing Agents ........................ 10
2.2.2 Halogenated Hydrocarbons ..................................................... 13
2.2.3 Hydrocarbons (HC) ................................................................. 20
2.2.4 Inert Gases ............................................................................... 22
2.2.5 Other Physical Blowing Agents ................................................ 24
2.2.6 Blends of Physical Blowing Agents ........................................... 24
2.2.7 Encapsulated Physical Blowing Agents .................................... 25
2.2.8 Physical Blowing Agent by Foam Type and Application .......... 25
2.3 Chemical Blowing Agents .................................................................... 25
2.3.1 Selection Criteria for Chemical Blowing Agents ...................... 29
2.3.2 Exothermic CBA ...................................................................... 30
2.3.3 Endothermic CBA .................................................................... 32
2.3.4 Endo/Exo Blends ...................................................................... 33

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Handbook of Polymer Foams

References ..................................................................................................... 34

3 Expanded Polystyrene: Development, Processing, Applications


and Key Issues ............................................................................................... 37
3.1 Introduction ......................................................................................... 37
3.1.1 Development of Expanded Polystyrene (EPS) .......................... 37
3.2 Manufacture of Expanded Polystyrene Mouldings .............................. 38
3.3 Applications for Expanded Polystyrene Packaging ............................... 41
3.3.1 Packaging ................................................................................ 41
3.3.2 Construction ............................................................................ 42
3.3.3 Other Applications .................................................................. 43
3.3.4 Novel Applications .................................................................. 44
3.4 Properties of EPS ................................................................................. 44
3.4.1 Mechanical Performance .......................................................... 45
3.4.2 Thermal Insulation .................................................................. 45
3.4.3 Chemical Properties ................................................................. 46
3.4.4 Recent Research on Properties of EPS: Value for
Fruit and Vegetables ................................................................ 46
3.5 Global Structure of Markets and Companies ....................................... 47
3.5.1 Europe ..................................................................................... 47
3.5.2 Asia .......................................................................................... 48
3.5.3 USA ......................................................................................... 49
3.6 Key Issues Facing the EPS Industry ...................................................... 50
3.6.1 Fire .......................................................................................... 50
3.6.2 Recycling ................................................................................. 51
3.6.2 Alternatives to Mechanical Recycling ...................................... 53
Further Information ...................................................................................... 54

4 Rigid Polyurethane Foams ............................................................................ 55


4.1 Introduction ......................................................................................... 55

ii
Contents

4.2 Materials.............................................................................................. 57
4.2.1 Polyols ..................................................................................... 57
4.2.2 Isocyanates .............................................................................. 60
4.2.3 Blowing Agents ........................................................................ 62
4.2.4 Other Additives ....................................................................... 71
4.3 Manufacturing Processes for Rigid Polyurethane Foam ....................... 73
4.4 Recycling Processes for Rigid Polyurethane Foam ............................... 75
4.5 Properties of Rigid Polyurethane Foams .............................................. 76
4.6 Applications ......................................................................................... 78
4.6.1 Applications in Construction ................................................... 78
4.6.2 Applications in the Appliance Industry .................................... 80
References ..................................................................................................... 82

5 Flexible Polyurethane Foam .......................................................................... 85


5.1 Introduction ......................................................................................... 85
5.2 Chemistry ............................................................................................ 85
5.3 Starting Materials ................................................................................ 87
5.3.1 Isocyanate ................................................................................ 88
5.3.2 Polyol ...................................................................................... 88
5.3.3 Water ....................................................................................... 90
5.3.4 Surfactant ................................................................................ 90
5.3.5 Catalyst ................................................................................... 91
5.3.6 Colorants ................................................................................. 92
5.3.7 Antioxidants ............................................................................ 92
5.3.8 Light Stabilisers ...................................................................... 93
5.3.9 Flame Retardants ..................................................................... 93
5.3.10 Adhesion Promoters ................................................................. 94
5.3.11 Other Additives ....................................................................... 94
5.4 The Foaming Process ........................................................................... 94

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Handbook of Polymer Foams

5.4.1 Raw Material Conditioning ..................................................... 95


5.4.2 Mixing ..................................................................................... 95
5.4.3 Growth .................................................................................... 96
5.4.4 Cell Opening ............................................................................ 97
5.4.5 Cure ......................................................................................... 98
5.5 Manufacturing Equipment ................................................................... 99
5.5.1 Storage and Delivery .............................................................. 100
5.5.2 Mixing ................................................................................... 101
5.5.3 Foam Rise and Cure .............................................................. 101
5.5.4 Innovations ............................................................................ 103
5.6 Foam Characterisation ....................................................................... 104
5.6.1 Density .................................................................................. 104
5.6.2 Hardness ................................................................................ 104
5.6.3 Resilience ............................................................................... 105
5.6.4 Porosity ................................................................................. 106
5.6.5 Strength Properties ................................................................. 106
5.6.6 Cell Structure ......................................................................... 107
5.6.7 Environmental Stability ......................................................... 107
5.6.8 Fatigue ................................................................................... 108
5.6.9 Compression Set .................................................................... 108
5.6.10 Flammability .......................................................................... 108
5.7 FPF Markets ...................................................................................... 109
5.7.1 Transportation ....................................................................... 110
5.7.2 Comfort ................................................................................. 110
5.7.3 Carpet Cushion ...................................................................... 110
5.7.4 Packaging .............................................................................. 111
5.7.5 Specialty Applications ............................................................ 111
5.8 Environmental Issues ......................................................................... 111
5.9 Organisations .................................................................................... 113
References ................................................................................................... 114

iv
Contents

6 Rigid PVC Foam ......................................................................................... 123


6.1 Introduction ....................................................................................... 123
6.2 Foam Extrusion ................................................................................. 124
6.2.1 Basic Principles ...................................................................... 125
6.2.2 Extrusion Processes ................................................................ 126
6.2.3 Effect of Processing Conditions ............................................. 131
6.3 Foam Formulation Technology .......................................................... 132
6.3.1 Blowing Agents ...................................................................... 133
6.3.2 Processing Aids ...................................................................... 138
6.3.3 Type of PVC .......................................................................... 140
6.3.4 Stabilisers ............................................................................... 140
6.3.5 Lubricants .............................................................................. 141
6.3.6 Typical Formulations ............................................................. 141
6.4 Properties ........................................................................................... 143
6.5 Novel Processes and Applications ...................................................... 145
6.5.1 Recycling ............................................................................... 145
6.5.2 Microcellular Foam ............................................................... 146
6.5.3 Foamed Composites ............................................................... 147
6.6 Summary ............................................................................................ 147
References ................................................................................................... 148

7 Flexible PVC Foams .................................................................................... 155


7.1 Introduction ....................................................................................... 155
7.2 Flexible Foam Types and PVC Types ................................................. 155
7.2.1 Flexible Foams Based on Suspension PVC ............................. 155
7.2.2 Flexible Foams Based on Dispersion or Paste Resins ............. 156
7.2.3 Chemically Blown Foams from PVC Plastisols:
Fundamentals ........................................................................ 156
7.2.4 PVC Resins used in Plastisol Foam Formation ....................... 160

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Handbook of Polymer Foams

7.2.5 Mineral Fillers ....................................................................... 161


7.2.6 Pigments ................................................................................ 162
7.2.7 Liquid Plasticiser .................................................................... 162
7.2.8 Blowing Agent Type and Level ............................................... 165
7.3 Products Utilising Foamed Plastisols .................................................. 166
7.3.1 Floorings and Carpet Backings .............................................. 166
7.3.2 Wallcoverings ......................................................................... 168
7.3.3 Synthetic Leather ................................................................... 169
7.3.4 General Foams ....................................................................... 170
References ................................................................................................... 171

8 Polyolefin Foams ......................................................................................... 173


8.1 Introduction ....................................................................................... 173
8.2 Manufacturing Processes and Materials ............................................. 174
8.2.1 Extruded Non-Crosslinked Foam .......................................... 174
8.2.2 Expanded (Non-Crosslinked) Polyolefin Beads ...................... 177
8.2.3 Extruded Crosslinked Foam - Processes ................................. 179
8.2.4 Press Moulded Crosslinked Foam Process ............................. 186
8.2.5 Injection Moulded Foam Process ........................................... 189
8.2.6 The Nitrogen Autoclave Process ............................................ 189
8.2.7 Recycling Processes ................................................................ 193
8.2.8 Post Manufacturing Operations ............................................. 194
8.3 Properties of Polyolefin Foams .......................................................... 195
8.4 Applications ....................................................................................... 197
8.5 Foam Specifications ........................................................................... 200
8.5.1 Packaging .............................................................................. 200
8.5.2 Automotive ............................................................................ 201
8.5.3 Furnishings ............................................................................ 201
8.5.4 Buoyancy ............................................................................... 201

vi
Contents

8.5.5 Aerospace .............................................................................. 201


8.5.6 Construction .......................................................................... 202
8.5.7 Toys ....................................................................................... 202
8.5.8 Food contact .......................................................................... 202
8.6 Markets ............................................................................................. 202
References ................................................................................................... 203

9 Latex Foam ................................................................................................. 207


9.1 Introduction ....................................................................................... 207
9.2 Dunlop Process .................................................................................. 208
9.2.1 Batch Process ......................................................................... 209
9.2.2 Selecting a Formulation for Latex Compounds ...................... 215
9.2.3 Selection of Other Compounding Ingredients ........................ 217
9.2.4 Continuous Process for Latex Foam Production .................... 229
9.3 Talalay Process ................................................................................... 230
9.4 Troubleshooting in Latex Foam Manufacture .................................... 235
9.5 Testing ............................................................................................... 236
9.5.1 Compression Set .................................................................... 236
9.5.2 Indentation Hardness ............................................................. 236
9.5.3 Flexing Resistance .................................................................. 238
9.5.4 Density .................................................................................. 238
9.5.5 Metallic Impurities ................................................................. 238
9.6 Important Uses of Latex Foam........................................................... 238
9.6.1 Transportation ....................................................................... 238
9.6.2 Furniture ................................................................................ 239
9.6.3 Special Uses ........................................................................... 239
References ................................................................................................... 239

10 Microcellular Foams ................................................................................... 243

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Handbook of Polymer Foams

10.1 Introduction ....................................................................................... 243


10.2 Processing of Microcellular Foams .................................................... 244
10.2.1 The Solid-State Batch Process ................................................ 244
10.2.2 The Semi-Continuous Process ................................................ 247
10.2.3 Extrusion and other Processing Methods ............................... 248
10.3 Properties of Microcellular Foams ..................................................... 249
10.4 Current Research Directions .............................................................. 254
10.4.1 Microcellular Materials for Construction .............................. 254
11.4.2 Open-Cell (Porous) Microcellular Foams ............................... 255
10.4.3 Sub-Micron Foams and Nanofoams ...................................... 256
10.5 Commercial Opportunities ................................................................ 261
References ................................................................................................... 262

Abbreviations .................................................................................................... 269

Contributors ...................................................................................................... 275

Index ................................................................................................................. 277

viii
Preface

Preface

The use of polymer foams is extremely widespread. Indeed, it is difficult to think of a


single industry where polymer foams do not have a significant application. They can be
found for example in sports and leisure products, in military applications, in vehicles, in
aircraft, and in the home. Most people will encounter polymer foams every day in one
form or another, whether it be in furniture, in packaging, in their car, in refrigerator
insulation, or in some other common application.

Although naturally occurring polymer foams have been known for a long time, (e.g.,
sponges, cork), synthetic polymer foams have only been introduced to the market over
the last fifty years or so. The development of a new polymer has usually been quickly
followed by its production in an expanded or foam form owing to the unique and useful
properties which can be realised in the expanded state.

Compressibility, thermal insulation and, of course, low density/lightness are all enhanced
in a foam as compared with the original polymer. Such properties can be tailored to meet
particular requirements and can increase substantially the potential applications of a
polymer. Foaming technology and the properties of expanded materials should therefore
be of interest to all those working in the polymer industry.

This Handbook aims to review the chemistry, manufacturing methods, properties and
applications of the synthetic polymer foams used in most applications. In addition, a
chapter is included on the fundamental principles which apply to all polymer foams.
There is also a chapter on the blowing agents used to expand polymers, blowing agents
having undergone considerable change and development in recent years in order to meet
the requirements of the Montreal Protocol in relation to the reduction and elimination
of chloroflurocarbons (CFC) and other ozone depleting agents. A chapter is also included
on microcellular foams - a relatively new development where applications are still being
explored. Each chapter has references to facilitate further exploration of the subject.

I am very much indebted to my co-authors for their contributions. They all have substantial
expertise on their particular topics and have given considerable time to the production

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Handbook of Polymer Foams

of their chapters. I am also indebted to the staff at RAPRA for their work in pursuing
and assembling the various contributions to produce the final composite, especially Frances
Powers (Commissioning Editor), Claire Griffiths (Editorial Assistant) and Sandra Hall
(Graphic Designer).

David Eaves
Harbury, UK
November 2003

x
Foam Fundamentals

1
Foam Fundamentals

David Eaves

1.1 Introduction

Although polymer foams are based on a wide variety of materials and are manufactured
in many different forms, there are some principles and concepts which apply to all foams.
These have been reviewed in depth elsewhere [1, 2]. Since these concepts are useful in
understanding the relationships between polymer properties and foam structure and can
facilitate the prediction of the physical behaviour of foams in typical applications, this
chapter provides a summary of some of these fundamentals.

1.2 Foam Structure

Most foams are formed by a process involving nucleation and growth of gas bubbles in
a polymer matrix (exceptions being syntactic foam where micro-beads of encapsulated
gas are compounded into a polymer system, and latex foam). As the bubbles grow, the
foam structure changes through stages which may be described as follows:

• Initially, small dispersed spherical bubbles are generated in a liquid matrix, with a
small reduction in density.

• Whilst the bubbles grow but still remain spherical, the lowest foam density is achieved
when bubbles reach close packed structure.

• Further growth and lower foam density then involves distortion of cells to form
polyhedral structures, sometimes idealised as pentagonal dodecahedrons.

• Viscous and surface tension effects subsequently cause material to flow towards
intersecting cell elements to form junctions of tricuspid cross-section.

• A final stage may involve rupture of cell walls to result in an open cell foam.

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Handbook of Polymer Foams

Depending on the degree of expansion and the particular formulation, foams can have
any or a combination of these structures. A comprehensive characterisation may therefore
include a measure of:

a) Foam density - usually expressed as kg/m3. A more fundamental measure is relative


density (φ), i.e., density of foam (ρf) compared with density of the original polymer
(ρs), or

φ = ρf/ρs

Relative density may also be regarded as the volume fraction of polymer in a foam.
Low density foams are generally regarded as those with volume fraction of polymer
<0.1.

b) Cell size which may be measured directly by inspection of a foam cross-section. A


convenient method is that described in the US Standard ASTM D3576 [3] in which a
count is made of the number of cells intersecting a specific length. The average chord
length t is determined and the average cell diameter d is calculated from d = t / 0.616.

In practice, there is usually a distribution of cell sizes, sometimes a very wide


distribution. Most foam manufacturers quote either an average cell size, or a range of
cell sizes for their foams. The production of cells of different sizes is caused partly
through cells being nucleated randomly in space and time, and partly through large
cells growing by diffusion of gas from small cells. A uniform cell size is not a stable
structure. Diffusion of gas from small to large cells can be understood from the classic
equations giving the pressure inside a bubble enclosed by liquid:

P = 2γ/r

where P is the pressure differential between gas and surrounding liquid, γ is the
interfacial surface tension and r is the bubble radius. Small bubbles contain gas at a
higher pressure than large ones; hence, diffusion is always from small to large.

c) Open cell/closed cell ratio - determined for example by water absorption or permeation.
This ratio is important in determining properties, especially in low density foams. In
flexible polyurethanes (PU), it is also important in the manufacturing process as,
unless the cells open at the end of the expansion step, the rapid diffusion of carbon
dioxide from the cells, much faster than air can diffuse in to replace it, will cause
foam collapse.

d) Anisotropy - unless foams are made in conditions allowing essentially free expansion
in three dimensions, they can exhibit substantial structural (and property) anisotropy.

2
Foam Fundamentals

This is frequently the case with foams produced by extrusion processes where cells
have some lateral distortion. This results in differences in physical properties measured
in the length and the width directions. Manufacturers will sometimes quote properties
measured in these two directions.

e) Cell shape - the topology of cells in foams has been studied extensively, perhaps first
by Robert Hooke in 1664 who observed and described the porous structure of cork
using his recently perfected microscope. Low density polymeric foams formed by the
growth of nucleated expanding gas bubbles are often considered to have cells in the
form of pentagonal dodecahedra. Five-sided faces are frequently identified in
microscopical observation, and the faces meet in tetrahedral junctions which closely
approximate the angles necessary to maintain a stable structure. However, this
geometry is not quite space filling, and a form which more closely fits many
observations is the β-tetrakaidecahedron, which includes some four sided faces. Cell
struts however are generally curved, more so as the foam density increases.

1.3 Foam Properties

1.3.1 Compression Properties

All foams show a compression stress-strain curve (Figure 1.1), which may be split into
three regions:

• Region 1 - linear ‘Hookian’ behaviour

• Region 2 - collapse plateau

• Region 3 - densification

In region 1, linear elastic behaviour is controlled by cell wall bending and, in closed cell
foams, by cell wall stretching due to the contained gas pressure. In region 2, the cells
collapse through cell wall buckling, or in brittle foams, by cell crushing and cell wall
fracture. In region 3, densification occurs. As foam density increases, Young’s modulus
increases in region 1, the plateau stress value increases, and the strain at which densification
starts reduces. In closed cell foams, the compression of gas in the cells also contributes,
more so in regions 2 and 3 than 1.

At large compressive strains the stress-strain curve increases sharply due to densification,
and tends towards a limiting slope (very considerably higher than the initial modulus) at

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Handbook of Polymer Foams

Figure 1.1 Schematic compression stress-strain curve for a foam

a limiting strain. This strain is lower than can be calculated by assuming it is the point at
which all porosity has been eliminated, as the cell walls join together at a somewhat
lower strain.

Using idealised cell structures, equations have been derived relating foam properties to
the foam structure, the matrix polymer properties, and the relative density of the foam.
Initial (Young’s) compression modulus, shear modulus, elastic collapse (plateau) stress,
and Poisson’s ratio (the negative ratio of lateral to axial strain) have all been considered.
However, for practical purposes and because in many foams the initial polymer properties
are modified by reactions during foam manufacture such as crosslinking, foam properties
are always measured directly and given by manufacturers in tables or figures.

4
Foam Fundamentals

1.3.2 Energy Absorption Properties

Many foam applications make use of the energy absorption capability of foam structures
which perform much better in this regard than the solid polymers from which they are
made. This arises from the ability of foams to keep the peak force (or deceleration G)
below the limit which results in damage to a packaged object, whilst absorbing the energy
of impact. Energy is absorbed essentially in the plateau region of the stress-strain curve
where cells deform by elastic buckling, plastic yielding or brittle crushing.

In elastomeric foams, such as flexible PU, the plateau stress is determined by elastic
buckling of the cells and much of the external work is stored during impact deformation
and released after impact. However, some energy is dissipated by hysteresis effects due
to viscous flow of the contained fluid (air) in open cell foams and by hysteresis in
polymer deformation. In plastic foams, the energy is absorbed by plastic flow of cells
and there is often little if any immediate recovery. Brittle foams also absorb energy with
little recovery, energy absorption occurring by cell fracture and crushing. Polystyrene
foams are an example of the latter showing good impact absorption with little recovery,
and hence are useful only for the first impact. Common applications therefore use
polystyrene foams for single transit packaging. Closed cell polyethylene foams are an
example of a material which absorbs energy mainly by plastic deformation of the cells.
Whilst there is no instant recovery after impact, such foams do show substantial recovery
longer term due to the restoring pressure of gas in the cells and, in crosslinked foams,
network restoring effects. These foams offer good performance in multiple impacts and
have applications in packaging designed for more than one journey (with consequent
environmental benefits).

Various methods have been put forward to enable the packaging, or cushioning, ability
of foams to be characterised. Most manufacturers of foams intended for cushion packaging
applications publish cushioning curves which are generated by measuring the peak
deceleration of a series of falling weights dropped onto the foam from a given height.
The peak deceleration, G, is plotted against cushion loading, i.e., the static load exerted
on the foam by the weight when at rest, to obtain a cushion curve. These always show a
minimum G at a particular static stress. At high static stress, i.e., greater falling weights
- the foam becomes densified and generates higher G. At low static stress, the foam is not
compressed sufficiently to reach the plastic deformation region, resulting again in higher G.
Cushion packaging design aims to create conditions at or near the minimum in the cushion
curve so as to provide the maximum protection.

Some further information on cushion packaging is given in Chapter 8, Polyolefin Foams,


and mathematical treatments of energy absorption in foams are given in [1, 2].

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Handbook of Polymer Foams

1.3.3 Thermal Properties

1.3.3.1 Thermal Conductivity

A major application for polymer foams is thermal insulation in areas including building
and construction (wall and floor insulation, pipe insulation), transportation (refrigerated
food trucks, liquefied gas tankers) and appliances (refrigerator linings). Although in
construction applications mineral wool remains the insulating material most used, the
superior properties of polymer foams, better insulation, easier handling, no water
absorption (in closed cell foams), compensates for their generally higher cost and
polystyrene foam with rigid PU foam are used in very significant amounts [4].

The thermal conductivity of a foam is governed by four factors:

• conduction of heat through the solid polymer

• conduction of heat through the gas

• convection of heat through the cells

• radiation through cell walls and across voids

Convection is only significant in foams having extremely large cell sizes greater than
some 10 mm, and may therefore be neglected in most commercial foams which have cell
sizes in the range 0.1–2 mm. The other factors all contribute significantly, with conduction
through the gas generally the major contributor, with radiation and conduction through
the solid together amounting only to about one-third of the gas conduction.

An example given by Gibson and Ashby [1] which shows the relative contributions of these
factors is for a closed cell polystyrene foam with a relative density of 0.025, containing air at
0.1 MPa. This has a thermal conductivity of 0.04 W/mK. The contribution from the polystyrene
solid was calculated as 0.003 W/mK, and that from the contained air 0.024 W/mK, which
leaves 0.013 W/mK as the radiative contribution, convection being assumed to be
insignificant. In this case the relative contributions amount to:

Solid 62.5%
Gas 7.5%
Radiation 32.5%

Work by Glicksman and Cunningham in the 1980s also showed contributions from
radiation to be about 30% of the total.

6
Foam Fundamentals

As the foam density reduces, the amount of thermal conduction through the solid polymer
reduces correspondingly and conductivity of the foam falls to a minimum at (for closed
cell foams) a relative density of around 0.05. Below this value the radiative contribution
increases steeply as the foam density approaches zero due to the increasing transparency of
the cell walls to radiation. Above this value, conduction through the solid begins to dominate.

At the minimum, foam conductivity is not much greater than that of the air contained in
the cells. The most used method of reducing conductivity further is to replace air with a
contained gas of lower conductivity, such as trichlorofluoromethane (TCFM). Thermal
conductivity values for air and TCFM are:

Air 0.025 W/mK


TCFM 0.08 W/mK

This has been done for some while, for example in insulating foams based on rigid PU,
development considerations then being the rate of diffusion of TCFM out of the foam
and replacement by air (with a resulting deterioration in insulation ability), and more
recently the replacement of chlorofluorocarbons (CFC) by alternative materials which
are less environmentally damaging but which generally have an inferior insulation
performance.

The effect of cell size on thermal conductivity in foams with cell diameters less than
2 mm is relatively small, but the tendency is for conductivity to reduce as the cell size
decreases. This is due not so much to lower convection effects as to reduced radiation
owing to the greater number of internal reflections from cell walls. Some minor
improvements (reductions) in thermal conductivity can be made by modifying the cell
structure to increase the reflectivity of cell walls and hence reduce radiation conduction.

Recent work on rigid PU foams for insulation applications has concentrated on CFC
replacements and consequent work to recover CFC insulation performance by reducing
radiation effects (by cell structure modification) and improving long term ageing [5].

Heat transfer through foams decreases sharply as the temperature is lowered, since the
thermal conductivity of solids and gases decreases with temperature and radiation is also
less at low temperatures. Thermal conductivities of foams are measured and quoted at a
standard temperature, usually 10 ºC.

1.3.3.2 Other Thermal Properties

Melting point, or softening point, of a foam is essentially that of the solid polymer. This
may be a relatively sharp transition, as for foam produced from high density polyethylene

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Handbook of Polymer Foams

(melting transition), or a wider transition, as with foams from low density polyethylene
(melting transition) or polystyrene (glass transition).

The specific heat of a foam is essentially that of the solid from which it is made, since the
contribution from the contained gas is very small.

Thermal expansion coefficient is, like specific heat, essentially that of the solid polymer,
and most polymer foams have an expansion coefficient of about 10-4/K. However, closed
cell plastic or elastic foams of low density tend to have higher expansion coefficients due
to the pressure exerted on the foam by the contained gas as temperature increases. The
initial expansion in such low density foams is often followed by a reduction in volume as
the gas diffuses out of the foam and, if the temperature is sufficiently high approaching
the softening point of the polymer, the volume can reduce to less than the original as the
foam cells begin to collapse.

References

1. L.J. Gibson and M.F. Ashby, Cellular Solids, 2nd Edition, Cambridge University
Press, Cambridge, UK, 1999.

2. Low Density Cellular Plastics, Physical Basis of Behaviour, Eds., N.C. Hilyard
and A. Cunningham, Chapman and Hall, London, UK, 1994.

3. ASTM D3576-98, Standard Test Method for Cell Size of Rigid Cellular Plastics,
1998.

4. D.E. Eaves, Polymer Foams, Trends in Use and Technology, Rapra Technology,
Shrewsbury, UK, 2001.

5. M.A. Schütz and L.R. Glicksman, Journal of Cellular Plastics, 1984, 20, 2, 114.

8
Blowing Agents

2
Blowing Agents

Sachchida N Singh

2.1 Introduction

A substance that produces a cellular structure in a polymer mass is defined as a blowing


agent. Alternatively, the gaseous phase in most polymeric foam material derives from the
blowing agent(s) used in the foam manufacturing process. Blowing agents include gases that
expand when pressure is released, liquids that develop cells when they change to gases, and
chemical agents that decompose or react under the influence of heat/catalyst to form a gas.

The blowing agent plays a very important role in both the manufacturing and performance
of polymer foam. The blowing agent is the dominant factor controlling density of the
foam. Besides density, it affects the cellular microstructure and morphology of the foam,
which in turn define the end-use performance. In some applications, such as insulation,
the blowing agent properties play a central role in the overall long-term performance of
the foam. In these and many other cases, the foam is closed cell and the blowing agent is
retained in the cellular structure of the foam, at least until it diffuses out, which in some
cases can be decades. In many others, such as packaging and cushioning, the cellular
structure of the foam is such that the blowing agent escapes almost immediately after the
foam is formed. In such cases, referred to as open cell foam, though the cellular structure
and morphology imprint of the blowing agent impact on the performance of the foam,
the blowing agent per se does not. Of course there are many applications, such as buoyancy,
impact resistance and load bearing where the role of blowing agents is intermediate.

During manufacturing of foam, the choice of blowing agent and the choice of processing
conditions/steps are inter-linked, i.e., each drives the other. In the case of foaming of high
molecular weight polymers, such as polystyrene (PS), polyolefins, polyamides and
polyester, the blowing agent modifies the melt viscosity and the thermal history of the
polymer and thus rheology during foam formation and shaping. In cases where
polymerisation, foaming and shaping all happens in one step, e.g., during the formation
of typical polyurethane (PU), epoxy or phenolic foam, the blowing agent not only affects
the liquid viscosity and heat history but also the compatibility, reactivity and phase-
mixing of the components. As the role of blowing agents is somewhat different in the

9
Handbook of Polymer Foams

two cases, henceforth we will refer to the first foaming of high weight polymers, as
thermoplastic foaming. The other, foaming of polyurethane, etc., will be referred to as
thermoset foaming. Undoubtedly, there is much in common among blowing agents used
for any polymer but there are also many unique requirements specific to a polymer used
in a specific application in a specific part of the world.

Carbon dioxide (CO2) generated by isocyanate-water reaction was the primary blowing
agent for PU foam in the early years of their use whereas low boiling point liquids, such
as methyl chloride or butylene were the primary blowing agent for thermoplastic foam
such as PS [1-3]. Over the years, the number of polymer foams in commercial use has
increased, each with its own set of unique performance and processing requirements.
There has been a corresponding increase in the range of blowing agent technology in
use. Currently, there are many different blowing agents and many more blends in use.
The blowing agents are generally classified as physical or chemical. Chemical blowing
agents are generally a solid at standard temperature and pressure (STP) and undergo a
chemical transformation when producing gas, while physical blowing agents, generally
a liquid or gas at STP, undergo either a reversible change of state or expansion. One
exception to this classification would be water, a liquid used extensively to make
polyurethane foam that reacts with isocyanate to liberate CO2 gas.

2.2 Physical Blowing Agents

Physical blowing agents (PBA) provide gas for the expansion of polymers by undergoing
a change in physical state. The change may involve volatilisation (boiling) of a liquid, or
the release of a compressed gas to atmospheric pressure after it has been incorporated
into a polymer, generally at elevated temperature and/or pressure. Common liquid physical
blowing agents are low boiling liquids and include short-chain (C5 to C7) aliphatic
hydrocarbons and halogenated C1 to C4 aliphatic hydrocarbons. Common gaseous
blowing agents include: CO2, nitrogen (N2), short-chain (C2 to C4) aliphatic hydrocarbons
and halogenated C1 to C4 aliphatic hydrocarbons. Physical blowing agents are used in
the production of all types of foamed plastics, both thermoplastics and thermosets over
the full range of density. They are almost the only types of blowing agent used when the
foam density is low (less than 50 kg/m3). PBA are relatively low in cost but may require
special equipment for use in some cases.

2.2.1 Selection Criteria for Physical Blowing Agents

Many factors must be considered prior to selecting the PBA. Some such characteristics
are common across all applications, polymers, and geographic location, whereas others

10
Blowing Agents

are specific. Environmental acceptability is one such common factor and includes
considerations of stratospheric ozone depletion, global warming, ground level air
pollution, tropospheric degradation, long-term breakdown products, halogen content,
acidification potential, etc. The stratospheric ozone depletion potential (ODP) of a blowing
agent is an index defined as stratospheric ozone depleted per unit mass of a given product
compared to that of trichlorofluoromethane (CFC-11). As discussed in Section 2.2.2, the
ODP of a blowing agent intimately affects the production and use of blowing agent in a
given application or at a given geographical location. Global warming and resultant
climate change is a consideration because it is thought that some of the blowing agents
when present in the lower atmosphere reflect infrared radiation (heat) back to earth and
thereby raise the earth’s surface temperature. How much a given mass of a blowing
agent contributes to global warming over a given time period, usually 100 years, compared
to the same mass of carbon dioxide is referred to as its global warming potential (GWP).
The GWP of a blowing agent is a function of its atmospheric lifetime and its ability to
absorb infrared radiation. Atmospheric lifetime characterises the overall stability of the
blowing agents in the atmosphere. Some of the blowing agents may undergo
photochemical reactions in the lower atmosphere and contribute to smog formation and
are classified as volatile organic compounds (VOC). Their use is strictly regulated in
some parts of the world, e.g., the USA, and may require monitoring and control measures
to limit emission during foam manufacturing. In cases where a foam product is exported,
environmental requirements of both the manufacturing and the country of use needs to
be considered.

Toxicity, flammability, compatibility with materials of construction, a safe and economic


manufacturing process are some of the other common factors considered while choosing
blowing agents. Toxicity concerns over human health impacts of blowing agents include
worker and consumer exposure of blowing agent and possible decomposition products
formed in foams. Both acute and chronic effects need to be considered. Many blowing
agents present varying degrees of flammability. To safely use flammable blowing agents,
it is necessary to evaluate manufacturing risks from ignition, storage and transportation
of blowing agent, and fire performance of foam products and finished product. Similar
considerations apply to compatibility with materials of construction.

Boiling point, molecular weight, vapour pressure in the temperature range used, heat of
vapourisation, solubility in raw material and finished foam, compatibility with materials
of construction are among the many performance attributes of a compound that must be
considered while choosing a blowing agent. Though some performance attributes such as
non-reactivity and compatibility of the blowing agents with materials of construction are
common to all, most depend on the final application of the foam product. There are still
some guidelines about preferred attributes across the applications. For example, lower
molecular weight, or perhaps lower cost per mole of a blowing agent that meets all the

11
Handbook of Polymer Foams

other performance criteria is a more desirable blowing agent. This is because generally, the
lower the molecular weight, the higher the gas volume that can be generated per unit
weight of the blowing agent. Good solubility of the blowing agents in polymer/oligomer
under foam formation conditions and poor solubility in the finished foam is another common
desired attribute though the specific reasons are somewhat different in thermoplastics
compared with thermoset foaming.

For thermoplastics, good solubility of the physical blowing agents in the melt means
relatively lower minimum melt pressure to get and keep the blowing agent in solution
and more plasticisation of the melt by the blowing agents. This allows the melt temperature
to be reduced which makes it easier to cool the melt to the optimum foaming temperature.
Conversely, if the blowing agent has poor solubility, a higher melt pressure and temperature
is required to force the blowing agents into solution. This can degrade the polymer and
make it more difficult to cool the melt to the optimum foaming temperature, leading to
poor cell structure, loss in blowing efficiency, surface imperfection, non-optimal closed
cell content etc. The lowest density that can be obtained with a given blowing agent
depends on the amount of gas that can be dissolved in the molten polymer. The solubility
of blowing agents in most commonly used polymers is found to follow Henry’s Law, i.e.,
amount of gas dissolved is directly proportional to the gas pressure [4]. Henry’s Law
constant depends strongly on the blowing agent and polymer under consideration.

In thermoset foams, poor solubility in the reactive liquid component means limited shelf
life for the resin components, larger cell size, etc. In either case, addition of additives
such as surfactant and compatabiliser is used to circumvent problems associated with
poor solubility. Low solubility of the physical blowing agent in the finished foam is
important to prevent weakening of the polymer by the solvent effect.

In general, high heat of vapourisation while still getting a high blowing efficiency is
desired. For thermoset foam, this reduces the maximum exotherm temperature thus
reducing any thermal degradation of foam and residual stress gradient in composite
products. In thermoplastics, it makes it easier to cool the melt to the optimum foaming
temperature, e.g., in the extrusion die.

For closed cell foam, the vapour pressure of the blowing agent(s) at room temperature
needs to be sufficient to withstand atmospheric pressure during usage conditions to avoid
foam shrinkage. Also the permeation rate of the blowing agent out of the foam needs to
be slower than that for air into the foam to avoid lowering the total pressure inside the
cells and thus foam shrinkage. This is obviously more critical with flexible foam such as
low-density polyethylene (LDPE) than more rigid foams, like PS. Vapour pressure of the
blowing agents also affects processing conditions. The higher the vapour pressure, the

12
Blowing Agents

higher the pressure required to keep it in the liquid phase in the polymer melt. Thus, for
example, use of butane will require a higher melt pressure than use of pentane.

The blowing agents used to make closed cell insulation foam have some additional, very
specific, requirements. The ideal blowing agent is a fluid with a low thermal conductivity
and a low diffusion coefficient through the foam. There are other application dependent,
very specific requirements for blowing agents, e.g., products used in food packaging
applications require appropriate FDA approval.

Ultimately, the choice of a blowing agent is dependent upon the performance, cost-
effectiveness and competitiveness of the finished product in a particular application. The
market price of the finished products is often the determining factor as to whether a
blowing agent can be used and sold competitively in the market.

A description follows of the different physical blowing agents currently in use or


consideration.

2.2.2 Halogenated Hydrocarbons

Many chlorinated and/or fluorinated aliphatic hydrocarbons (C1 to C4) have unique
attributes that make them very suitable blowing agents for all types of polymers.
Halogenated hydrocarbons were one of the earliest blowing agents used to make foam.
Though methyl chloride was used to make PS foam in the 1930s, large-scale use of
polymer foam was greatly accelerated by discovery and use of chlorofluorocarbons (CFC)
as physical blowing agents in late 1950s.

2.2.2.1 Chlorofluorocarbons (CFC)

The use of CFC, in particular trichlorofluoromethane (CFC-11) to make rigid PU foam,


chlorofluorocarbon-12 (CFC-12) to make extruded polystyrene (XPS) and 1,1-
dichloro,1,2,2,2-tetrafluoroethane (CFC-114) to make LDPE and phenolic foam, led to
the production of closed cell rigid foam with low densities, good mechanical properties
and extremely good thermal insulation performance. It led to the attainment of low
density and tailored load-bearing properties for many cushioning products using flexible
PU. As shown in Table 2.1, CFC have near ideal characteristics to be blowing agents:
low molecular weight, boiling point around room temperature, low toxicity, non-
flammability, and low thermal conductivity. This along with excellent chemical and
thermal stability and low cost made CFC the blowing agents of choice for most polymer

13
Handbook of Polymer Foams

Table 2.1 Properties of CFC and other blowing agents


CFC-11 CFC-12 CFC-114 Methyl Methylene
Chloride Chloride
Chemical formula CCl3F CCl2F2 CClF2CClF2 CH3Cl CH2Cl2
CAS number 75-69-4 75-71-8 76-14-2 74-87-3 75-09-2
Molecular weight 137.4 120.9 170.9 50.5 85
Boiling point, °C 23.8 -29.8 3.8 -24.2 40
Critical temperature, °C 19 8 112 145.7 14 3 235
Critical pressure, MPa 4.41 4.11 3.39 6.71 6.35
Liquid specific gravity at 1.477 1.31 1.456 1.10 1.33
25 °C
Heat of vapourisation at 24.8 20.0 23.2 21.5 28.0
boiling point (BP),
kJ/mole
Gas conductivity,
mW/m°K at 10 °C 7.4 9.2 - - N/A
at 25 °C 7.9 9.9 10.4 10.6 8.4
Vapour pressure, kPa
at 10 °C 60 418 31
at 25 °C 106 644 213 567 57
Flammable limit in air None None None 8.1-17.2 12-19
(vol.%)
TLV (ACGIH) or OEL, 1000 1000 1000 50 35-100
ppm
ODP (with CFC-11 = 1) 1 1 1 0.02 0.007
GWP (100 y, CO2 = 1 4600 10600 9800 16 10
Atmospheric lifetime, 45 100 300 1.3 0.5
years
TLV: Threshold Limit Value as determined by the American Conference of
Governmental Industrial Hygienists
OEL: Occupational Exposure Limit as measured by manufacturer

properties of methyl chloride methylene chloride

14
Blowing Agents

foams, but especially for rigid thermal insulation foam, both thermoset and thermoplastic.
Solubility of CFC were high in many thermoplastics and thus they were used to make
foam from many different thermoplastics. The only other halogenated hydrocarbon in
wide use until the 1980s was methylene chloride as a blowing agent for flexible and
integral skin PU foam.

The chemical stability of CFC, however, led a number of scientists to question their
ultimate environmental fate as it was recognised that almost all usage of CFC resulted in
release to the atmosphere. In 1974, Rowland and Molina published their now famous
ozone depletion hypothesis in which they claimed that CFC would diffuse into the
stratosphere where they break down to release chlorine atoms which would catalytically
destroy ozone [5]. Rowland and Molina shared the Nobel Prize for Chemistry in 1995
for this work. Destruction of stratospheric ozone leads to an increase in UV-B radiation
in the 290-320 nm region at the earth’s surface with consequent implications for human
health, and other biological systems. This resulted in the development of an international
protocol, known as the Montreal Protocol, which required a sharp curtailment in
production and use of substances that deplete the ozone layer. The Montreal Protocol
profoundly changed the direction and the pace of technology development in polymer
foam industry. The choice of blowing agent in many different applications of polymer
foam across the globe continue to be intricately affected by the Montreal Protocol.

The Montreal Protocol and subsequent amendment sets out a time schedule for freeze
and reduction of ozone depleting substance (ODS) based on whether a country is deemed
developed (referred as to non-Article 5(1) parties) or developing (referred as Article 5(1)
parties), based on their annual per capita calculated consumption level of ODS. Australia,
Canada, Czech Republic, France, Germany, Greece, Italy, Japan, Netherlands, Russia,
Spain, UK and USA are the non-Article 5(1) parties. Brazil, Chile, China, India, Indonesia,
Mexico, Saudi Arabia, South Africa and Zimbabwe are among the 113 countries listed
as Article 5(1) party. Table 2.2 shows the phaseout schedule of CFC [6].

2.2.2.2 Hydrochloroflurocarbons (HCFC)

Featuring at least one carbon hydrogen bond in the molecule, HCFC are chemically less
stable than CFC and tend to breakdown in the lower atmosphere into simple inorganic
species, such as hydrogen halides and formyl fluoride. Consequently, the ability of HCFC
to migrate to the atmosphere and to decompose into ozone-damaging chlorine is much
lower than CFC. Also the breakdown products do not contribute significantly to the
photochemical smog formation in urban areas or to acid rain. Thus, HCFC have low
ODP, generally between 0.01 – 0.13 and are not VOC. Nevertheless, use of HCFC is
severely restricted, e.g., in USA, these are allowed only in applications where the thermal

15
Handbook of Polymer Foams

Table 2.2 Montreal Protocol phase out schedule for CFC1


Date Control Measure (ODP Weighted % Reduction)
Non-Article 5(1) Parties Article 5(1) Parties
July 1, 1989 Freeze at 1986 level -
January 1, 1994 75% of 1986 level -
January 1, 1996 Phased out -
July 1, 1999 - Freeze at 1995-97 average level
January 1, 2005 - 50% of 1995-97 average level
January 1, 2007 - 85% of 1995-97 average level
January 1, 2010 - Phased out
1
Up to and including 1999 Beijing Amendment and applicable to production and
consumption

insulation value of the foam is of critical importance. In most other, non-essential


applications, such as automotive interiors, furniture, flotation, packaging, etc., use of
HCFC is not permitted in USA. Table 2.3 lists the properties of most widely used HCFC.

Generally speaking, thermal insulation foam using CFC-11 switched to HCFC-141b


(CH3CCl2F), those using CFC-12 switched to HCFC-22 (CHClF2) and HCFC-142b
(CH3CClF2) and those using CFC-114 to HCFC-124 (CF3CHClF). However, there are
some notable exceptions to this general guideline. For example, flexible faced polyurethane
thermal insulation laminate producers in Europe switched from CFC-11 to pentanes.
However, many PU insulation foam in many part of the world still use HCFC-141b and
HCFC-22. For production of XPS insulation board, HCFC-142b is preferred in USA
whereas a non-flammable blend of HCFC-142b/HCFC-22 (60:40) is preferred in Europe.
In some cases, ethyl chloride or ethanol is used as a co-blowing agent with HCFC-142b.

Due to their ozone depleting potential, HCFC are viewed as only the transitional
alternatives to be used till zero ODP alternatives are available. In 1992, the Parties to the
Montreal Protocol added the Copenhagen Amendment outlining allowable HCFC
consumption (see Table 2.4) from 1996 to 2040. In addition to the restrictions imposed
by Montreal Protocol, other bodies such as the European Union (EU) and national
governments have imposed more strict regulations and phase out schedule for HCFC.

16
HCFC blowing agents
properties of

Blowing Agents

Table 2.3 Properties of HCFC blowing agents


HCFC-141b HCFC-22 HCFC-142b HCFC-124
Chemical formula CH3CCl2F CHClF2 CH3CClF2 CHFClCF3
CAS number 1717-00-6 75-45-6 75-68-3 2837-89-0
Molecular weight 116.9 86.5 100.5 136.5
Boiling point, °C 32.9 -40.8 -9.8 -12.0
Critical temperature, °C 210.3 96 137.1 122.2
Critical pressure, MPa 4.64 4.97 4.12 3.57
Liquid specific gravity at 1.233 1.19 1.12 1.36
25 °C
Heat of vapourisation at 25.8 20.2 22.4 22.9
BP, kJ/mole
Gas conductivity
mW/m°K at 10 °C 8.8 9.9 8.4 -
at 25 °C 10 10.7 9.5 12.9
Vapour pressure, kPa
at 10 °C 46 665 209 220
at 25 °C 79 934 337 385
Flammable limit in air 7.6-17.7 None 6.4-14.9 None
(vol%)
TLV or OEL, ppm 500 1000 1000 500
ODP (with CFC-11 = 1) 0.11 0.055 0.065 0.02
GWP (100 y, CO2 = 1) 700 1900 2300 470
Atmospheric lifetime, 9.2 11.8 18.5 6.1
years

Effects of the mandated US and EU regulations are shown in Table 2.4 [7-8]. There are
numerous other, often evolving, restrictions on use of HCFC, many specific to a country,
corporation, application, and blowing agent. It is best to consult the environmental
protection agency of the country where the foam will be manufactured and used along
with any corporate policy of manufacturer and user before using HCFC.

17
Montreal Protocol HCFC phase
out schedule
Handbook of Polymer Foams

Table 2.4 Phase out schedule for HCFC


Date Montreal Protocol Reduction1 US Reduction2 EU Reduction3
Non-Article 5(1) Article 5(1)
Parties Parties
January 1, 1996 Freeze at cap4 - - -
January 1, 2003 - - 141b – 100%5 100%
appliances, and
lamination6
January 1, 2004 35% of cap4 - - Phased out
January 1, 2010 65% of cap4 - 142b and 22 – -
100% 7
January 1, 2015 90% of cap4 - Phased out8 -
January 1, 2016 - Freeze at 2015 - -
level
January 1, 2020 99.5% of cap9 - 142b and 22 – -
100%
January 1, 2030 Phased out - Phased out -
January 1, 2040 - Phased out - -
1
Up to and including 1999 Beijing Amendment and applicable to production only
2
As of May 1, 2003
3
As of September 1, 2002
4
ODP weighted HCFC consumption cap = 100% 1989 HCFC + 2.8% (Montreal
Protocol) or 2.6% (EU) of 1989 CFC consumption
5
Production only for domestic foam use
6
Except in refrigerated transport
7
Except for use in equipment manufactured before 1/1/2010
8
Except for use in equipment manufactured before 1/1/2020
9
Phased out except for service of existing refrigeration and air-conditioning equipment

2.2.2.3 Hydrofluorocarbons (HFC)

These are compounds with no chlorine in them and thus have zero ODP. Two liquid
HFC, HFC-245fa (CF3CH2CHF2) and HFC-365mfc (CF3CH2CF2CH3) and two gaseous
HFC, HFC-134a (CH2FCF3) and HFC-152a (CHF2CH3) are most widely used [2].
Table 2.5 lists the properties of these HFC. The flammability limit of HFC-365mfc in air

18
HFC blowing agents properties of
Blowing Agents

Table 2.5 Properties of HFC blowing agents


HFC-134a HFC-245fa HFC-365mfc HFC-152a
Chemical formula CH2FCF3 CF3CH2CHF2 CF3CH2CF2CH3 CHF2CH3
CAS number 811-97-2 460-73-1 406-58-6 75-37-6
Molecular weight 102 134 14 8 66
Boiling point, °C -26.5 15.3 40.2 -24.7
Critical temperature, °C 100.6 157.5 189.7 113.5
Critical pressure, MPa 4.06 3.62 2.75 4.48
Liquid specific gravity at 1.20 1.32 1.25 0.90
25 °C
Heat of vapourisation at 22.1 28 26.2 21.7
BP, kJ/mole
Gas conductivity
mW/m°K at 10 °C 12.4 12.5 10.6 -
at 25 °C 13.8 13.3 11.6 14.7
Vapour pressure, kPa
at 10 °C 425 85 26 273
at 25 °C 670 145 59 500
Flammable limit in air None None 3.8-13.3 3.9-16.9
(vol%)
TLV or OEL, ppm 1000 500 N/A 1000
ODP (with CFC-11 = 1) 0 0 0 0
GWP (100 y, CO2 = 1) 1600 990 910 140
Atmospheric lifetime, 14 7.4 10.8 1.7
years

has caused introduction of a non-flammable blend with HFC-227ea (CF3CHFCF3) in


the weight ratio of 94:6 [9].

Zero ODP of HFC means that it is permissible to use them in all applications including
non-insulation. However, use of HFC as a PBA is not as widespread as that of CFC in the
1980s and 1990s or of HCFC in the 1990s or 2000s. This is primarily because of their

19
Handbook of Polymer Foams

high cost, relatively smaller benefit in insulation performance as compared to alternatives,


(e.g., hydrocarbons, CO2), and high GWP. High GWP is an especially controversial issue
and regulations related to global warming are divergent and emerging. Thus use of HFC
is very application, geographical location and time dependent (as related to HCFC
phaseout schedule shown in Table 2.4) and somewhat tentative. At the present time,
HFC-245fa is the leading HCFC replacement candidate blowing agent in the USA for
use in many PU foam especially domestic appliance, spray and integral skin foam [2].
HFC-152a, HFC-134a and their blends are the leading candidates in USA for use in XPS
insulation board and polyolefin pipe-wrap insulation [10-12]. HFC-134a is currently
being used in many applications, such as PU flotation, extruded PS sheet in USA and
many European countries [12]. HFC-134a is also a leading HCFC replacement candidate
blowing agent for use in many PU foams. Use of HFC-365mfc as a replacement for
HCFC-141b is primarily limited to Europe due to some patent related issues. Other than
the previously mentioned insulation and integral skin applications, HFC are not being
pursued as a blowing agents for polymer foam.

2.2.3 Hydrocarbons (HC)

Many low boiling aliphatic hydrocarbons have desirable characteristics, namely, low
cost, high specific volume, zero ODP, nearly zero GWP, halogen-free, compatibility with
common polymers, universality and easy availability. Properties of a few HC are listed in
Table 2.6. Such HC do present one big hazard though, fire. For example, the flammability
limit of pentanes in air is about 1.4 to 8.0 volume %, the energy of ignition is extremely
low and the density of pentane vapour is about 2.5-times that of air. Such flammability
characteristics blocked serious consideration of HC as blowing agents in the early years
of making foam but this changed more recently. A careful consideration of equipment
and procedures used in storage, handling, manufacturing, monitoring and shipping of
both the HC and the finished foams, made it possible to use HC as blowing agents in a
wide range of foams. Though the extent of plant modifications required to use HC may
vary significantly, depending on local codes and regulations, in general, improved
ventilation, explosion-proofing and alarm systems are required. Hydrocarbons are classified
as VOC and are subject to emissions control in many urban areas, especially in USA.

HC are used to blow foam using a large range of polymers, in a wide range of densities
for use in a large variety of applications. They are used to make insulation from PU, PS
and polyolefins, foams for floral arrangements from phenolics, energy absorbing
(acoustical and impact) and food packaging foam from polyolefins, etc. This is because
the solubility of many HC is high in many thermoplastics [13]. Though many HC are
suitable for most polymer/application, preferences have emerged. Pentanes have emerged

20
HC blowing agents properties of Cyclo-pentant n-pentane Iso-pentane n-butane
Isobutane Propane
Blowing Agents

Table 2.6 Properties of HC blowing agents


Cyclo- n- Iso- n- Iso- Propane
pentane pentane pentane butane butane
Chemical formula (CH2)5 C5H12 C5H12 C4H10 C4H10 C3H8
CAS number 287-92-3 109-66-0 78-78-4 106-97-8 75-28-5 74-98-6
Molecular weight 70.1 72.0 72.0 58.1 58.1 44.1
Boiling point, °C 49.3 36.2 27.8 -0.5 -12 -42.1
Critical temperature, 238.6 196.7 188 149.9 134.6 96.8
°C
Critical pressure, MPa 4.51 3.36 3.38 3.8 3.65 4.25
Liquid specific gravity 0.75 0.63 0.62 0.57 0.55 -
at 25 °C
Heat of vapourisation 27.3 25.7 24.6 22.4 21.3 18.8
at BP, kJ/mole
Gas conductivity
mW/m°K at 10 °C 11.4 13.7 12.8 - 14.8 -
at 25 °C 12.8 15.0 14.3 16.1 16.2 17.9
Vapour pressure, kPa
at 10 °C 24 40 54 - 220 -
at 25 °C 43 69 91 243 350 951
Flammable limit in air 1.4 – 8.0 1.3 – 8.0 1.4 – 7.8 1.8-8.4 1.8 – 8.4 2.9 – 9.5
(vol.%)
TLV or OEL, ppm 60 0 600 600 600 N/A 2500
ODP (CFC-11 = 1) 0 0 0 0 0 0
GWP (with CO2 = 1) 11 11 11 <10 11 11
Atmospheric lifetime, Few days Few days Few days Few days Few days Few days
years

as the dominant blowing agents for use in many PU foam insulation and expanded
polystyrene (EPS) foams [12]. Butanes and propane are the dominant blowing agents in
use to make protective wrapping and cushioning foam from polyolefins.

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Handbook of Polymer Foams

2.2.4 Inert Gases

Inert gases especially carbon dioxide and nitrogen are among the most widely used blowing
agents. This is partly because nitrogen is cheap, abundant and by far the most
environmentally acceptable as it is simply borrowed from the atmosphere. The same is
true for CO2 even though it is a greenhouse gas. This is because it can be deemed
‘greenhouse neutral’ whether produced as a by-product of ammonia manufacture or
fermentation processes, or extracted from air or other natural resources. Table 2.7 lists
the properties of CO2, N2 and O2. Oxygen is not used as a blowing agent but is still
relevant as it diffuses into the cellular space of closed cell foams.

Table 2.7 Properties of inert gases used as blowing agents


Carbon Dioxide Nitrogen Oxygen
Chemical formula C O2 N2 O2
CAS number 124-38-9 7727-37-9 7782-44-7
Molecular weight 44 28 32
Boiling point, °C -78.3 -195.8 -183.0
Critical temperature, °C 31 -146.9 -118.3
Critical pressure, MPa 7.38 3.4 5.0
Liquid specific gravity at 25 °C N/ A N/A N/A
Heat of vapourisation at BP, kJ/mole 6.8 - -
Gas conductivity
mW/m°K at 10 °C 15.3 24.6 25.2
at 25 °C 16.4 25.8 26.6
Vapour pressure, kPa
at 10 °C 4502 Very Very
at 25 °C 6434 high high
Flammable limit in air (vol.%) None None None
TLV or OEL, ppm N/A N/A N/A
ODP (CFC-11 = 1) 0 0 0
GWP (with CO2 = 1) 1 N/A N/A
Atmospheric lifetime, years 120 N/A N/A

22
Blowing Agents

One reason CO2 and N2 are widely used as blowing agents is their relatively moderate
critical temperature and pressure, especially for CO2. As is well known, a material is in a
supercritical fluid state when it is maintained at a temperature and pressure exceeding its
critical temperature and pressure. In the supercritical state, the material becomes dense
like a liquid yet maintains a gas like ability to flow with almost no viscosity or surface
tension. Its solubility in a polymer increases significantly and this lowers the glass transition
temperature (Tg) of most polymers. When a polymer melt saturated with supercritical
fluid is depressurised rapidly, the polymer becomes supersaturated with the gas, nucleation
of cells occurs at a very high concentration and growth of these cells continues until the
polymer vitrifies. This phenomena is used to make cellular (typical cell size >70 μm),
microcellular (cell size between 1-70 μm) and super-microcellular (cell size below 1 μm)
with a variety of polymers using CO2 and N2 [14].

Though many gases exhibit supercritical behaviour within the typical ranges of
temperature and pressure used for processing thermoplastics, CO2 is in a supercritical
state when its temperature exceeds a modest 31 °C and pressure exceeds a modest
7.38 MPa. In the supercritical state, CO2 is a supersolvent for many polymers but especially
PS where the Tg can be lowered to near ambient conditions. This makes the rapid
depressurisation step relatively easy for the PS/CO2 system and many insulation and
impact energy absorption foams are made using these materials [1]. For essentially the
same reasons, CO2 is being used to make low density foam with many other plastics
including, high density polyethylene (HDPE), and polypropylene (PP), for use in a whole
range of applications [15]. In addition, CO2 is being used to make foam from many
different thermoplastics using conventional CO 2 injection along with use of a
heterogeneous nucleating agent. CO2 is also being evaluated as an alternative to chemical
blowing agents (see Section 2.3) to make high density foams [16].

Carbon dioxide in all its physical states, i.e., gas, liquid and supercritical fluid is the
single largest blowing agent in use today to make polymer foam. In addition to the use
described previously to make thermoplastic foam, CO2 is used extensively to make PU
foam. Here it is either generated chemically from the reaction of water and isocyanate,
henceforth referred as CO2(water), or added as a liquid, referred as CO2 (LCD) or as a
gas, referred to as CO2 (GCD). All rigid and flexible PU foams made today are at least
partially blown with CO2(water). Many flexible foams such as slabstock use CO2 (LCD)
and others, such as moulded foams use CO2 (GCD) in addition to CO2(water) [17, 18].
It is the ability to handle CO2 in liquid form under moderate conditions that has made it
the auxiliary blowing agent of choice in flexible slabstock PU foam.

Nitrogen is also used to make microcellular foam [15] and conventional foam using
many different thermoplastic polymers [19]. Compressed N2 is used in specialised injection
moulding processes for structural foam, and in a unique high pressure gas solution process

23
Handbook of Polymer Foams

for polyethylene packaging foam [19]. The solubility of N2 in most common polymers is
lower than that of CO2 and thus higher melt pressure is required to get to same density
when using N2 than CO2 [4]. Generally N2 is used for plastics with higher melt viscosities
or for injection moulding parts that are difficult to fill. Nitrogen or air are occasionally
used as nucleating agents for some thermoset foams but are rarely used as the primary
blowing agent. Other inert gases such as argon and helium have been mentioned as
blowing agents in many patents, but they are rarely, if at all, used commercially [20, 21].

2.2.5 Other Physical Blowing Agents

As indicated in Section 2.2.4, water is used extensively as a blowing agent in the


polyurethane industry where it reacts with isocyanate to give CO2. Lately, water is also
being investigated as a physical blowing agent, especially for thermoplastic elastomers
(TPE) such as PP/ethylene-propylene diene monomer and styrene-ethylene/butylene-
styrene [22]. Besides low cost and environmental benefits, water brings some unique
characteristics as a PBA. It has low volatility, low solubility and low foaming pressure
compared to other PBA, especially CO2 and N2.

Methyl chloroform (CCl3CH3, ODP =0.1, GWP = 140, boiling point = 74 °C), acetone
(CH3COCH3, ODP = 0, boiling point = 56.1 °C) and alcohol are some other physical
blowing agents that have been used to make primarily non-insulation foams.
Perfluorocarbons, e.g., perfluoropentane (C5F12) and perfluorohexane (C6F14), have been
evaluated as blowing agents and as a co-blowing agent with HCFC [23]. They are not
considered to be a viable blowing agent option as they are characterised by very long
atmospheric lifetimes of the order of hundreds to thousands of years and are very infrared-
active and thus have high GWP.

Fluorinated ethers, such as HFE-245 (CF3CH2OCF2H), HFE-356 (CF3CHFCF2OCH3),


and HFE-254mf (CF3CH2OCHF2) have been evaluated in the laboratory in rigid PU
foam applications but their commercial viability is dubious because of cost, toxicity for
some of them and performance [24]. Similarly fluoroiodocarbons such as heptafluoro-2-
iodopropane and hydrogen containing fluoromorpholine have been evaluated in the
laboratory but high cost has meant no commercial use [25].

2.2.6 Blends of Physical Blowing Agents

Blends of two or more PBA are often used to meet all the performance requirements of
the end use and/or the processing requirements of foaming. For example, in PU foam,
mixtures of a liquid and a gaseous blowing agent is often used to balance the flow,

24
Blowing Agents

dimensional stability and thermal resistance requirements for use as insulation for
appliances, construction, etc. Low boiling blowing agents such as HCFC-22, HFC-134a,
and isobutane have been used to improve flow and dimensional stability of PU foam
blown with more insulating gases HCFC-141b, HFC-365mfc and pentane, respectively
[26]. Similarly, blends of blowing agents are often used to solve processing issues. For
example, extrusion of polyethylene terephthalate (PET) foam to give a density reduction
of over 60% using a single blowing agent such as CO2, HCFC-22 or butane leads to cell
collapse due to the high volatility of the blowing agents before crystalline PET can be
cooled from melt temperature to it’s Tg. A blend of blowing agents, one having a high
boiling point, such as n-octane, with a low boiling point blowing agent, such as n-pentane,
leads to over 80% reduction in density with no cell collapse [27]. This is because n-
octane provides plasticisation required for foaming and n-pentane provides the vapour
pressure needed to prevent foam cell collapse during the cooling.

2.2.7 Encapsulated Physical Blowing Agents

While a number of physical blowing agents are widely used, their use typically requires
special storage, handling, and processing equipment. Physical blowing agent encapsulated
in a thermoplastic shell is used to avoid such equipment and to make a very controlled
cell structure. Generally referred to as expanding fillers, the thermoplastic shell and the
physical blowing agent, generally a hydrocarbon, are chosen to meet the processing and
application requirements [28]. They are generally used to expand thermoplastic polymers
to a density range of 300-900 kg/m3.

2.2.8 Physical Blowing Agent by Foam Type and Application

The choice of blowing agents depends on the end product performance requirements,
manufacturing process, country of manufacturing and country of use. Table 2.8 lists the
PBA currently in use in different foams and the anticipated blowing agent in year 2007
to 2010 based on current understanding of market dynamics and regulatory environment.
Though various sources have been used to compile this list, periodic reports written by
the Flexible and Rigid Foams Technical Options Committee of the United Nations
Environmental Programme (UNEP) has been a key source [12].

2.3 Chemical Blowing Agents

Chemical blowing agents (CBA) are compounds that liberate gas(es) under the foam
processing conditions, either due to thermal decomposition or due to chemical reaction.

25
physical foam type application

Handbook of Polymer Foams

Table 2.8 Physical blowing agents by foam type and application1


Foam type Blowing Agent in Anticipated blowing agents in 2007-2010
use (2003/2004)
Non-Article 5(1) Article 5(1) parties
parties
Rigid Polyurethane2
Domestic HC, HFC-245fa, HC, HFC-245fa, HCFC-141b, HC
refrigerators and HFC-134a, HCFC- HFC-134a
freezers 141b, HCFC-
141b/22, HCFC-
142b/22
Water heater, Picnic HC, HCFC-141b, HC, HFC-245fa, HCFC-141b, HC,
cooler HCFC-141b/22, HFC-365mfc/227ea, CO2 (water)
HFC-245fa, HFC- HFC-134a, CO2
134a, CO2 (water) (water)
Boardstock (flexible HC, HCFC-141b HC N/A
faced lamination)
Metal panel - HC, HCFC-141b, HC, HFC-134a, HCFC-141b, HC
continuous HCFC-22, HCFC- HFC-365mfc/227ea,
142b/22 HFC-245fa
Metal panel - HFC-134a, HCFC- HC, HFC-134a, HCFC-141b
discontinuous 141b, HFC-134a HFC-365mfc/227ea,
HFC-245fa
Spray HCFC-141b CO2 (water), HFC- HCFC-141b
245fa, HFC-
365mfc/227ea
Blocks HC, HCFC-141b, HC, HFC-245fa, HCFC-141b
HFC-245fa, HFC- HFC-365mfc/227ea
365mfc/227ea
Pipe HC, CO2 (water), HC, CO2 (water), HCFC-141b
HCFC-141b HFC-245fa, HFC-
365mfc/227ea
One component Dimethylether/ DPB, HFC-134a, DBP, HFC-134a,
foam propane/butane HFC-152a HFC-152a
(DPB), HCFC-22
Flotation HFC-134a, HFC-134a HFC-134a
HCFC-22
Packaging, floral CO2 (water, LCD) CO2 (water, LCD) CO2 (water)

26
physical foam type application
Blowing Agents

Table 2.8 Continued


Foam type Blowing Agent in Anticipated blowing agents in 2007-2010
use (2003/2004)
Non-Article 5(1) Article 5(1) parties
parties
Flexible Polyurethane
Slabstock and box CO2 (water, LCD), CO2 (water, LCD) CO2 (water, LCD),
Methylene chloride Methylene chloride
Moulded CO2 (water, LCD, CO2 (water, LCD, CO2 (water, LCD,
GCD) GCD) GCD)
Integral skin CO2 (water), CO2 (water), HFC- CO2 (water),
HFC-134a, HC, 134a, HC, HFC- HFC-134a, HC
HFC-245fa 245fa, HFC-
365mfc/227ea
Phenolic foam - HC HC HC
floral
Phenolic foam - HCFC-141b, HFC- HFC-245fa, HFC- N/A
insulation 245fa, HFC- 365mfc/227ea, HC,
365mfc/227ea, HC, 2-chloropropane
2-chloropropane
Polystyrene
Extruded HC, HFC-134a, HC, HFC-134a, HC
sheet/dunnage HFC-152a, CO2 HFC-152a, CO2
(LCD), N2 (LCD), N2
Extruded board HCFC-142b, CO2 (LCD), HFC- HC, HCFC-142b
HCFC-142b/22 152a/134a, HC
Expanded HC, water HC, water HC
Polyolefins, pipe- HCFC-142b, HFC-152a, HCFC-142b/22
wrap HCFC-142b/22 HFC-134a
Polyolefins, all HC, CO2 (LCD), HC, CO2, N2 HC
others CO2, N2
Polycarbonate (PC) CO2 (LCD), HC CO2 (LCD), HC N/A
1
Blowing agents specified here cover ~98% of total commercial production of foam,
remainder may use other blowing agents
2
All PU rigid foams are blown partially with CO2 (water) along with the specified
blowing agents

27
chemical
Handbook of Polymer Foams

In general, use of CBA results in the decomposition of the original molecule, one or more
gases for polymer expansion, and one or more solid residues that remain in the foamed
polymer. Table 2.9 lists the common CBA along with their decomposition temperature
range, gases evolved and gas yield. As can be seen from Table 2.9, the gases produced are
generally N2 and CO2 and once produced, they behave much like a PBA but with some
effects due to presence of the decomposition products. Thus much of the discussions in
Section 2.2.4 on inert gas, especially about solubility in polymers applies here too.

CBA are widely used to make high and medium density foam plastics and rubbers. Typical
densities of foams produced using CBA are in the range of 400-800 kg/m3, i.e., a density
reduction of about 20-45% from full polymer density. CBA are rarely used to make
foam with densities below 400 kg/m3 because they are essentially too expensive. For
example, CO2 and N2 liberated from CBA cost about 10 times that used from a cylinder

Table 2.9 Properties of chemical blowing agents


Description Type Decomposition Gas yield Gases
temperature, °C @STP x 10-3
m3/kg
Azodicarbonamide (ADC) Exo 200-230 220-245 N2, CO,
NH3, O2
4,4-Oxybis(benzenesulfonyl- Exo 150-160 120-125 N2, H2O
hydrazide) (OBSH)
p-Toluenesulfonylhydrazide Exo 110-120 110-115 N2, H2O
(TSH)
p-Toluenesulfonylsemicarbazide Exo 215-235 120-140 N2, CO2
(TSS)
Dinitrosopentamethlenetetramine Exo 19 5 190-200 N2, NH3,
HCHO
Polyphenylene sulfoxide (PPSO) Exo 300-340 80-100 SO2, CO,
CO2
Sodium bicarbonate Endo 120-150 130-170 CO2, H2O
Zinc carbonate Endo CO2
Citric acid derivatives Endo 200-220 110-150 CO2, H2O
5-Phenyltetrazole Endo 240-250 190-210 N2

28
Blowing Agents

[4]. The primary reason many CBA are used is because their use requires little modification
to an existing thermoplastics processing line. This makes it the preferred approach for
many smaller processors as use of PBA generally requires additional investment in
specialised extrusion equipment. Certain foam processing methods are especially well
suited for the use of CBA. For example, the low-pressure (atmospheric) nature of the
rotational foam moulding process requires use of only CBA [29]. Other benefits of CBA
include broader operating window, self-nucleation and finer cell size. Some of the
disadvantages of CBA include difficulty of recycling non-conforming products or
contamination due to unreacted or solid residue from the reacted CBA.

Almost all CBA are finely divided solids and no special storage or handling equipment is
generally needed to utilise them in plastics processing. They are either blended with the
plastics before processing or fed directly into a hopper. CBA may be incorporated into
virtually any thermoplastic process to produce foam, such as extrusion, injection moulding,
calendering, coating, expansion casting, and rotational moulding.

Almost half of all CBA are used to blow polyvinyl chloride (PVC) followed by polyolefins
and rubber [30, 31]. PVC applications include foam core pipes, profiles and sheets,
textured wall covering and cushion vinyl flooring. Polyolefin sheets and foamed rubber
profiles for the automotive industry, thermoformed polyolefin foam for food packaging
industry are some other key applications. CBA are widely used for structural foaming, as
an additive for the elimination of sink marks during plastic moulding, and as a nucleating
agent for the physical foaming process. CBA are being evaluated to foam wood-plastics
composites [32]. CBA still plays a relatively minor role in foaming many thermosets.
The high cost of CBA compared to PBA has discouraged research into PU foam
applications or for that matter any low density (<30 kg/m3), foam applications.

2.3.1 Selection Criteria for Chemical Blowing Agents

A number of factors must be considered when selecting a CBA. The first and foremost is
that the gas release temperature closely matches the processing temperature of the polymer.
If the CBA decomposition temperature is significantly above the polymer process
temperature, little or no foaming will occur. If the CBA decomposition temperature is
significantly below the polymer process temperature, poor (overblown, ruptured) cell
structure and surface skin quality is likely to result. Along with the correct decomposition
temperature, the CBA must release the gas at a controllable but rapid rate. Gas yield
must be commensurate with the target density.

Most CBA are stable under normal storage conditions and generally easy to handle, mix
and dose. A key consideration while selecting CBA is that the reaction products and

29
Handbook of Polymer Foams

residue of CBA must be compatible with the material to be foamed and have little or no
detrimental effect on properties or colour of the end product. The decomposition products
must not interfere with the flame retardant, stabiliser or other additives. In addition, the
decomposition products should not cause corrosion of equipment and tools, i.e., no
plate-out deposits on screws and moulds. For applications that involve contact with
food, the toxicity of both the CBA and the decomposition products must be considered.

Certain CBA yield water upon decomposition which can be problematic for moisture
sensitive polymers such as PC, thermoplastic polyesters, polyamide, and acetals. Such
polymers can chemically degrade in presence of water causing noticeable loss of properties.
The same can be true for CBA that generate ammonia or other alkaline or acidic gases.

Like PBA, the choice of a CBA depends upon the performance, cost-effectiveness and
competitiveness of the finished product in a particular application. Table 2.9 gives a
description of the different chemical blowing agents currently in use or consideration.
CBA are generally subdivided into two major categories: exothermic, and endothermic.

2.3.2 Exothermic CBA

By definition, exothermic CBA generate heat during their decomposition. This manifests
itself not in terms of significantly changing the polymer melt temperature but once the
decomposition starts, it is difficult to stop it before it reaches full decomposition. This
results in rapid decomposition in a narrow temperature range. Generally speaking, the
exothermic CBA are associated as those giving N2 as the main blowing gas. Thus, much
of the discussion about N2 in Section 4.2.4 will apply here too.

The level of usage for exothermic CBA (100% active) is usually 0.3-0.5% by weight for
foam applications [33]. For the elimination of sink marks, the best starting level is 0.1%.
Given in Section 2.3.2.1 are some of the common exothermic CBA in use today.

2.3.2.1 Azo Compounds

Azodicarbonamide (ADC), also known as azodicarbonic acid diamide or 1,1´-


azobisformamide, and its blends continue to be the world’s most commonly used chemical
blowing agent. For example, it accounts for around 90% of the chemical blowing agents
consumed in Western Europe [30]. The pure material decomposes at temperatures of
205-215 oC, evolving ~220 x 10-3 m3/kg of gas, primarily N2, with lesser amounts of
CO, CO2 and NH3. Its decomposition temperature can be reduced to as low as ~150 oC
through the addition of activators or kickers, to match the desired processing method

30
Blowing Agents

and polymer to be foamed. Common activators include zinc oxide, zinc stearate, many
tin or zinc-containing PVC stabilisers, urea, alcohol amines, and some organic acids
such as stearic acid.

In it’s most basic form, ADC is a fine powder with a range of particle diameters of 3-30 μm
corresponding to specific surface areas from 3 to 0.5 x 106 m2/m3 and apparent densities of
300 to 700 kg/m3. It is also available as formulated material in powder form, or basic or
modified material in pre-dispersion or masterbatch form. Modifications of ADC include
flow conditioned grades which disperse more easily, damped grades to reduce dust, and
nonplateout grades which eliminate plating out on die and mould tooling [30]. ADC is a
yellow to yellow-orange material which generates white to off-white residue upon
decomposition. The solid decomposition products of ADC include biurea, cyamelide, cyanuric
acid and urazol, and may cause plateout in extrusion and injection moulding [31].

Virtually all rubber and plastics grades can be foamed with ADC. The exceptions are the
ammonia-sensitive polymers such as PC and thermoplastic polyester that undergo
molecular weight degradation during the foaming process. Rigid PVC pipe, sheet and
profile; vinyl flooring, earplugs, coated-fabric, sealing tape, HDPE wire insulation and
crosslinked polyolefin foams are just some of the many products which use ADC as a
blowing agent [33].

Other azo compounds investigated as CBA include azobisisobutyronitrile which yields N2


upon decomposition and diisopropyl azodicarboxylate which yields N2, CO, and CO2 [34]

2.3.2.2 Hydrazine Derivates

Hydrazine derivates generally break into N2 and H2O at relatively low decomposition
temperature in the range of 110-160 oC. OBSH, a white powder, is the most common
hydrazine derivative as it forms non-volatile and non-toxic oligomeric decomposition
residues and yields 120-150 x 10-3 m3/kg of gas at STP [30]. Another product, TSH, was
widely used at one time but its use has severely declined in recent years in favour of
OBSH and azo compounds [30]. Hydrazine derivates are most widely used to blow
polymers requiring relatively low temperature processing such as rubber, PVC plastisols,
LDPE wire and cable insulation and epoxy foams.

2.3.2.3 Sulfonyl Semicarbazides

TSS is the most commercially significant semicarbazide. It decomposes in the temperature


range of 215-235 oC into a mixture of N2 and CO2 [33]. It is a white powder and

31
Handbook of Polymer Foams

generates 120-140 x 10-3 m3/kg of gas at STP. It is considered as an intermediate high


temperature CBA and is used in PS, PP, polyamide and modified polypropylene oxide.

2.3.2.4 N-nitroso Compounds

Dinitrosopentamethlenetetramine is the best known of such compounds which yield


ammonia, formaldehyde and nitrogen, in the temperature range of 190-200 oC. Used
widely in the past due to relatively low cost per unit of gas yield, its use has largely
disappeared due to toxicity and odour concerns [30].

2.3.2.5 Other Compounds

PPSO is a relatively high temperature CBA used especially where the evolved sulfur
dioxide can act also as a crosslinker to the polymer matrix [35].

2.3.3 Endothermic CBA

These absorb heat during their decomposition which leads to broader decomposition
temperature and time range. Most commercially used endothermic CBA generate CO2
as the main blowing gas. Thus much of the discussion about CO2 in Section 2.2.4 will
apply here too. They are generally white in colour with a white residue. As the components
of endothermic CBA are essentially food additives, they are ‘generally regarded as a safe’
(GRAS) as regards toxicity considerations [33]. The use level of endothermic products
(100% active) is usually twice that of exothermic CBA [33].

Endothermic CBA are often used in applications where a rapid diffusion rate of CO2 gas
through polymers allows post-finishing of foamed parts right out of the mould without the
need for a degassing period. They are the preferred CBA type for extruding rigid PVC
foam profiles where their cooling effect and slower rate of decomposition helps in the
formation of a thick skin. Nucleation of physically foamed materials, especially those used
for food packaging, has become a well established application area for endothermic CBA.

2.3.3.1 Bicarbonates/carbonates

Generically referred as inorganic CBA, these decompose endothermically into CO2 and
in some cases into water. Sodium bicarbonate and zinc carbonate are the most common

32
Blowing Agents

such products though other bicarbonate and carbonate salts have been used over the
years [31].

2.3.3.2 Polycarboxylic Acid Derivatives

Bicarbonates and carbonates are often used with a selected polycarboxylic acid such as
citric acid, or a selected salt or ester of a polycarboxylic acid. Sodium citrate and the
trimethyl ester of sodium citrate are examples of the latter. Such combinations allow the
decomposition temperature to be tailored to polymer processing temperature [3, 36].

2.3.3.3 Tetrazoles

Tetrazoles decompose into N2 alone and are thus especially suited for ammonia and
moisture sensitive polymers. 5-Phenyltetrazole, a white powder, is the primary product
in this class and it decomposes in the temperature range of 240-250 oC yielding 190-
210 x 10-3 m3/kg of gas at STP. Considered a high temperature CBA, it is used in
polycarbonates and thermoplastic polyesters [33].

2.3.3.4 Other Compounds

Other compounds such as dihydrooxadiazinone, which generates nitrogen, have been


used to blow/nucleate polycarbonates [33].

2.3.4 Endo/Exo Blends

Often the variety of demanded properties are such that that no single type of chemical
blowing agents can satisfy all of the requirements. Blends of exo- and endothermic
CBA have been used in many such cases [36]. Because of favourable price/performance
balance, ADC is the key exothermic CBA component. In most cases, selected
endothermic systems have been physically blended with ADC to provide a boost in the
expanding ability of the endothermic components, while taking advantage of their
cooling, stabilising effect and faster degassing characteristic. Some examples are blends
of sodium bicarbonate and ADC for extrusion of rigid PVC and PVC/wood composite
and zinc carbonate and ADC to foam crosslinked PE and plasticised PVC [37]. Most
of these products are available in various physical forms including powder, pellets, and
often proprietary dispersions.

33
Handbook of Polymer Foams

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Blowing Agents

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31. S. Quinn, Plastics Additives & Compounding, 2001, 3, 5, 16.

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Handbook of Polymer Foams

32. G. Luebke, Proceedings of Rapra Blowing Agents and Foaming Processes


Conference, Frankfurt, Germany, 2001, Paper No.2.

33. R.L. Heck, Proceedings of Retec on Polymer Additives: What’s New and Review,
Ft. Mitchell, KY, USA, 1997, p.277.

34. Plastics Additives: An A-Z Reference, Ed., G. Pritchard, Kluwer, London, UK,
1998.

35. R. Heinz, K. Breyer and W. Michaeli, Proceedings of Blowing Agents ’99,


Manchester, UK, 1999, Paper No.4.

36. R.L. Heck, Modern Plastics, 1999, 76, B-26.

37. G. Luebke, Proceedings of Blowing Agent Systems: Formulations and Processes,


1998, Shawbury, UK, Paper No.11

36
Expanded Polystyrene: Development, Processing, Applications and Key Issues

3
Expanded Polystyrene: Development,
Processing, Applications and Key Issues

Andrew Barnetson

3.1 Introduction

Expanded polystyrene (EPS) has rightly taken its place in modern society as an important
material in, for example, insulation in construction applications and as a packaging
material for a wide range of industrial appliances and foodstuffs.

Throughout this chapter we will consider the product in its many forms, looking at the
origins of EPS with its development by BASF in 1950 and the manufacturing process,
which is similar for both construction and packaging applications. Applications will be
considered for both the construction and packaging industries and the broad global
structure of the industry will be discussed. Key issues will be addressed for both the
construction and packaging industries.

It should be noted that throughout this chapter we refer solely to a specific product
belonging to the family of polystyrenes recognised within the industry as ‘EPS’. Other
expanded polystyrenes such as ‘extruded polystyrene’, which is used solely in the
construction industry, and ‘polystyrene paper’, the material used to make trays for
wrapping small portions of foodstuffs and which we usually see at the supermarket, will
not be covered here. Confusingly, both of these types of polystyrene are referred to by
the abbreviation XPS.

3.1.1 Development of Expanded Polystyrene (EPS)

Over half a century ago, EPS was first produced experimentally by chemists at BASF. A
patent was awarded to Stastny and Gäth in February 1950 for the ‘process of producing
porous masses from polymers’ and this became the basis for the production of EPS.

The earliest opportunities for EPS were exploited in the construction industry, where it
quickly become popular in a wide range of insulating roles due to its excellent thermal
insulating properties. It was not long before its advantages as a packaging material were

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Handbook of Polymer Foams

also apparent. The ability to protect merchandise from large shocks meant that goods
were rarely damaged during the transportation process and straw and wood were
gradually replaced by EPS packaging. Big users of the new product included the mechanical
typewriter companies, the fish industry, Kodak and the Meccano Toy Company. IBM -
perhaps the most technologically advanced company of the time - also used EPS packaging
when delivering its range of computers.

Before considering the manufacturing process for expanded polystyrene foam, there are
two specific comments that need to be made on the chemical structure of the material.
There are many misconceptions about EPS and it is important to note that:

• EPS is based on the monomer styrene which is not just a synthetic product but occurs
commonly in a range of natural foodstuffs such as strawberries and coffee beans.

• EPS products do not now contain chlorofluorocarbon or hydrochlorofluorocarbon


blowing agents, indeed, a large proportion of the industry never used these at all,
while other sectors have replaced them with other agents such as hydrocarbons which
readily decompose in the atmosphere and as a result, EPS does not have any adverse
impact on the ozone layer.

3.2 Manufacture of Expanded Polystyrene Mouldings

It is important to differentiate between the product that is manufactured by the raw


material manufacturer (commonly referred to in the industry as ‘bead’ supplier) and the
product that is produced by the processor/converter. The bead supplier produces an
expandable polystyrene that has a spherical shape and takes the form of small grains
(similar to sugar in appearance). The expandable polystyrene (bead) is typically purchased
in one tonne containers known as octabins. At the point of purchase, expandable
polystyrene contains 4-7% (by weight) of a hydrocarbon blowing agent (usually pentane).

To make EPS, tiny spherical polystyrene beads are expanded to about 40 times their
original size. The manufacturing process, in brief, involves the heating of beads using a
flow of steam, which causes the blowing agent to boil and a honeycomb of closed cells is
formed. After a maturing stage in silos, these expanded beads are transferred to a mould
and heated again with steam, They expand further and fuse together to form the shape
required. In this form EPS is made up of 98% air; making it one of the lightest packaging
materials available.

Bead suppliers offer a range of grades of material and specifications but there are two
basic types, flame retardant and non-flame retardant. The former grade is used mainly in
the building industry, the latter is used in packaging.

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Expanded Polystyrene: Development, Processing, Applications and Key Issues

During polymerisation the batches follow a ‘normal distribution’ in the range of bead
sizes produced. These are then sieved and the companies involved normally market three
bead size ranges, which can be referred to as large, medium and small. Large is used
exclusively for block manufacture for the construction industry, medium is the major
material used in packaging and the small material is used only where the packaging
product has very thin sections which are difficult to fill with the medium material.

The customer generally specifies only one property, namely the density of the finished
product. For packaging electronic items this is generally in the range of 18-25 g/l.

Note: it is commonplace in the EPS industry for density to be quoted as g/l rather than
kg/m3 but the numbers involved are interchangeable.

3.2.1 Conversion of Bead to Product

The conversion process is carried out in three stages: pre-expansion, maturing and final
moulding.

3.2.2 Pre-expansion

The raw material is heated (in special machines called pre-expanders or pre-foamers)
with steam at temperatures between approximately 80 and 100 ºC. The density of the
material falls from approximately 630 kg/m3 to values of between 10 and 35 kg/m3.
During the process of pre-expansion the compact beads turn into cellular plastic beads
with small closed cells that hold air in their interior.

The pre-expander is, essentially, a cylindrical container with diameter of 1 m, height of


2 m, and a central stirring mechanism with the facility to introduce low-pressure steam.
There are two types of pre-expansion equipment: continuous and batch.

Continuous pre-foam equipment is less favoured today by package moulding companies


because the accuracy of producing density is insufficient for subsequent moulding. It is
however commonly used by the moulding companies where large volumes of pre-foam
material are required on a continuous basis.

The batch pre-foaming process involves a pre-weighed amount of the raw material, which
is dropped into the pre-foamer machine before the steam is introduced. Steam is introduced
and the volume is allowed to increase to a predetermined point in the vessel before the
steam is shut off. A previous experiment determines this point which is based on the
weight of the material that is charged into the pre-foaming machine.

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Handbook of Polymer Foams

During the process, the low pressure, low temperature steam is mixed with the raw
material, it softens the polystyrene and raises the temperature until the blowing agent
boils. The granules expand dramatically by up to 40-50 times. This pre-foam material is
then conveyed to large storage hoppers where it is left to stand for approximately 12 hours.

3.2.2 Maturing

During the pre-foam process as a result of the rapid bead size expansion a vacuum has
been created inside the bead which leaves it with a low mechanical strength. The
permeation of air inside the bead to create atmospheric pressure is essential to the quality
of the mouldings at the final stage of manufacture.

In addition, the pre-foaming stage leaves moisture inside each bead and it is advantageous
to the final moulding process if the bead is dry as less energy is required.

It is for these reasons that the pre-expanded beads are blown, through pipes, to large
silos (hoppers) where they are dried and the internal pressure is equalised.

This is how the beads achieve greater mechanical elasticity and expansion capacity is
improved, something very useful in the subsequent transformation stage.

3.2.3 Final Moulding

In this final stage the stabilised pre-expanded beads are transported to moulds where
they are again subjected to steam so that the beads bind together. This enables large
blocks to be produced (that are later sectioned to the required shape like boards, panels,
cylinders, etc). Alternatively products are moulded in their final finished shape.

Moulding machines used for EPS throughout most of the world are predominantly
manufactured in Germany and Italy. The machines operate on the basis of the use of
aluminium moulds which are fitted as a male and female design, the shape between the
two halves of the mould being the shape required. These are fitted into a press which has
the facility to introduce steam from behind each half of the tool through small slotted
core vents which have been built into the tool.

The dimensions of any foam product are difficult to measure precisely and in most
instances plus or minus 1.5 mm is no great difficulty as the product can generally take up
this difference when it is fitted into a pack.

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Expanded Polystyrene: Development, Processing, Applications and Key Issues

3.3 Applications for Expanded Polystyrene Packaging

Over half a century, the uses of EPS have become numerous both within the packaging
industry, where it can offer excellent impact resistance, and within the building industry,
where its excellent thermal insulating properties mean that it is often used in the insulation
of homes and offices. The reasons for this and the broad areas of application concerned
will be considered in this section. However, both of these areas are now mature and
established markets and real growth is expected from other, more novel applications
that are outside the conventional packaging and construction sectors. These applications
are addressed separately under a broader category of other applications.

3.3.1 Packaging

EPS is an extremely important material for the modern packaging industry offering an
excellent combination of protection, cost-effectiveness and environmental performance.
In short, there are many reasons to use EPS as a packaging material. The distinct packaging
advantages that EPS offers means that it has become the predominant packaging material
for industries as diverse as electronic consumer goods, horticultural products and fish,
throughout the world. Its versatility means that whether it is moulded or hand cut, EPS
will protect the smallest electronic component through to the largest fridge freezer. The
outstanding shock absorbency of EPS packaging ensures the protection of a broad range
of products. Moreover, its compression resistance means that EPS is ideal for stackable
packaging goods.

For example most white goods, such as fridges and washing machines, and brown goods,
such as TVs and videos come packed in EPS to prevent damage in transit. Since it is such
a light material it adds very little to the weight of the package so transport costs and
consequent vehicle emissions are kept to a minimum.

The thermal insulation properties of EPS help keep food fresh and prevent condensation
throughout the distribution chain. It is widely used in the agricultural sector for the
packaging of fruit and vegetables.

There is no loss of strength in damp conditions, making EPS ideal for cool-chain products.
Furthermore, the fact that the material is moisture resistant means that the highest hygiene
requirements are met. Another common use for EPS is therefore to package fish for
transportation, which can be packed with ice and so remain chilled until reaching the
final destination. In this case the EPS primarily provides thermal insulation rather than
mechanical protection.

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Handbook of Polymer Foams

Garden centres are also using EPS with a number of smaller plants and flowers now
coming in EPS containers. It is easier to break plants out of these than from the usual
plastic pots and, here again, EPS provides an important level of thermal insulation that
protects the plants from frost in the early stages of growth.

When safety is paramount, EPS comes into its own. It is used in the manufacture of
children’s car seats and cycling helmets, where its protective qualities, strength and shock-
absorbency are vital.

3.3.2 Construction

The characteristics of EPS make it ideal for use as lightweight filler, insulation, as an
element for decorating or adding imaginative finishing touches, as a lightweight filling
material in roads, to facilitate land drainage, etc. Visit a construction site or examine the
structure of a wide range of buildings and you find products made from EPS carrying
out diverse and important functions.

Low thermal conductivity: due to its closed air-filled cell structure which inhibits the
passage of heat or cold, a high capacity for thermal insulation is achieved.

Low weight: densities of between 10 and 35 kg/m3 allow light but safe construction
works.

Mechanical resistance: although they are light, EPS products enjoy good mechanical
properties which are important for certain applications (load-bearing roof insulation,
sub-pavement flooring, etc).

Low water absorption: this helps in maintaining the thermal and mechanical properties
which might otherwise be affected by humidity.

Ease of handling and installation: the material can be worked with the usual tools and
guarantees perfect finishing and adjustments. At the same time, its low weight makes it
easy to transport materials to the site and provides economy of installation.

Chemical resistance: Expanded polystyrene materials are perfectly compatible with the
materials usually used in the construction industry including cements, plasters, salt or
fresh water, etc., but not solvents.

Versatility: it can come in many different shapes and sizes, to meet the specific requirements
of the specific application.

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Expanded Polystyrene: Development, Processing, Applications and Key Issues

Ageing resistance: all of these properties are retained over the whole of the material’s life
which can be expected to be as long as the building itself. EPS products are not altered by
external agents or by fungi or parasites as these will find no nutritional value whatsoever
in the material.

The main use of EPS in building applications is for thermal insulation, where EPS is used
to insulate wall structures (in the cavity, internally or externally), roofs and floors. It is
equally appropriate in new or refurbished buildings.

Installing EPS insulation means that less heating fuel is required as the EPS panels that
are placed in the cavity of a house wall can reduce heat loss up to five times that of a wall
with no insulation. Put another way, heat loss can be reduced by more than 70%. For
every kilogram of oil used on the manufacture of EPS insulation board, about 200 kg of
oil will be saved in terms of reduced heating demand over the lifetime of the building.

EPS is also used as a ‘fill’ material or void former, where it can help to overcome problems
caused by poor ground in the construction of bridges and road embankments, dams and
dock harbour walls.

EPS can also be used to improve impact sound insulation in office blocks with solid
concrete floors by damping impact vibrations. Large slabs can be laid quickly with no
special equipment.

Since it is so buoyant, EPS can also be used to make floating pontoons for yachting
marinas. Further applications of EPS in the field of construction are possible and
enormously varied. In fact, we can find EPS in all building requirements. What’s more it
can be used in building work including large structures like roads, bridges and railway
lines.

All manufacturers of EPS are aware of the need to consider the impact of the product on
the environment. The manufacturers are also aware of the need to minimise the energy
used in making the product and to maximise the amount of energy which can be reclaimed.

3.3.3 Other Applications

In addition to the conventional application sectors of packaging and construction, there


are other markets that fall outside these areas. For the sake of completion, they are
worthy of note but most do not currently use significant volumes of material and remain
minority applications.

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Handbook of Polymer Foams

The use of EPS in the automotive industry has become more widespread in recent years,
alongside its ‘sister’ product expanded polypropylene (EPP). However, where EPP is
used in structural applications such as front and rear bumpers, EPS is being used as a
lightweight voidfill under floors. Avoided for a long time due to the acoustic ‘squeak’,
manufacturers have now overcome the problem and the opportunities for use are
increasing.

The production levels for cycle helmets have undergone a steady increase over recent
years as the usage becomes more popular. Incorporating the impact resistance and light
weight that has made the material successful for many packaging applications, EPS can
now add a level of protection to a new sector.

In other applications, surf boards have been a popular leisure tool throughout the world
for many years and EPS is chosen for its light weight and durability. The opportunities
for aerating soil are also addressed by including small amounts of EPS beads.

3.3.4 Novel Applications

One of the most important and most novel construction applications that has come to
prominence in recent years is the insulated concrete form (ICF). This enables quick and
energy efficient construction of a building by establishing a wall comprising two separate
end walls in EPS. The gap between the two layers of EPS is then filled with concrete to
give strength.

The EPS shapes are custom moulded in the same way as a typical package moulding but
a metal or plastic member is inserted into the mould. Each EPS piece then has two
opposing, parallel sheets of EPS that are held at a fixed distance by the inserted member.

Pieces can be fitted together quickly and, once concrete is added, the resultant structure
has an exceptional combination of strength and thermal insulation. Sound transmission
tests have also demonstrated that sound transmission is reduced to one-third that of a
conventional wall structure.

3.4 Properties of EPS

Expanded polystyrene has primarily been developed for use in the construction and
packaging industries where the properties of thermal insulation and mechanical protection
have been paramount.

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Expanded Polystyrene: Development, Processing, Applications and Key Issues

Construction applications such as underfloor or wall insulation, benefit from the very
high levels of thermal insulation, while the packaging of fragile electronic goods requires
high mechanical (impact) protection. Increasingly though, EPS is used for the transport
of food, and packaging (fish, fruit and vegetables) and in these cases, both the mechanical
and the thermal insulation play an important role.

It should be noted that the properties of an expanded polystyrene foam are intrinsically
linked to the density of the material and are often quoted in a range.

3.4.1 Mechanical Performance

The closed cell structure of EPS foams – incorporating 98% air – enables it to react to
impact by deforming and returning to shape. This process absorbs the energy associated
with sudden impact and offers a superb level of protection, refer to Table 3.1.

It may be noted that expanded polystyrene foams may absorb very small amounts of
water but the product is not hygroscopic and the mechanical properties are unaffected
by moisture content.

Table 3.1 Physical properties of EPS foam at varying densities


Density (g/cm3) 15 25 40 50
Tensile strength (kPa) 200 350 600 750
Flexural strength (kPa) 200 400 700 900
Compressive stress at 10% compression (kPa) 90 180 320 400
Source: BASF

3.4.2 Thermal Insulation

Apart from a vacuum, air is the simplest and lowest cost thermal insulator and thin
layers of air (up to 6 mm) have a very low thermal conductivity. However, it is not
always practical to rely on air as an insulator and, for packaged goods a material is
required to form the package.

physical properties BASF


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Handbook of Polymer Foams

Expanded polystyrene is ideal in this case as it has outstanding thermal insulating


properties due to its closed-cell foam structure consisting of microscopically small air
bubbles. Due to the inert nature, expanded polystyrene foams do not directly affect
other substances such as food.

It may be noted that thermal conductivity for EPS foams is greater at very low densities
(10-15 g/cm3) and falls with an increase in density so that optimum thermal performance
occurs in the range 30-50 g/cm3. After that, the thermal conductivity starts to rise again,
refer to Table 3.2.

Table 3.2 Thermal properties of EPS foam at varying densities


Density (g/cm3) 10 20 40 50 60
Thermal conductivity (W/mK) 0.043 0.035 0.033 0.033 0.034
Source: BASF

physical properties BASF

3.4.3 Chemical Properties

The performance of expanded polystyrene in the presence of chemicals can vary widely.
It is unaffected by prolonged contact with brine, soaps solutions, bleaches and most
dilute acids. However it is extremely susceptible to the presence of many organic solvents.

EPS foams may undergo the same changes following prolonged exposure to UV radiation
that can occur in other polymers. However, by the nature of the applications due to the
short life associated with packaging, in most cases this does not feature significantly.
Construction applications have a greater life span but are unlikely to be exposed to UV
radiation.

EPS does not have any nutritional value for animals and does not support mould growth.
It does not emit any water soluble substances that might be considered to contaminate
groundwater.

3.4.4 Recent Research on Properties of EPS: Value for Fruit and Vegetables

Research has demonstrated the value of using expanded polystyrene for the packaging
of foodstuffs. It is recognised that carbon dioxide is formed by fruit as a product of

46
Expanded Polystyrene: Development, Processing, Applications and Key Issues

metabolism and that the release will lead to an increased concentration in the package,
slowing the ripening process.

EPS packaging retains the nutritional value of fruit and vegetables better than any other
packaging, according to new research conducted by the Korean Food Research Institute
and confirmed by the Michigan State University School of Packaging. Tests showed that
vitamin C levels were preserved in both fruits and vegetables packed in EPS at a higher
level than those packed in other materials.

Researchers selected three fruits - apples, pears and grapes - along with three kinds of
vegetables - squash, cucumbers and tomatoes - and separated, packed and stored the
produce at controlled temperatures. They then routinely monitored the freshness and
nutritional value of the items using a variety of established tests. On virtually every
property measured, EPS outperformed the other materials.

One of the primary reasons the study was undertaken was because such a high percentage
of agricultural produce harvested today is lost due to spoilage. The research found that
EPS could effectively slow the rate of spoilage, which is up to 45% in some countries.

The specific findings on vitamin C show that certain vegetables retain up to 44% more
vitamin C after a week of storage. The fruits, which were monitored for the study over
varying periods of time, were shown to hold between 6.6% and 41% more vitamin C
than those packed in corrugated paperboard boxes.

3.5 Global Structure of Markets and Companies

3.5.1 Europe

All of the major countries throughout Europe, produce EPS for both packaging and
construction applications. However, it can be noted that almost without exception, every
country produces significantly more EPS for construction than for packaging.

In some few cases, such as Denmark and UK, the difference between the two application
sectors is small. However, for most countries there is a pronounced difference and in
some cases, most notably Germany and Poland, the production for construction is 5-
600% that of packaging. The net effect is that throughout Europe, construction is the
major user of EPS, refer to Table 3.3.

In recent years, packaging manufacturers have seen the production facilities for electronic
equipment moving to central Europe and the Far East. EPS manufacture has been forced

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Handbook of Polymer Foams

Table 3.3 EPS Production in European countries (Source: EUMEPS)


Packaging (tonnes) Construction (tonnes)
European EPS production (2001) 200,000 600,000

to follow and several major European moulding companies have established


manufacturing sites throughout the Czech Republic, Slovakia and Poland.

Thus, while EPS packaging production has declined by a small amount across current
EU member states, much of this will be regained when accession states join the EU.

There are increasing demands from Building Regulations for the energy efficiency that
follows from high levels of thermal insulation and this is complemented by some innovative
new approaches to the methods of house assembly. As a result, construction applications
are still enjoying a small but significant level of growth throughout Europe and this is
expected to continue for some years.

When the number of manufacturing companies are considered, both the EPS construction
and packaging industries have seen significant consolidation in recent years. Many major
producing countries – notably Germany, France and UK – now have a small number of
large, influential manufacturers and this has had a bearing on their negotiations with the
raw material manufacturers. Other countries, such as Italy and Spain, still have a very
large number of small moulding companies and consolidation in the future may be likely.

3.5.2 Asia

Unlike other regions of the world, the production of EPS construction products in Asia is
extremely unusual and tonnages are very low. By comparison, the production of EPS
packaging for consumer electronic goods and household appliances is very significant
with much of this being exported to Europe and USA. The production of EPS boxes for
fresh fish remains a very significant area of application.

In numerical terms, total Asian production of EPS dominates the world market. Some
countries such as Japan and Korea have maintained large levels of production over many
years while one country in particular – China – has seen very dramatic growth in recent
years, refer to Table 3.4.

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Expanded Polystyrene: Development, Processing, Applications and Key Issues

Table 3.4 EPS Production in Asian countries


Country EPS packaging production, tonnes (2001)
China 700,000
Korea 228,000
Japan 201,000
Thailand 37,000
Taiwan 32,000
Malaysia 29,000
India 25,000
Others 50,000
Total 1,302,000
Source: AMEPS

production in Asia

3.5.3 USA

In the USA, levels of production for EPS packaging and construction applications are
largely similar. However, it may be noted that the production of EPS trays and other
containers for food service is much more significant in USA than in Europe, refer to
Table 3.5.

Table 3.5 EPS Production in USA


Production, 2001 (tonnes)
Total EPS sales 394,000
EPS block 180,000
EPS packaging 214,000
Source: EPSMA

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Handbook of Polymer Foams

3.6 Key Issues Facing the EPS Industry

3.6.1 Fire

The performance of EPS in a fire needs to be well understood because it is commonly used
in construction applications. To do this effectively, it is important that an assessment of the
material is based on performance in end-use conditions and this depends not only on the
chemistry of the material but also on the physical state of the EPS.

Almost every organic material is susceptible to fire and polystyrene foam is combustible.
However, in practice, the burning behaviour depends on the conditions under which it is
used, as well as the inherent properties of the material. These inherent properties differ
chemically, depending on whether or not it contains a fire retardant additive but the burning
behaviour also depends on the nature of bonding of EPS to other materials, the location of
the product and the availability of oxygen (ventilation). The important point to note is that,
when installed correctly, expanded polystyrene products do not present an undue fire hazard.

The presence of fire retardants leads to significant improvements in the fire behaviour of
EPS. In the presence of large ignition sources from fires involving other materials, fire
retarded grades will eventually burn but in such cases the building may be considered to be
beyond the point of rescue.

The presence of the fire retardant has a beneficial effect when EPS is exposed to a smaller
fire source. In these cases, the foam shrinks away from the fire source, reducing the likelihood
of ignition. Decomposition products of the fire retardant additive cause quenching so that
on removal of the ignition source, the EPS will not continue to burn.

The most commonly used flame retardant is HBCD (hexabrominated cyclododecane) and
there are currently few alternatives. HBCD is currently undergoing a risk assessment but
this has a long way to go. However, some labelling of the chemical in relation to aquatic
organisms appears likely. The European Chemical Industry Council (CEFIC) has set up a
steering committee to review the position.

Smoke is an important factor in fires since a high density of smoke can be toxic and can
inhibit the search for an emergency exit. In actual fires where smoke is produced, it is often
anticipated that this originates from EPS insulation. In fact, most of the smoke originates
from materials such as burning wood, asphalt felt and furniture.

EPS is flammable, as are many other building materials but this is only relevant if EPS is
assessed as an exposed insulating material. Fire safety philosophy correctly considers ‘end
use conditions’ and recognises that EPS does not present an undue hazard.

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Expanded Polystyrene: Development, Processing, Applications and Key Issues

3.6.2 Recycling

Environmental legislation is developing throughout the world and the polystyrene industry
is affected along with all other materials. In Europe, the Packaging industry has been at
the forefront of developing legislation (Packaging and Packaging Waste - 94/62/EC).

Following the implementation of this Directive into national legislation in each member
state (1999), targets were established for the recycling of all packaging materials.

It is important to remember that the Packaging and Packaging Waste Directive makes no
specific reference to EPS and it is only ever considered under the general plastics target
(15% recycling in 2001). Throughout Europe, the expanded polystyrene industry has
exchanged information on recycling and promoted best practice and, as a direct result, in
most European countries the levels of recycling already exceed targets. Likewise, moves to
reduce the presence of EPS in landfill – either through an increasing tax or through localised
bans – are being pre-empted by the significant levels of recycling that are being achieved.

Further legislation is being developed to tackle other applications such as such as Waste
Electrical and Electronic Equipment (WEEE) and End of Life Vehicles but neither of
these are expected to have any impact on EPS.

It is unclear how additional future legislation will develop but there is no current or
pending European legislation that discriminates against the use of EPS packaging.

With this vast increase in the amount of environmental legislation across a broad range
of industry and in the light of recent legislative developments, some companies became
concerned that the use of EPS packaging would make it difficult to meet this legislation.
Indeed, a perception has continued in all too many cases that EPS cannot be recycled.
This could not be further from the truth as levels for EPS recycling across Europe already
exceed legislative requirements and are amongst the highest for any plastic material.

The EPS industry throughout Europe has worked for many years to actively encourage
the recycling of used packaging material and many large electronics companies are
successfully collecting and recycling their EPS.

The low weight of EPS is an advantage during its life as a packaging material but can
cause complications in recycling, as it becomes difficult to transport over any distance.
When uncompacted EPS packaging is placed in a typical (12 m) container, it will be filled
with less than half a tonne of material. This is not economically viable for transport.

The EPS industry has addressed this point however and a wide range of compaction and
densification machinery is now available to ensure that recycling continues to be viable.

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Handbook of Polymer Foams

The majority of these compaction machines operate in a mechanical mode with a rotating
screw of varying pitch that causes the material to be physically compacted by up 35:1 or
even 40:1. Once compacted, material can be transported much larger distances and
transport to a recycling site becomes a viable option.

It is less common for companies to use a thermal system, which melts the polystyrene,
returning it to the original, solid material. These thermal systems tend to be slower and
more energy intensive for the waste holder, as well as producing a solid block that may
be more difficult for the recycler to process. However, new developments in technology
may make this method of size reduction more popular in future.

Solvent-based systems have also been proposed whereby the EPS is added to a vat of
solvent and dissolved to produce a slurry that can be transported for recycling. Given
that EPS is only 2% material and 98% air, the material readily dissolves and there are a
wide range of solvents that could be used for this operation but – due to modern concerns
about volatile organic compounds (VOC) – are not generally acceptable.

Some research has been carried out into the use of a chemical that is extracted from
citrus fruits, negating the concerns about VOC. However, the logistics and economics of
processing the slurry have still proved complicated and this process has not received
widespread acceptance and the physical compaction process remains most common.

Once collected by a recycler, EPS is recycled in a number of different ways. Firstly it can
go back into new EPS foam and is widely used by the construction industry where recycled
packaging is added to insulation board. Studies have demonstrated that, done correctly,
the introduction of recycled material to new foam polystyrene has no detrimental effect
on the properties of the new product.

Throughout Europe, recycled material is also returned to the packaging industry where it is
either incorporated into new package mouldings or it is used in the form of ‘loosefill’ packaging.

Once the air content is removed, EPS is no different from crystal polystyrene and it can
be used in a range of non-foam applications. Thus recycled EPS can be widely used in
office equipment, coat hangers, videocassettes and plant pots.

One of the most novel uses for recycled EPS is a wood substitute that can be used in a
vast range of areas. Recycled polystyrene can be converted into a product that looks and
acts like wood and can be sawn, nailed or screwed, just like wood. It can be used for
simple products such as park benches and fence posts and is already found in garden
furniture and marine walkways. The product costs less than hardwood but really has a

52
Expanded Polystyrene: Development, Processing, Applications and Key Issues

value when used to replace hardwoods such as mahogany and teak where it can save the
impact on the rainforests. A major UK retail store has announced that they will be using
the product in their counter tops where it is extremely durable and resistant to impact
from trolleys.

One UK recycler has now developed the replacement idea further and is now marketing
a slate replacement that is made from recycled polystyrene and slate dust. This product
closely resembles conventional slate but it is expected to last longer and cost less. The
project involves the manufacture of housing roof slate replacement made from a 50:50
blend of slate dust and recycled EPS Packaging. It has the full backing of a major
conventional slate manufacturing company and it is expected that once the site is running
it will require very large amounts of polystyrene.

3.6.2 Alternatives to Mechanical Recycling

When mechanical recycling options are not appropriate, incineration with energy recovery
is a viable alternative. This enables the energy content of EPS to be recovered to generate
substantial amounts of energy since EPS has a higher calorific value than coal and
approximately the same value as fuel oil.

Emissions from incineration plants are strictly regulated and control systems have been
developed to the level where incineration plants can be run with no adverse effects on
the surrounding environment or population. Tests conducted at the SELCHP energy
from waste plant in London have shown that combustion can be accomplished within
stringent emission limits.

EPS in the waste stream can readily be treated in a modern energy from waste plant. This
is an environmentally acceptable option for dealing with that portion of plastics waste
which cannot be sensibly recycled.

In any modern waste management programme, landfill should only be used as a last
resort. Well-managed sites should be stable enough not to suffer from subsidence and
EPS is an ideal material for disposal in landfill, being mechanically stable and inert.

No company or individual should have any concerns about the use of EPS on
environmental grounds. There is no European environmental legislation that specifically
targets EPS and in many European countries it is already recycled to a higher degree than
legislation requires.

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Handbook of Polymer Foams

Further Information

There is limited information currently in print about expanded polystyrene foam and the
majority of available literature comes from the raw material manufacturers and trade
associations.

Major manufacturers of expandable Regional Trade Associations:


polystyrene:

BASF AG European Manufacturers of EPS


Carl Bosch Strasse 38 (EUMEPS)
67056 Ludwigshafen Avenue Marcel Thiry, 204
Germany B-1200 Brussels
www.basf.de Belgium
www.eumeps.org
Nova Chemicals Corporation
1000 Seventh Avenue SW EPS Moulders Association (EPSMA)
PO Box 2518, Station M 1298 Cronson Boulevard
Calgary Suite 201
Alberta Crofton
Canada MD 21114
T2P 5C6 USA
www.novachemicals.com www.epspackaging.org

BP Asian Manufacturers of EPS (AMEPS)


European Customer Service Centre 6F Showa Akihabara Building Bld
Building A 2-20 Kanda Sakuma-Cho
Chertsey Road Chiyoda-Ku
Sunbury-on-Thames Tokyo 101-0025
Middlesex Japan
TW16 7LL www.ameps.org
http://www.bpchemicals.com/

54
Rigid Polyurethane Foams

4
Rigid Polyurethane Foams

David Eaves

4.1 Introduction

The term ‘polyurethane’ covers a wide range of materials produced by the reaction of
polyfunctional isocyanates with substances containing at least two hydroxyl groups.
The main chemical moiety resulting from this reaction is the urethane group:

-NH-CO-O-

Other groups which may be formed include urea, amide, biuret, allophanate, ether and
ester linkages, depending on reaction conditions and the particular catalysts used. Hence,
the term ‘polyurethane’ is a very general one covering materials having very different
properties and including both expanded and non-expanded products. The materials
discussed in this chapter are hard, expanded polyurethanes having low flexibility and a
high load bearing capacity in relation to their density. Compression deflection curves of
these materials show a pronounced yield point and hence the foams have a significant
permanent set after compression. In contrast to the open cell structure of flexible
polyurethane foams, rigid foams have a mainly closed cell structure. They are expanded
using physical blowing agents which are retained in the closed cells and which have a
significant influence on some of the foam properties, particularly thermal insulation.

Isocyanate-based rigid foams for insulation applications were introduced in the early
1950s and can be made by both one shot or prepolymer processes using either toluene
di-isocyanate (TDI) or di-phenyl methane di-isocyanate (MDI). In the one shot process,
isocyanate and polyol are reacted to provide the final foam in a single step. In the
prepolymer process, some polyol and excess isocyanate are reacted to provide an
isocyanate tipped prepolymer which is then reacted with further polyol in a subsequent
step to produce the final polymer. The prepolymer process has the advantage of low free
isocyanate levels (and hence low toxicity) together with better regulation and control of
the reaction and lower exotherm. The main disadvantage is the extra process of prepolymer
production which adds to the cost.

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Handbook of Polymer Foams

The isocyanate/polyol reaction is exothermic generating high temperatures within the


reaction mix. Expansion of rigid polyurethane foams results largely from the consequent
evaporation of a liquid physical blowing agent which is added as a solution to one of the
components. Alternatively, it is possible to use a gas with a boiling point well below
room temperature. The gas is dissolved under pressure in one of the components and
subsequently comes out of solution when the mixed components are depressurised.

Reactions are affected by additional factors including the presence of catalysts, surfactants
and fire retardants. Such additives regulate the rate of reaction, the type of chemical structure
formed, the foam morphology and ultimately the physical properties of the foam.

The general class of rigid polyurethane foam can be divided into rigid polyurethane, or
PU foams, and polyisocyanurate, or PIR foams. PU foams are produced by reaction of
isocyanates (usually MDI) with short chain polyols whilst PIR foams result from reactions
in which MDI is used at levels substantially higher than stoichiometric (around 50%
higher) in the presence of special metal salt catalysts. The excess MDI is the key to PIR
production as under the reaction conditions it reacts with itself to form cyclic trimeric
isocyanurate groups. The final structure contains both urethane and isocyanurate groups
and the materials are more correctly referred to as modified polyisocyanurate foams.
PIR foams are intrinsically more thermally stable than PU foams and have a superior fire
resistance. However, there are some disadvantages with PIR foams such as generally
poorer adhesion and friability.

The rapid increase in the use of these rigid polyurethane foams following their introduction
in the early 1950s was due mainly to their enhanced water resistance (both liquid and
vapour) and low thermal conductivity. Hitherto, isocyanate foams had a generally open
cell structure through which water or water vapour could easily penetrate, together with
thermal conductivities around 32 mW/m.K at 10 °C. The new rigid, closed cell, isocyanate
based foams were essentially impervious to water and, using low thermal conductivity
expansion gases such as CFC-11 or CFC-12, thermal conductivities were reduced to
typically 17 mW/m.K. Hence, insulation thicknesses could be reduced to half that of the
old products which depended on the presence of air trapped in cells and foam interstices
for their insulation performance. It was soon realised, however, that insulation
performance of the new closed cell products decreased with time as the chlorofluorocarbon
(CFC) gas diffused out of the cells, but even so a superior thermal performance was
maintained. Thermal insulation of appliances, e.g., refrigerators and freezers, and buildings
remain the main applications of these foams.

The basic chemistry involved in the manufacture of PU and PIR foams has been discussed
at length elsewhere [1, 2]. Some trends which have been reported recently are the move

56
Rigid Polyurethane Foams

towards the use of polyisocyanurate foams incorporating aromatic polyester polyols [3,
4] due to the higher fire resistance and, most importantly, the move away from
chlorofluorocarbon-11 (CFC-11) and chlorofluorocarbon-12 (CFC-12) to blowing agents
having greater environmental acceptability to meet Montreal Protocol requirements.

4.2 Materials

4.2.1 Polyols

4.2.1.1 Polyether Polyols

Polyols used for the production of polyurethane foams are oligomers, (i.e., low molecular
weight polymers), containing at least two hydroxyl groups. They may be polyethers,
polyesters, polyolefins or vegetable oils. Polyether and polyester polyols are the main
compounds used in both rigid and flexible foams. Polyester polyols were used to a
significant extent in the early development period of rigid polyurethane foams but were
later discontinued except for special applications owing to their high cost coupled with
generally low functionality, high viscosity and low dimensional stability of the resulting
foam. More recently however, polyester polyols are being increasingly used in the
production of rigid PU foams for the construction industry owing to the enhanced fire
retardancy that can be achieved.

Polyether polyols are produced by the anionic polymerisation of alkylene oxides, (e.g.,
propylene oxide, ethylene oxide), in the presence of an initiator and catalyst. The
functionality and equivalent weight of the polyol can be controlled within wide limits
and the materials are widely used for both rigid and flexible polyurethane foams. Initiators
are low molecular weight hydroxylated compounds whose functionality determines that
of the resulting polyol. Some commonly used substances are shown in Table 4.1.

Polyether polyols for rigid PU foams are produced using high functionality initiators
such as glycerol, sorbitol and sucrose. Some polyol characteristics are shown in Table 4.2.

The most widely used catalyst is potassium hydroxide although this does result in some side
reactions which lead to the production of undesirable monols. Improved catalysts have been
developed which eliminate this problem and this is particularly important for the production
of high molecular weight diols for the manufacture of flexible polyurethane foam.

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Handbook of Polymer Foams

Table 4.1 Functionality of some common polyols


Hydroxylated Compound Functionality
Ethylene Glycol 2
Glycerol 3
Trimethylol Propane 3
1,2,6-Hexane Triol 3
Triethanolamine 4
Sorbitol 6
Sucrose 8

Table 4.2 Polyols for polyurethane foams


Polyol property Rigid foam Semi-rigid foam Flexible foam
OH number 350-560 100-200 5.6-70
(mg KOH/g)
OH equivalent 160-100 560-280 10,000-800
(56,110/OH No)
Functionality 3.0-8.0 3.0-3.5 2.0-3.0
Elastic modulus at >700 700-70 <70
23 °C (MPa)
Reproduced with permission from Handbook of Plastic Foams, Ed., A.H. Landrock,
Noyes Publications, Chapter 2, Thermosetting Foams
Note: OH Number - mg KOH/g
OH Equivalent - 56,110/OH Number

4.2.1.2 Polyester Polyols

Polyester polyols for polyurethane foams can be produced by the reaction of di-basic
acids, (e.g., adipic acid, phthalic acid) with glycols, (e.g., ethylene glycol, propylene glycol);
alternatively, they can be made by the ring opening polymerisation of lactones. These
materials are used in the manufacture of flexible polyurethanes. However, for rigid
polyurethane foams, aromatic polyester polyols are the preferred polyol type.
functionality of Polyols polyols for Polyurethane foams Landrock A.H.

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Rigid Polyurethane Foams

4.2.1.3 Aromatic Polyester Polyols

Aromatic polyester polyols (APP) have in recent years become the materials of choice for
rigid polyurethane foams used for insulating board in the construction industry [4].
Initially these materials were used as low cost extenders to replace just part of the polyether
polyol, but it was soon realised that such foams had improved fire resistant properties,
i.e., low flammability and low smoke production. In Europe, where hydrocarbon blowing
agents have, for environmental reasons, largely replaced the original CFC types, the use
of APP in conjunction with PIR foam chemistry has counteracted the adverse effects on
flammability characteristics resulting from the change in blowing agents. The trimeric
isocyanurate structure of PIR foams gives them enhanced thermal stability compared
with PUR foams and char formation during thermal decomposition is high - around
50% compared with 20% from PU foams. This char, by virtue of its low thermal
conductivity and ability to reflect a high proportion of incident radiation, is the main
reason for the better fire resistance of these materials. By incorporation of polyols
containing aromatic ring structures, char formation is even further enhanced - hence the
additional benefit conferred by APP [4].

The manufacture of APP involves the reaction of carboxylic acids with alcohols. The
acids are obtained from three sources, namely: di-methyl terephthalate (DMT);
polyethylene terephthalate (PET); and phthalic acid or anhydride (PA).

DMT is available as a residue from PET production where, to avoid transport problems,
it is generally converted on site to polyesters by glycolysis. Process residues include
aromatic esters of di- and tri-carboxylic acids, and the functionality of the APP resulting
from glycolysis (with di-ethylene glycol) is increased to 2.2-2.3. This, together with
improved viscosity stability attributed to the heterogeneous nature of the mix, gives APP
produced from a DMT source an advantage over materials from PET or PA.

Production of APP from PET, like the DMT process, involves utilisation of otherwise
waste material. PET waste is obtained either from post consumer scrap or as waste from
PET production. Environmental initiatives, (e.g., the European Packaging Waste Directive
which requires member states to introduce legislation stipulating minimum recycling
and recovery rates for packaging waste), together with generally heightened environmental
awareness is likely to lead to greater pressure for PET recycling by the glycolysis route
and PET-based APP are likely to become increasingly and widely available. Recyclers
have developed proprietary methods for dealing with such wastes. These require the
contaminated nature and varied source of such waste to be taken into account, together
with the necessity of removing catalyst residues which could have an adverse and
unpredictable effect on subsequent foam production.

59
melting points of Polyesters Tideswell R.B.

Handbook of Polymer Foams

A recently developed process which offers better control over molecular structure has in
Europe provided APP with improved consistency and lower viscosity. These ‘second
generation’ APP are very suitable for rigid PU foam production.

Polyols made from PA, a substance widely used for the production of phthalate plasticisers
for polyvinyl chloride (PVC), are pure, clearly defined materials used in formulations
where precise functionality and fixed mix ratios are needed. However, for many
applications this is unnecessary.

The improved fire resistance of PIR foams incorporating APP is maximised using APP
based on DMT or PET. This has been attributed to the higher softening temperature and
greater heat stability of polymers based on terephthalic acid. The foams also have greater
thermal stability. Approximate melting points of phthalic acid ester isomers are shown
in Table 4.3.

Table 4.3 Approximate melting points of polyesters from phthalic acid


(PA) isomers (°C)
Phthalic acid isomer
Glycol Ortho PA Iso PA Tere PA
Ethylene 63-65 103-108 25 6
Diethylene 10-11 55-60 65-70
Reproduced with permission from R.B. Tideswell, SPI Annual PU Conference 1988,
Philadelphia, PA, USA, p.374 [4]. Copyright SPI, 1988

4.2.2 Isocyanates

The two isocyanates used for the production of almost all polyurethane foams, both
rigid and flexible, are TDI and MDI. The original production method for isocyanates
was based on the phosgenation of aromatic or aliphatic amines:

R-NH2 + COCl2 ———> R-NH-COCl + HCl (4.1)

R-NH-COCl ———> R-NCO + HCl (4.2)

More recently phosgene free methods have been developed, for example, reductive
carbonylation of a nitro compound in the presence of an alcohol to produce a urethane
which thermally dissociates to give an isocyanate:

60
Rigid Polyurethane Foams

R-NO2 + 3CO + R´-OH ————> R-NH-CO-O-R´ + 2CO2 (4.3)

R-NH-CO-O-R´ ————> R-NCO + R´-OH (4.4)

Several other phosgene free routes are also available.

MDI is obtained initially as a mixture of di-cyclic monomeric MDI (MMDI) and polycyclic
polyisocyanates (PMDI) with approximate proportions as shown in Table 4.4.

MMDI is separated from the polymeric form by distillation and exists in two isomeric
forms: 2,4-MDI and 4,4-MDI. Both are solid materials at room temperature (melting
point 38 °C), the latter with a tendency to dimerise. The main applications for MMDI
are prepolymers for flexible foams, shoe soles and thermoplastic polyurethanes (TPU).

The more important form of MDI in terms of volume is PMDI which is a mixture of
isocyanates with two or more aromatic rings remaining in the distillation residue. PMDI is
a yellow to dark brown material, liquid at room temperature (melting point less than
10 °C) with a higher functionality than MMDI but, owing to the lower NCO content, of
reduced reactivity. The higher functionality of PMDI facilitating the production of a rigid,
crosslinked, network coupled with the highly aromatic character which contributes to
flame resistance, makes PMDI the isocyanate of choice for most rigid polyurethane foams.

TDI, produced from toluene diamine, is a colourless liquid commercially available as a


mixture of the 2,4 and 2,6 isomers in the ratio of 20:80 (TDI T-80) or 65:35 (TDI T-65).
Its main use is in the production of flexible polyurethane foams.

Other isocyanates are available, such as, 1,6-hexamethylene diisocyanate, isophorone


diisocyanate and tetra-methyl xylene diisocyanate. These are used for special applications
such as light, weather and heat resistant coatings, but have little application as rigid
foams.

Table 4.4 Composition of MDI as manufactured


2 ring monomeric MDI 48%
3 ring compounds 27%
4 ring compounds 5%
5 ring compounds 4%
Higher homologues 16%
Source: [5]

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Handbook of Polymer Foams

Isocyanates may be modified by including linkages such as allophanate, carbodiimide


and isocyanate to control reactivity and lower vapour pressure. They may also be ‘blocked’
by reaction with compounds containing labile hydrogen atoms, e.g., phenols and
nitrophenols. Blocked isocyanates have the advantage of being inert at room temperature
but liberate free isocyanate groups for reaction when the temperature is raised. This
technology has application in heat activated coatings but again is not commonly used
for rigid foam production.

4.2.3 Blowing Agents

Rigid polyurethane foams produced in the 1960s used CFC-11 (trichlorofluoromethane)


as the principle blowing agent. The type of blowing agent used, which is retained as
vapour in the closed cells of the foam, is a major factor controlling the thermal conductivity
and such foams had conductivity values around 17 mW/m.K. With the introduction of
aromatic-based polyethers and esters, and further work adjusting formulations,
conductivities down to 15 mW/m.K were achieved and these later foams also showed
good long-term retention of the low conductivity values. Development work at that time
aimed for even further improvements in insulation to achieve satisfactory performance
from increasingly thinner, and hence more cost effective, sheets.

However, by the late 1980s, CFC-11 and CFC-12 (dichlorodifluoromethane) had been
recognised as chemicals very effective at depleting the protective ozone layer in the
atmosphere and were environmentally unacceptable. This resulted in the introduction in
1987, of the now well known Montreal Protocol in which international action was agreed
to combat the effects of these substances. The Protocol came into force in 1989 and
provided a timetable whereby, in developed countries, use of CFC would be phased out
by 1st January 1996. In Europe, this was advanced to 1st January 1995 with the adoption
of regulation EC3093/94. Since it was recognised that products like rigid PU foams
made an important environmental contribution through their insulative qualities which
reduce energy requirements and hence carbon dioxide emissions, the phase-out
arrangements were of a gradual nature with an interim period. During this time, CFC
could be replaced with ‘transitional substances’ of much reduced ozone depletion potential
(ODP) which would be phased out in the period 2003-2015, or earlier if possible.

The phase-out schedule agreed at the Montreal meeting of September 1997 for ozone
depleting substances (ODS) is shown in Table 4.5 (developed countries) and Table 4.6
(developing countries). The Annexes refer to various classes of ODS with CFC-11 and
CFC-12 in Annex A and hydrochlorofluorocarbon (HCFC) in Annex C, Group 1.

There are some exemptions for essential use but these do not include use for blowing
agents.

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consumption phase-out of ODS

Rigid Polyurethane Foams

Table 4.5 Consumption phase-out of ODS in developed countries


Date Central Measure
1st July 1989 Freeze Annex A (CFC)
1st January 1992 Freeze of halons
1st January 1993 • Annex B CFC reduced by 20% from 1989 levels
• Freeze of methyl chloroform
1st January 1994 • Annex B: CFC reduced by 75% from 1989 levels
• Annex A: CFC reduced by 75% from 1986 levels
• Halons phased out
• Methyl chloroform reduced by 50%
1st January 1995 • Methyl bromide frozen at 1991 levels
• Carbon tetrachloride reduced by 85% from 1989 levels
1st January 1996 • HBFC phased out
• Carbon tetrachloride phased out
ª Annex A and B: CFC phased out
• Methyl chloroform phased out
• HCFC frozen at 1989 level + 2.8% of 1989 consumption of
CFCs (base level)
1st January 1999 Methyl bromide reduced by 25% from 1991 levels
1st January 2001 Methyl bromide reduced by 50% from 1991 levels
1st January 2003 Methyl bromide reduced by 70% from 1991 levels
1st January 2004 HCFC reduced by 35% below base levels
1st January 2005 Methyl bromide phased out
1st January 2010 HCFC reduced by 65%
1st January 2015 HCFC reduced by 90%
1st January 2020 HCFC phased out, allowing for a service tail of 0.5% until 2030
for existing refrigerators and air conditioning equipment
HBFC: Hydro bromo fluorocarbons

Some developed countries including USA, Japan and the European Union (EU) have
brought these targets forward. The EU has agreed that from 1st January, 2003, the use
of HCFC in appliances and sandwich panels (except for insulation trucks) will be
prohibited. From 1st January, 2004, prohibition extends to HCFC in other rigid foams

63
consumption phase-out of ODS

Handbook of Polymer Foams

Table 4.6 Consumption phase-out of ODS in developing countries


Date Central Measure
1st July 1999 Freeze of Annex A CFC at 1995-1997 average levels
1st January 2002 • Freeze of halons at 1995-1997 average levels
• Freeze of methyl bromide at 1995-1998 average levels
1st January 2003 • Annex B: CFC reduced by 20% from 1998-2000 average levels
• Freeze of methyl chloroform at 1998-2000 average levels
1st January 2005 • Annex A: CFC reduced by 50% from 1995-1997 average levels
• Halons reduced by 50%
• Carbon tetrachloride reduced by 85% from 1998-2000 average
levels
• Methyl chloroform reduced by 30% from 1998-2000 average
levels
1st January 2007 • Annex A: CFC reduced by 85% from 1995-1997 average levels
• Annex B: CFC reduced by 85% from 1998-2000 average levels
1st January 2010 • CFC, Halons and CCl4 phased out
• Methyl chloroform reduced by 75% from 1998-2000 average
levels
1st January 2015 Methyl chloroform phased out
1st January 2016 Freeze of CFC at baseline figure of year 2015 average levels
1st January 2040 HCFC phased out
Source: [6]

such as spray, block and polyisocyanurate. An EU amendment to bring dates forward by


another 12 months narrowly failed.

The replacement of CFC has been the main development target of the rigid PU foam
industry since 1986, and the repercussions of this, in optimising the performance of
alternative non CFC formulations and moving away from transitional substances,
continue.

The success of work to replace CFC can be judged from Table 4.7, which shows the use
of ozone depleting substances by the European foam industry since 1986.

64
Ozone depleting substances

Rigid Polyurethane Foams

Table 4.7 Use of ozone depleting substances


by the European foam industry
Year ODP (000s weighted tonnes)
1986 63
1987 67
1988 70
1989 70
1990 69
1991 51
1992 39
1993 22
1994 4
1995 4
1996 4
1997 4
1998 4
1999 4
Derived from data in [7]

The desirable characteristics of blowing agents for rigid PU foams are well understood,
and are:

• Boiling point in the range –20 to +30 °C

• Good solubility in the foam precursors

• Poor solubility in the foam polymer

• Low thermal conductivity of gas/vapour

• Low diffusion rate of gas/vapour through the polymer (for long-term retention in the
cells)

65
Handbook of Polymer Foams

• Zero ODP

• Low flammability both as liquid and gas

• Chemically inert

Initial work on alternatives resulted in the development of so-called 50% reduced CFC-11
systems which were adopted in the late 1980s [8]. These systems were very much an
interim measure to meet the short term reductions of ODP substances specified by the
Montreal Protocol. Development to meet the longer term requirements have resulted
essentially in two types of blowing agent - HCFC (such as HCFC-141b) and hydrocarbons
(such as n-pentane). Some characteristics of these substances are shown in Table 4.8.

Table 4.8 Characteristics of some alternative blowing agents


Property CFC-11 HCFC-141b HFC-134a CO2 n-pentane cyclo-
pentane
Formula CCl3F CH3CCl2F CH2FCF3 CO2 C5H12 C5H10
Molecular weight 13 7 117 102 44 72 70
Boiling point (°C) 24 32 -26.5 - 36 49
Vapour pressure at 0.08 0.082 0.053
30 °C (MPa)
Vapour 8 9 14 15 13 11
conductivity at
20 °C (mW/m.K)
Flash point (°C) none none none none < -50 -42
Explosion limits in none 7.4-15.5 none none 1.4-7.8 1.4-8.0
air (% by volume)
TLV (ppm) 1000 500 1000 - 1000 600
ODP (cf CFC-11) 1.0 0.11 0 0 0 0
Permanency in good good good poor good good
cells
Adapted from data in [7], with permission from Rapra Technology
HFC: Hydrofluorocarbon
TLV: Threshold limit value

66
Rigid Polyurethane Foams

From Table 4.8 it may be seen that there is no ideal replacement for CFC-11. HCFC-
141b, whilst giving a very substantial reduction in ODP does not have a zero ODP factor
and the Protocol requires eventual phase-out. In addition, thermal conductivity is slightly
worse and mixtures with air are explosive (within defined limits). HFC, such as HFC-
134a, do have zero ODP and are acceptable under the Protocol (although they do have
some potential for global warming). They are non-flammable and non-explosive, but
thermal conductivity is significantly worse than CFC-11. Carbon dioxide is a very safe
gas to work with, but again has worse thermal insulation properties which are exacerbated
by the impermanence of the gas in the cells, leading to a gradual deterioration in insulation
and some dimensional stability problems. It also contributes to global warming, so is not
totally environmentally acceptable (though it may be argued that environmental
deterioration due to the use of carbon dioxide as a blowing agent is vastly outweighed
by contributions of carbon dioxide to the atmosphere from transport and energy
production). Hydrocarbons have zero ODP (and negligible global warming potential)
and hence offer a permanent solution to Protocol requirements, but they are flammable
and form explosive mixtures with air. Compared with CFC-11 there is also a significant
worsening of thermal insulation.

In addition to the intrinsic properties of alternative blowing agents and the properties
they consequently impart to the foam, effect on processing is also very important. Whereas
HCFC-141b is essentially a drop-in agent which can be run with relatively minor
adjustments on conventional machines, engineering solutions have had to be found to
introduce gases and flammable blowing agents.

Worldwide, no single blowing agent technology has been universally adopted [9]. The
phase-out of CFC has resulted in a broad diversification of rigid PU foam processes
using HCFC-141b, HCFC-22 with HCFC-142b, HFC-134a, pentane isomers and carbon
dioxide.

HCFC-141b is currently used in the manufacture of metal faced sandwich boards. Whilst
it is ‘drop-in’ technology, greater control of processing is needed and some dimensional
stability problems require higher foam densities. This technology has been in place for
some time producing foams of density 38-43 kg/m3 (continuous process) and 41-43 kg/
m3 discontinuous. This is the main technology adopted in the USA owing to the large
emphasis placed on energy conservation and the environmental penalties exacted for
units with large energy demands.

HCFC-141b has also been used for appliance insulation applications, (e.g., in the Pacific
area), where it is also a ‘drop in’ technology in terms of the foaming process. However,
the solvent effect of HCFC-141b on acrylonitrile-butadiene-styrene or high impact
polystyrene thermoplastics has required the development of special liners to prevent
cracking, resulting in extra cost. In both appliance and board insulation, the early phase-

67
Handbook of Polymer Foams

out of HCFC-141b in such countries as USA, Japan and the EU will considerably reduce
its use.

HCFC-22/142b has been used particularly in Germany and offers advantages of good
dimensional stability but with some worsening of thermal conductivity.

HFC-134a, in low amount, has been used industrially in both the continuous and discontinuous
processes. The substance is dosed into the high pressure polyol stream in continuous operations,
or used in a fully saturated polyol component in discontinuous operations.

Carbon dioxide water blown foams are also produced successfully by panel manufacturers,
with densities ranging from 43 to 48 kg/m3. The inferior long-term ageing (loss of
insulation) due to diffusion of carbon dioxide from the cells can be mitigated by use of
an impervious facing. It is claimed that with such composites, thermal conductivity remains
practically unchanged for a long time in the largest part of the panel [9]. A recent variant
is the use of liquid carbon dioxide to partially replace water. The carbon dioxide is
metered and fed in the high pressure polyol stream at a level of some 3 pbw. Some
process advantages have been described, but engineering modifications are necessary to
handle and meter the gas and the technology has not so far been used industrially for
sandwich panels due to unclear economics in comparison with all water blown technology.

The use of pentane - either n-pentane or cyclopentane - is now widespread in the European
industry for the production of metal faced rigid PU panels. Technology has been developed
to deal with the problems imposed by flammability, including membrane pumps for
dosing and static mixers for blending with the polyol stream. Strict precautions are taken
to ensure there is no build-up of explosive vapours, and continuous monitoring ensures
vapour levels are maintained below 10% of the lower explosion limit. Ignition sources
must be eliminated. With these precautions, pentane can be used safely and the first
equipment for production of pentane blown rigid PU was introduced in 1990. Pentane
may be partially emulsified (and not solubilised) in the polyol stream depending on the
amount used and its solubility in the polyol. Blends of n-pentane and methylene chloride
have also been used and have some advantage since methylene chloride in non-flammable.
However, concerns over environmental and toxicity issues have prevented any significant
use as a blowing agent.

Pentane has some advantages over other blowing agents - it has zero ODP, poor solubility
and low permeability in the PU matrix, gives acceptable foam insulation values (though
inferior to those of CFC foams) and low price. The obvious disadvantage is its
flammability. In addition to the necessity of introducing new equipment to provide
adequate operating safety there is an adverse contribution of the hydrocarbons to the
foam combustion behaviour, and inferior fire performance results. This may be combated
by the introduction of additional fire retardants or, as indicated previously, by use of

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comparative costs Rigid PU foam

Rigid Polyurethane Foams

polyisocyanurate foam chemistry, but this results in a cost penalty. Thus, the economics
of pentane blown foam versus other technologies depends on the fire classification
requirements. Some data given by Bertucelli and co-workers are shown in Table 4.9.

Cyclopentane and n-pentane (or n-i pentane blends) are sufficiently different in properties
to give rise to significant differences in processing and foam properties. Where a
homogeneous blend is preferable (discontinuous processes) cyclopentane is preferred,
and this also provides optimum thermal properties. N-pentane has lower cost and gives
a lower foam density, resulting in better foam economics.

There is significant work still ongoing in the polyurethane industry to fully replace HCFC-
141b in developed countries. Whilst pentane and carbon dioxide technologies are already
in place, neither provides the advantageous process and product characteristics given by
CFC-11. For a few years now, HFC-245fa (structure CF3-CH2-CHF2) and HFC-365mfc
(structure CF3-CH2-CF2-CH3) have been identified as the leading candidates. It has been
reported by Zipfel and co-workers [12] that whilst neither of these substances entirely
matches CFC-11, a blend of HFC-365mfc with either HFC-134a or HFC-245fa provides
a non-flammable blowing agent with good thermal insulation performance and a
convenient boiling point in the range 20-25 °C. Such a blend would provide a ‘drop-in’
replacement for HCFC-141b (and CFC-11), but is the most expensive option of those
under examination. A further possibility for the future is an azeotropic blend of HFC-
365mfc with any of the three pentane isomers (n, i, or cyclo). Although these azeotropes
are flammable, they do provide a more cost effective solution than use of HFC-365mfc
alone, and results show good thermal insulation values for foams based on such systems.
Some characteristics of these ‘third generation’ blowing agents are shown in Tables 4.10,
4.11 and 4.12.

These recent developments, which have included foaming trials, have focused attention
on the possibilities afforded by HFC-365mfc, and Solvay took a decision to develop

Table 4.9 Comparative costs of rigid PU foam


Blowing agent Comparative cost (%) of 1 m3 of foam to meet
DIN EN 1363-2 [10] DIN EN 1363-1 [11]
HCFC-141b 100 107
CO2 - water 111 114
n-Pentane 96 126
Data from [9]. Reproduced with permission of Rapra Technology

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characteristics of HFC blowing agents

Handbook of Polymer Foams

Table 4.10 Main characteristics of HFC blowing agents


Property HFC-245fa HFC-365mfc
Boiling point (°C) 15.3 40.2
Vapour pressure (MPa at 20 °C) 0.124 0.047
Vapour thermal conductivity at 25 °C 12.2 10.6
(mW/m.K)
Flash point none none
Flame limits (% by volume) none 3.5-9.0
GWP relative to CO2 = 1 820 840
GWP: Global warming potential
Reproduced with permission from [12]. Copyright Rapra Technology, 1999

Table 4.11 Main characteristics of HFC-365mfc/HFC-245fa blends


Blend ratio 50/50 95/5 93/7
Boiling point (°C) 24 37 20
Flash point none none none
Vapour thermal conductivity at 25 °C 11.4 10.7 10.8
(mW/m.K)
Reproduced with permission from [12]. Copyright Rapra Technology, 1999

Table 4.12 Main characteristics of HFC-365 mfc/pentane azeotropes


Pentane isomer cyclopentane isopentane n-pentane
HFC/pentane ratio 73/27 46/54 58/42
Boiling point (°C) 32 22.5 27
Flash point yes yes yes
Vapour thermal conductivity at 25 °C 11.1 13 13
(mW/m.K) (calculated)
Reproduced with permission from [12]. Copyright Rapra Technology, 1999

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Rigid Polyurethane Foams

production at pilot scale level with a view to making this substance available as an
HCFC-141b substitute [12].

The scenario for blowing agents over the next few years is likely to be:

The replacement of polycyclic polyisocyanates -141b in the USA by HFC-365mfc,


or a blend thereof;

The continued domination in Europe of pentane technology, as it meets Protocol


requirements and the safety problems involved with production operations have
been solved.

In Asia, a mixture of technologies, with some countries (such as China and Korea)
still relying on CFC-11. Money is being made available by the World Bank and the
United Nations Development Program to subsidise the considerable capital costs
involved in changing to flammable blowing agents. Whilst some manufacturers in
the Pacific region have made the (relatively easy) change to HCFC-141b, most are
now looking at pentane technology to comply with the Protocol and to achieve
cost reductions which are important in view of the economic turmoil in Asia. In
Japan, conversion to pentane technology is well advanced.

4.2.4 Other Additives

4.2.4.1 Catalysts

Foam catalysts have a very substantial influence on process rheology, process latitude,
dimensional stability and physical properties. They comprise:

• Tin compounds, e.g., Stannous 2-ethylhexanoate


Di-butyl tin di-laurate

• Tertiary amines, e.g., Polycat 5 (pentamethyldiethylene triamine)


Polycat 8 (dimethylcyclohexylamine)
Polycat 41 (tris-dimethylaminopropyl
hexahydrotriazine)

• Quaternary ammonium salts, e.g., Dabco TMR series

• Potassium salts, e.g., Dabco K-15 (Potassium octoate)


Polycat 46 (Potassium acetate)

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Handbook of Polymer Foams

Tin catalysts mainly promote the reaction between isocyanate and hydroxyl groups,
whilst tertiary amines promote both this and the water - isocyanate reaction. Potassium
salts catalyse the trimerisation of isocyanates to form isocyanurates. A comprehensive
list of catalysts is given in reference [13].

The main technical development in rigid PU foams has been the move away from CFC
blowing agents, but there has been substantial formulation development to support this,
and to mitigate property changes resulting from use of CFC alternatives. The main
suppliers have produced new catalysts which minimise the problems of such formulation
changes [14].

4.2.4.2 Surfactants

By reducing the surface tension of the polyol, surfactants can perform several useful
functions in foam manufacture. They can stabilise the initial liquid-air dispersion
(controlling the number of cells); they can emulsify and stabilise a blend of incompatible
reagents; and they can stabilise the rising foam. Appliance foam generally incorporates
highly functional polyols and isocyanates which results in a relatively high liquid phase
viscosity and good foam stability. The surfactant is used mainly to control cell size and
to enable blend miscibility of incompatible reagents. Surfactants commonly used, e.g.,
Dabco DC5357, are copolymers of polydimethyl siloxane and polyalkylene oxide.

In all rigid polyurethane foams the change to pentane blowing agents to replace CFC has
required surfactant development to overcome the poor solubility of pentane in the polyol
(resulting in high viscosities) and a generally higher foam density with a coarser cell
structure. Recently developed surfactants, e.g., Nitroil’s PC STAB EP 26+, are claimed to
overcome these problems, combining the properties of a foam stabiliser and pentane
compatibiliser.

4.2.4.3 Cell Openers

The normal open cell ratio in rigid polyurethane foams is 10-20% and for the main
application of thermal insulation it is advantageous to retain the blowing agent in closed
cells to maintain a low thermal conductivity. In contrast to flexible polyurethane foams,
cell opening at the end of the reaction is not required to prevent shrinkage. However,
where insulation performance is not the prime concern, cell openers are sometimes
recommended to improve dimensional stability. Whereas cell opening of flexible foams
can be achieved by mechanical crushing, with rigid foams this would result in permanent
compressive deformation. Hence, a chemical method is necessary.

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Rigid Polyurethane Foams

A cell opener for rigid foams, Dabco DC5000, has been described [15]. It is designed as
a separate additive for use with traditional silicone-polyether surfactants to allow good
formulation flexibility. The additive is incorporated in small amounts up to 0.25 parts
per hundred (pph) polyol to promote cell window rupture immediately prior to the rapid
viscosity build up as the polymeric crosslinked network is formed. It acts by replacing
the foam-producing surface film with an alternative film with little or no surface elasticity
which rapidly thins and breaks as the foam expands.

4.2.4.4 Blend Compatiblisers

One of the major limitations of hydrocarbons as blowing agents is their poor solubility
in polyol. Use of higher amounts is desirable, particularly in PIR applications, as it would
allow an improvement in reaction kinetics by the reduction or elimination of water.
Higher levels of hydrocarbon above the solubility limits can result in phase separation
during and before the foam reaction leading to foam inhomogeneity.

Goldschmidt, for example, have developed Ortegol 410 which helps to solubilise pentane
in rigid foam polyols. Using technical cyclopentane (70% cyclopentane plus mainly n
and i isomers) in a European appliance polyol system, clarity up to 11 pph pentane is
achieved without additive; with 5.0 pph of Ortegol 410, clarity was maintained up to
15 pph; at 10 pph Ortegol 410, clarity was maintained up to 18 pph pentane [16].

4.2.4.5 Glass Fibre

There are few examples of the use of non-reactive fillers in rigid polyurethane foams, but
glass fibre is one that was originally developed by Celotex Corporation. Incorporation
in PIR foams was found to give additional stability to the protective char formed in a fire
situation, hence improving fire performance to meet the USA requirements for built up
roofs. An additional benefit is a lower thermal expansion coefficient which leads to
improved durability and helps to prevent cracking when hot bitumen is poured onto
laminate panels for roofing.

4.3 Manufacturing Processes for Rigid Polyurethane Foam

The original method for production of rigid PU foam was simply to pour the foam mix
into a box mould. The product was subsequently cut to form boards, pipe shells and
other complex shapes. This method is essentially that now used for ‘pour in place’
applications such as insulative linings for refrigerators and similar appliances. Increasing

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Handbook of Polymer Foams

volumes required more economic production methods, and a continuous process for
block foam was developed, followed later by continuous lamination technology for panel
production. The latter allows efficient production of rigid PU board with different facing
materials like bituminous paper, glass fibre reinforced bitumen sheets, multi layer papers
or metal sheets.

Currently, both discontinuous and continuous processes operate for production of


laminated rigid PU panels, although the continuous process (introduced in the late 1960s)
is dominant. In a typical continuous process (CONTIMAT), galvanised steel sheets (0.5-
0.8 mm) are wound off large coils and fed through a profiling unit to provide edge and
surface profiles. Lower and upper facings pass through simultaneously and are then
preheated to the process temperature required. The reactive PU mix is dispensed onto
the lower facing using a linear application method whereby the mix head oscillates across
the entire plate width. Sophisticated control ensures uniform distribution giving expansion
only in the vertical direction, resulting in uniform density through the sheet and optimum
production output. An adjustable gap between upper and lower conveyors controls panel
thickness. Conveyor lengths are typically 20 to 30 m. Panels are cut to length some 10 m
after leaving the conveyor. Output rates of a double conveyor plant with a 30 m length
pressure zone and 1.2 m width are typically 860 m2/h (50 mm thickness) and 390 m2/h
(150 mm thickness) [17]. Output rate is directly dependent on conveyor length, being
30% lower for a length of 20 m.

The discontinuous process comprises a series of steps linked to provide a manufacturing


operation. These steps are:

• Preparation and positioning of metal sheets, either from a coil of metal or by use of
stacked sheets.

• Profiling the edge and surfaces of the sheets.

• Feeding the sheets to a multiple daylight press characterised by a central pressing


plate.

The pressing plate moves so as to close an upper mould in preparation for dispensing the
PU foam mix whilst releasing the lower mould for removal of the finished panel and
insertion of further facing sheets. Such presses may be configured, e.g., as 1+1, 2+2, 3+3
or 4+4. Optimum output of a discontinuous process is achieved when curing time and
operating time are of equal duration and when the platen area of the presses is fully
utilised. Typical output rate of a 4+4 daylight press, 6 m long, 1.2 m wide, maximum
platen area utilised, is 150 -170 m2/h (50 mm thickness) and 40 -50 m2/h (150 mm
thickness) [17].

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Rigid Polyurethane Foams

A joint cooperation between Hennecke GmbH and Bayer AG has resulted in the VarioCast
process which is claimed to not only reduce the cycle time for discontinuous panel foaming
operations but also to improve cell structure, increase dimensional stability and reduce
raw material costs by 5%. The equipment is modular, is said to give cycle time savings
up to 30% and is compatible with various blowing agents including pentane.

The continuous process has higher output rates and there is no technical limitation on
panel length (in Europe, currently up to 18 m). Foam densities are generally lower than
those of foam produced by the discontinuous process (40-45 kg/m3 versus 45-55 kg/m3).
In the discontinuous process, panel length is limited by press dimensions, but there is
greater flexibility in the use of facing materials (these may include chipboard, plywood,
or light building board, in addition to the usual steel or aluminium sheet). Cell structure
and uniformity is inferior in the discontinuous process since the distribution of reaction
mixture is non uniform and expansion occurs sideways as well as vertically. Dimensional
stability of the foam is adequate but inferior to that from the continuous process. There
is, however, more scope for sheet profiling, including ends as well as sides, which is not
feasible in the continuous system.

It is also possible to spray foam in place for insulative or sealing applications. Formulations
are required with high reactivity and low odour.

Considerable development has been carried out on rigid polyurethane foam processes in
recent years to overcome the problems imposed by the change from CFC blowing agents
to hydrocarbons. The main problem is the flammable nature of hydrocarbon blowing
agents which requires special precautions to enclose the process to ensure there is no
chance of any vapours escaping, and removing any possible source of ignition. The
necessary technology is now well developed and equipment capable of handling these
substances is now available from all the main manufacturers.

4.4 Recycling Processes for Rigid Polyurethane Foam

Whilst rigid PU foam is a stable product with a long lifetime, material for disposal can
arise when, for example, appliances are scrapped or when underground insulated pipes
are replaced. It naturally arises also from within a process from trimming and from out
of specification foam during start-up and change-over. Companies are giving increasing
attention to the problems of waste due to environmental concern and the cost of disposal.

Many companies use glycolysis to process their relatively pure PU scrap whilst other wastes
are dealt with by a mechanical process. Glycolysis turns the PU waste back into polyols for
new rigid PU slabstock production and is a process which has been used for many years.

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Handbook of Polymer Foams

In a recycling method developed by Puren Schaumstoffe [18], PU waste is mixed with


scrap PET from, for example, soft drink bottles. This has the advantage of reducing
methylene diphenylamine levels arising from MDI based PU which can reach undesirable
levels if only PU waste is used.

Contaminated waste, i.e., waste containing PU foam mixed with covering paper, mineral
wool, glass wool, aluminium sheet, etc., is first separated and pressed into briquettes
which are then granulated and transported to a mixing system. An MDI-based binder is
added and the mixture pressed at 140-160 °C at a pressure of 1-3 MPa for about 30-
60 seconds to form boards which are subsequently cut to size. The product is said to
have good mechanical properties, low heat conduction and is moisture resistant.
Thicknesses range from 5 to 60 mm and densities from 250 to 850 kg/m3. Various
construction applications are envisaged, including floor insulation and sandwich elements.
The process was sufficiently successful for Puren to decide in 1997 to build a second
plant to increase capacity.

BASF have developed a ‘second generation chemistry’ using glycolysis to recover polyols
from a variety of PU systems including rigid PU foam. Residual amine is claimed to be
less than 1%. The polyols are said to be reusable in polyisocyanurate foam, insulation
non-critical foam, structural foam, friable energy absorbing foam, low density void filling
foam, elastomeric coatings, rigid non-cellular PU, and moulded semi-rigid foam.

4.5 Properties of Rigid Polyurethane Foams

Some of the properties of rigid PU foam important in its applications are:

• High insulating capacity with low thickness

• Lightweight, with high mechanical strength

• Chemically and biologically resistant

• Durable

• Satisfies fire regulations for particular applications

• Quickly and easily processed on site. Can be sprayed in place.

Physical properties of a continuously produced pentane blown PIR (insulating panel) are
shown in Table 4.13.

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properties of Pentane blown PIR foam
Rigid Polyurethane Foams

Table 4.13 Properties of pentane blown PIR foam


Property Value
Density (kg/m3) 32
Compressive strength (MPa) - perpendicular 0.22
Compressive strength (MPa) - in belt direction 0.12
Compressive strength (MPa) - across belt 0.13
Flexural strength (MPa) 0.42
Brittleness (%) 25
DIN EN 1363-1 [11] (cm) 12
Closed cell count (%) 98
Dimensional stability (70 °C/95% RH) (%) +1.04
Thermal conductivity (mW/m.K) - initial 19.9
Thermal conductivity (mW/m.K) - after 3 months at 70 °C 23.9
Reproduced with permission from [19]. Copyright 1999, Carl Hanser Verlag

In many applications, insulation is the characteristic of most importance, and considerable


work has been done to investigate the performance of rigid foams with the newer blowing
agents, in particular their long-term performance. Predicting long-term performance from
short-term accelerated ageing tests has also received recent attention.

Some published data are shown in Table 4.14.

Analysis of gas in the cells showed the loss of blowing agent and its replacement by air
associated with the deterioration in insulation performance. Thicker foams show a slower
loss, as expected. The loss at 70 °C after 39 weeks, whilst substantial, was still less than
the value after 5 years at 23 °C.

Ball has described a method for predicting long-term (25 years) ageing values based on
measuring the increase in thermal conductivity after 25 weeks at 70 °C [7]. It is claimed
the method is satisfactory irrespective of rate of ageing and the presence of facings. This
work indicates that HCFC-141b and n-pentane blowing agents are similar to CFC-11
and CFC-12 in that a stable thermal conductivity value is reached in less than 25 years,

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Handbook of Polymer Foams

Table 4.14 Thermal conductivity of rigid PU foam boards after ageing


Blowing agent Product Thermal conductivity at 10 °C (W/m.K) after ageing at 23
thickness °C or 70 °C
6 weeks 2 years 5 years 25 weeks 39 weeks
at 23 °C at 70 °C
Pentane 40 mm 0.0237 0.0267 0.0272 0.0266 0.0266
Pentane 80 mm 0.0230 0.0252 0.0263 0.0255 0.0257
HCFC-141b 50 mm 0.0203 0.0243 0.0252 0.0229 0.0231
HCFC-141b 60 mm 0.0192 0.0247 0.0257 0.0229 0.0231
Data used [20] with permission from Rapra Technology

and this value is likely to be maintained well beyond 50 years. the predictive formulae
given by Ball for 25 year values (Æ25) are :

CFC blown Æ25 = (Æ1 - 6.5) mW / m.K


Pentane blown Æ25 = (Æ1 - 5.4) mW / m.K
HCFC-141b blown Æ25 = (Æ1 - 6.7) mW / m.K

where Æ1 is the initial value (measured after less than two days ageing for thin samples).

4.6 Applications

The two major applications for rigid PU foam are in construction and in appliances such
as household refrigerator liners.

4.6.1 Applications in Construction

In the construction industry, rigid PU foam is used both as insulating boards and panels,
and as an in situ material for sprayed-in-place insulation and as a one component bonding
foam. Boards are used in pitched and flat roofs, in suspended ceilings, in floor slabs with
or without underfloor heating, in walls for external, internal or cavity insulation (with
rendering if required) and in a wide range of buildings from multi-storey car parks to

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Rigid Polyurethane Foams

farms. Load bearing rigid sandwich panels formed by combining the rigid PU foam with
rigid wood or metal sheet facings are used for insulating roof and wall cladding. In
thicknesses greater than 100 mm, PU sandwich panels are used for cold storage facilities
and for refrigerated storage and transport. Roofs and industrial components such as
tanks or pipes may be insulated by using polyurethane spray to produce an insitu foam.
Doors and window frames can be fixed and joints sealed using one component bonding
foams.

In roof, wall, floor and ceiling applications, rigid PU foam has much in common with
polystyrene foam which is used for similar insulation applications. The insulation market,
however, is dominated by mineral or glass fibre wool which, whilst less technically
attractive, costs less as a material and more easily meets fire resistance requirements.
Some data given by Kaufung, Bayer AG, on the market share of various materials for
insulation applications [21] are shown in Table 4.15.

Table 4.15 Insulation material - Western Europe market (1995)


Material Volume (106 m3) Share (%)
Mineral wool/glass fibre wool 52.6 60.5
Phenolic foam 0.9 1.0
Rigid PU foam 6.4 7.4
Expanded polystyrene foam 24.1 27.7
Extruded polystyrene foam 3.0 3.4
Total 87 100
Data from [21]. Copyright SPI, 1997

The demand in construction has been growing and this growth is expected to continue at
a rate greater than that of the construction industry itself, in line with increasing demands
for the improved comfort provided by insulation, and the energy savings available when
insulation is used. Environmental as well as economic pressures are driving this. Weigand
[22] has examined the environmental benefits of rigid PU insulation by carrying out an
‘eco-balance’ calculation for pitched roof insulation and floor insulation. Savings in energy
used for heating during use far outweigh the environmental ‘costs’ of production and
eventual recovery. The positive environmental effect of using an appropriate level of
insulation has also been shown by Ashford [23].

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Handbook of Polymer Foams

4.6.2 Applications in the Appliance Industry

The use of rigid PU foam for refrigerator insulation is the other main application for the
material. In 1997, the consumption of PU worldwide in refrigerators was 464 tonnes,
some 40% of the amount used in construction. A breakdown given by Bayer [24] is
shown in Table 4.16.

Table 4.16 Shipments and PU consumption of refrigerators and freezers in


main world regions (1997)
Region Shipment PU consumption Share
(millions of units) (k tonnes) (%)
Europe 18.9 155 33
USA 11.5 98 21
Japan 4.8 28 6
South America and 10.7 54 12
Mexico
China 13.2 78 17
Far East and India 12.0 51 11
World Total 71.1 464 100
Data from [24]

The larger markets in Europe, North America and Japan are well developed [24] and
although there is a trend towards larger and more sophisticated appliance models to
meet customer demand, the growth of the market in these countries is small or nil.
Worldwide, these countries account for 60% of the total. The market in less developed
countries however, is not yet saturated and still shows significant growth.

Between 1993 and 1995, European refrigerator manufacturers moved away from CFC
blowing agents, mostly to cyclopentane, although HCFC-141b, HCFC-141b/HCFC-22
blend, and hydrocarbon blends have also been used. In the USA, as with rigid PU foams
for construction, HCFC-141b was the preferred blowing agent.

In Europe, whilst initially the resulting poorer performance of the non-CFC foams was
accepted (higher density and hence higher shot weight, lower insulation value), subsequent
development work has aimed to meet the overall properties of the original CFC foams.

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Rigid Polyurethane Foams

Legislation has been one of the driving forces, involving not only the Montreal Protocol,
but also regulations on the reduction of appliance energy consumption introduced by the
EU, and the voluntary Eco-Label of the EU. The key requirements for the Eco-Label are:

• Sufficient insulation for the refrigerator to be rated A or B according to the 94/2/EC


Energy Efficiency Index regulation. For an A rating, energy consumption must be
below 55% of the standard value defined by the EU directive, whilst for a B rating
energy consumption must be between 55 and 75% of this value.

• Foam blowing agent must have an ODP of zero and a GWP of no more than 15 CO2
equivalents.

The blowing agent requirements rule out both HCFC and HFC, limiting candidates to
hydrocarbons or carbon dioxide.

The appliance energy consumption regulations and the Eco-Label arrangements came
into force in 1999 (96/57/EC).

In the USA, HCFC-141b use is allowed by the US Environmental Protection Agency


(EPA) as a transition measure until energy efficient, zero ODP, replacements become
available. Formulation development has enabled such foams essentially to match the
insulation performance of the CFC foams they replace, enabling refrigerator and freezer
manufacturers to remain in compliance with US Department of Energy (DOE)
consumption regulations.

The deadline for replacing HCFC-141b in the USA was set by the US EPA as 1st January
2003. Additionally, the US DOE issued an energy consumption regulation for refrigerators
and freezers sold from July 1st 2001. This calls for up to 30% reduction in energy
consumption from the levels permitted under the 1993 regulations. The US DOE has
estimated that this will result in significant savings in primary energy consumption and a
consequent reduction in carbon dioxide emissions amounting to some 465 million tonnes
over 30 years.

In Japan, there are no regulations for energy consumption for appliances although the
importance of energy saving is well recognised in the industry and strongly supported by
the government. The saturation of the market in Japan is illustrated by the figure of
1.2 refrigerators, on average, for each Japanese household.

The growth regions of South America and South-East Asia are less advanced in both
CFC replacement and energy reduction regulations, but the technologies now available
are being put in place and Brazil, for instance, has a regulation to eliminate CFC in
household refrigerators which came into force on January lst 2001.

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Handbook of Polymer Foams

China and India are areas where the relatively low market saturation offers good market
growth potential. The change over from CFC is happening - albeit slowly as use of CFC
is still permitted under the Montreal Protocol - the trend being initially to the ‘drop-in’
HCFC systems with hydrocarbons being used in some joint venture foam plants involving
European companies.

Development trends in the industrial countries are targeted on cost reduction whilst
continuing to meet environmental legislation for blowing agents and energy consumption.
In Europe and Japan, this focuses on improving hydrocarbon blown foams either by
improving existing pentane-based systems or by development of systems based on
cyclopentane blends with various butane and/or pentane isomers. The latest systems are
claimed to match the properties of CFC-11 foams [24], having lower cabinet fill weights,
shorter demould times and improved insulation factors. This has been achieved by tailoring
the basic polyol and isocyanate materials to the requirements of the new blowing agents
formulated for use with CFC.

In the USA, HFC-245fa has been identified as the most suitable replacement for HFC-
141b in appliances. Work done by ARC and Bayer has shown that appliance insulation
made using this blowing agent has an energy consumption matching that of HCFC-141b
systems. Vacuum insulation panels are also receiving attention as this technology is able
to provide improved k factors (a measure of insulation). However, manufacturing and
installation costs are high and only a few manufacturers in USA, Europe and Japan offer
appliances with such insulation. This may change with further tightening of energy
consumption regulations.

It can be expected that development will continue so as to satisfy customer and legislative
requirements, and it will be some time before formulations world wide focus on one or
a few systems recognised as economically and environmentally optimal.

References

1. C.J. Benning, Plastic Foams: the Physics and Chemistry of Product Performance
and Process Technology, Wiley-Interscience, New York, NY, USA, 1969.

2. Polyurethane Technology, Ed., P.F. Bruins, Interscience, New York, NY, USA,
1969.

3. D. Reed, Urethanes Technology, 1999, 16, 1, 32.

4. R. Brooks, Urethanes Technology, 1999, 16, 1, 34.

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Rigid Polyurethane Foams

5. Dow Polyurethanes - Flexible Foams, 2nd Edition, Ed., R. Herrington, Dow


Chemical Company, Midland, MI, USA, 1997.

6. UNEP web site, www.unepie.org

7. G.W. Ball, A. Simpson and H. Fleming, Cellular Polymers, 1997, 16, 2, 110.

8. A. Cunningham, I.D. Rosbotham, and A.K. Thomas in Proceedings of the SPI


32nd Annual Conference, Polyurethanes ‘89, San Francisco, CA, USA, 1989,
p.522.

9. L. Bertucelli, M. Vreys, F. Pignagnoli, A. Ottens and P. Keller, Proceedings of


Utech Asia ‘99, Suntec City, Singapore, 1999, Building and Construction, Paper
No.6.

10. DIN EN 1363-2, Fire Resistance Tests - Part 2: Alternative And Additional
Procedures, 1977.

11. DIN EN 1363-3, Fire Resistance Tests - Part 1: General Requirements, 1999.

12. L. Zipfel, P. Dournal and W. Kruecke in Proceedings of Utech Asia ‘99, Suntec
City, Singapore, 1999, Building and Construction, Paper No.7.

13. K. Ashida and K. Iwasaki in Handbook of Plastic Foams: Types, Properties,


Manufacturers and Applications, Ed., A.H. Landrock, Noyes Publications, Park
Ridge, PA, USA, 1995, Chapter 2, p.30-38.

14. D.E. Eaves, Polymer Foams, Trends in Use and Technology, Rapra Technology,
Shawbury, Shrewsbury, UK, 2001.

15. K.F. Mansfield, J.W. Miller and W. Wong, Proceedings of Utech Asia ‘99, Suntec
City, Singapore, 1999, Appliance, Paper No.5.

16. G. Burkhart and M. Klincke in Proceedings of Utech Asia ‘97, Suntec City,
Singapore, 1997, Paper No.27.

17. D. Chua, Proceedings of Utech Asia ‘99, Suntec City, Singapore, Building and
Construction, Paper No.4.

18. M. Knoedgen, Urethanes Technology, 1998, 15, 6, 34.

19. H. Schmidt and E. Calgua, Kunstoffe Plast Europe, 1999, 89, 2, 36.

20. W. Albrecht and H. Zehendner, Cellular Polymers, 1997, 16, 1, 35.

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Handbook of Polymer Foams

21. R. Kaufung in Proceedings of the SPI Polyurethanes ’97 World Congress, 1997,
Amsterdam, The Netherlands, p.2.

22. E. Weigand, Insulation Journal, 1999, March/April, 11.

23. P. Ashford in Proceedings of SPI Polyurethanes World Congress ‘97, Amsterdam,


The Netherlands, p.612.

24. Urethanes Technology, 1997, 14, 4, 42.

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Flexible Polyurethane Foam

5
Flexible Polyurethane Foam

Tyler Housel

5.1 Introduction

Polymer foams that are made primarily from polyol, isocyanate and water are known as
flexible polyurethane foams (FPF). In this chapter, we will discuss both slabstock and
moulded FPF with a density of less than about 100 kg/m3. The goal is to provide a general
introduction to the chemistry, manufacturing, testing, and commercial aspects of FPF. Rigid
polyurethane foams are covered elsewhere in this book. Readers are encouraged to use the
citations to obtain more detailed information in areas of particular interest.

The earliest work on FPF was published in Germany in the 1940s [1]. A viable commercial
process was quickly developed, and within a decade there were manufacturing sites in
both Europe and North America. By the year 2000, more than three million tonnes of
FPF were produced around the globe [2]. The industry continues to grow and expand
into new markets, and foam grades are constantly being developed and improved to
meet the ever-increasing demands of the end users.

5.2 Chemistry

The solid polymer that makes up the struts and membranes of an FPF is called polyurethane
by convention, but is really much more than that. It is a polymer with ester and/or ether
bonds from the polyol portion, and urethane and urea bonds from the reactions of
isocyanate. Polyurethane foam starts out as a liquid mixture of three reactants with a
number of additives. Within a few minutes it becomes a solid network of polymer that
can have 99% of its volume filled by air. Despite the complexity of the system, the
chemistry used to describe it is actually quite simple.

Isocyanates are involved in all of the chemistry that occurs during polyurethane foam
manufacturing. The two major reactions are known as the ‘gel’ and ‘blow’ reactions.
The gel reaction takes place between isocyanate and hydroxyl groups to yield a urethane
linkage that builds molecular weight and gels the polymer. The blow reaction occurs in

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two steps and consumes one water molecule and two isocyanate groups. Water first
reacts with isocyanate to produce a carbamic acid intermediate that quickly decomposes
to give an amine and carbon dioxide. Carbon dioxide is the blowing gas which fills the
cells. The amine reacts with a second isocyanate to form a urea linkage. Both the gel and
blow reactions build molecular weight and therefore cause the polymer to gel, but the
blowing gas is only produced from the water reaction. These reactions are shown in
Figures 5.1 and 5.2.

Figure 5.1 Gel reaction

a)

b)

c)

Figure 5.2 a) Blow reaction - first stage; b) blow reaction - decomposition step;
c) blow reaction - urea formation

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Flexible Polyurethane Foam

For completeness, it must be mentioned that isocyanate will react with any active hydrogen
compound, including the urethane or urea group formed earlier. It will also react with
itself to form dimers and trimers [3]. These crosslinking reactions occur to varying degrees
in all foam systems but are generally slower than the gel and blow reactions. Rather than
consider each individually, the isocyanate index allows the formulator to account for the
minor reactions as a group. The isocyanate index is the percentage of isocyanate groups
relative to the total active hydrogen groups from water and hydroxyl in the formula.
Remember, each water molecule reacts with two isocyanates so the following formula
must be used:

Isocyanate index = equivalents isocyanate x 100 _


equivalents hydroxyl + 2 x equivalents water

An index of 100 means that there are exactly enough isocyanate groups to completely
consume the water and hydroxyl groups in the formula. This means that a foam with an
index of 110 was made with 10% extra isocyanate. There is no active isocyanate in a
cured block of foam [4], so the extra isocyanate must be consumed by the various side
reactions. Increasing the isocyanate index makes the foam stiffer, presumably because
the extra isocyanate reactions increase crosslinking in the polymer matrix. Most FPF has
an index between 90 and 110 although there are special grades outside that range.

While the chemistry is easy to describe, it becomes more complicated when considering
the number of possible permutations. In most foam systems the reactive groups include
three types of active hydrogen (primary hydroxyl, secondary hydroxyl and water) and
two types of isocyanate (hindered and unhindered). Even ignoring the minor reactions,
this gives six possible reactions that can occur, and each has a different sensitivity to
catalyst and temperature. Beyond that, the ingredients are not mutually soluble so some
groups may be more available to the isocyanate than others [5]. All of this also changes
with time as polymer is formed [6]. A skilled formulator knows how different variables
will affect the final product, but inevitably, some trial and error is used to optimise the
formula.

5.3 Starting Materials

There are five ingredients that are common to all flexible polyurethane foams: isocyanate,
polyol, water, catalyst, and surfactant. However, few formulations are actually that simple.
There are a number of other additives that can be used to improve processing, performance,
appearance, or stability of the foam. By choosing the raw materials and process conditions

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carefully, the manufacturer controls the physical properties, mechanical properties and
appearance of the foam [7].

5.3.1 Isocyanate

As previously mentioned, all of the reactive chemistry that occurs during the foam
manufacturing process involves isocyanate groups. Several isocyanates are commercially
used in the polyurethane industry, but the majority of slabstock foams (those made in
long, continuous blocks) are made with toluene diisocyanate (TDI) (see Figure 5.3). This
is a low viscosity aromatic isocyanate that has hindered and unhindered isocyanate groups
that react at different rates. The most common grade is known as TDI-80, which has an
80/20 mole ratio of the 2,4 and 2,6 isomers of TDI. TDI-65 is also popular in Europe,
but infrequently used in the rest of the world. With its higher content of the 2,6 isomer,
TDI-65 gives a stiffer foam with a more open cell structure.

Figure 5.3 Isomers of TDI

Isocyanates derived from methylene diphenyl diisocyanate (MDI) are used in both moulded
(those made in a closed mould) and slabstock [8] foams. These are also preferred for low
resilience viscoelastic foams [9]. MDI types cover a number of related chemical structures.
Pure MDI is not often used in flexible foams because it is a solid that must be used in its
molten form. Foam grade liquid MDI derivatives can be unpurified intermediates from
the pure MDI process or can be chemically modified to impart desired properties. Besides
TDI and MDI types, aliphatic isocyanates are used in a few highly specialised formulas
where light stability is an absolute necessity.

5.3.2 Polyol

In the polyurethane industry, the term polyol describes any oligomer with two or more
active hydroxyl groups that react with isocyanates during the foaming process. Flexible

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foams are normally made with polyols that have molecular weights from several hundred
to several thousand and hydroxyl functionalities from two to three. The polyol gives
flexibility to the polymer, so lower molecular weight and/or higher functionality polyols
will produce a stiffer foam.

In the foam industry, three major types of polyol are prevalent, and each has its own
advantages as shown in Table 5.1. The greater use is from polyether polyols. Most of
these start with a trifunctional initiator such as glycerine. Ethylene and propylene oxides
then react with the initiator to give polyether chains terminated with hydroxyl groups.
Moulded foams often work better with more reactive polyols, so ether polyols for moulded
foams are terminated with ethylene oxide (EO) to give more reactive primary hydroxyl groups
on the ends. These ‘EO capped’ polyethers are less commonly used in slabstock foams.

Polyester polyols are made from diacids and diols that react to give polymer chains with
repeating ester bonds. Essentially all polyester slabstock polyols are made from diethylene
glycol (DEG) and adipic acid. Glycerine or trimethyl propane (TMP) are added to the
charge to increase the hydroxyl functionality to the 2.5 to 3.0 range. Flexible moulded
polyester foams are made from adipates of short chain glycols such as DEG, ethylene
glycol and butanediol. If higher functionality is required, small amounts of TMP are
reacted into the polyol. Moulded foams are more prone to shrinkage, so these polyester
polyols rarely have functionalities above 2.5.

Copolymer polyols are normally derived from polyether polyols. They are sometimes
called polymer, graft or filled polyols [10] (note: some sources use the term ‘filled’ to
refer to polyols filled with mineral fillers only, excluding the copolymer polyols [11]).
These are primarily used to increase strength, hardness and resilience. One type of polymer
polyol uses a free radical initiator to polymerise unsaturated monomers such as styrene
and acrylonitrile (SAN polyols) that are added to a polyether polyol. The free radical

Table 5.1 Foam polyol property summary


Property Polyether polyol Polyester polyol Copolymer polyol
Viscosity low high medium

Hydrolytic stability excellent fair excellent


Oil/solvent stability fair excellent good
Strength fair excellent very good
Resilience good fair excellent

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will occasionally react with the polyether chain, grafting the polymer to the polyol. The
other main type of polymer polyols are the PHD polyols. The name comes from
‘PolyHarnstoff Dispersion’ which is German for polyurea. These are made by adding
amines and isocyanates to a polyol. The isocyanate will react much more quickly with
the amine, so they are essentially dispersions of polyurea in polyol. Either of these
techniques gives the polyol a milky appearance and causes a significant increase in viscosity.
Most copolymer polyols are based on low viscosity polyethers despite the excellent
properties of copolymer polyester polyols [12].

5.3.3 Water

Water reacts with isocyanate to produce the carbon dioxide (CO2) that eventually fills
the cells and foams the polymer. Flexible foams normally use between 1 and 6 parts of
water, with higher water levels leading to a lower density foam. The water-isocyanate
reaction is extremely exothermic, so low density water blown foams are prone to thermal
discoloration in the centre of the bun where the temperature is hottest for the longest
time. In extreme cases, it becomes dangerous to produce very low density water blown
foams as they can self ignite. For this reason, most foams below 15 kg/m3 are blown with
a combination of water and a non-reactive blowing agent. Variable pressure foaming
(VPF) is another way to produce low density foams with moderate water levels.

5.3.4 Surfactant

Surfactants (or stabilisers) are essential, multifunctional additives that make polyurethane
foam possible. These are often a combination of ingredients that serve three purposes
during the foaming process. The first role of the surfactant is to lower the surface tension
of the liquid in the mix head so that bubble nuclei can form from the available energy
[13]. These nuclei determine the size and structure of the cells in the foam. The second
role is to emulsify the water, polyol, isocyanate and additives. If the dissimilar liquid
components do not emulsify properly, large scale deformities are produced in the final
foam. As the foam rises, cell membranes form between gas bubbles, and the surfactant is
also responsible for stabilising these membranes. Yet the surfactant must also allow the
thinned membranes to rupture during the cell opening phase. This balance of stability
and instability is the key to developing a successful foam formulation.

There are many types of foam surfactants and each is usually specific to the type of
formulation being poured. For example, surfactants designed for polyester foams will
not work in polyether systems and vice versa. Within each category, different surfactants
are available depending on the density, porosity, cell structure and other properties desired.

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Flexible Polyurethane Foam

Most have a combination of emulsifying, stabilising and destabilising ingredients that


are engineered to work together. While it is possible to meter the individual components
to the mix head as separate streams, this is rarely done in practice because the surfactant
supplier blends them in the appropriate ratio.

5.3.5 Catalyst

Most FPF systems reach full rise in less than two minutes, and parts or slabs are handled
only a few minutes after that. Not only does a fast reaction improve manufacturing
efficiency, it also minimises the critical time between cell opening and strength development
that determines whether the product is good. Foams with longer reaction times are more
likely to have a poor cell structure and problems with shrinking, settling or collapse.

Isocyanates react sluggishly with water and alcohols at room temperature, so catalysts
are added to accelerate and control the rise and cure of moulded and slabstock foams.
There are several competing chemical reactions that take place during the foaming process,
and every catalyst affects each reaction differently. Nothing is completely selective, but
gel catalysts primarily speed the reaction between polyol and isocyanate, and blow
catalysts are more selective to the reaction between isocyanate and water that generates
the blowing gas. A balanced catalyst has similar activity for both reactions.

It is important to remember that the type of polyol strongly affects the catalyst requirement.
Polyether polyols with a high percentage of secondary hydroxyl groups require much
stronger gel catalysts than EO capped or polyester polyols. Catalysts also show varying
degrees of activity toward the different side reactions such as allophanate, biuret, and
isocyanurate. In rigid foams, these can be critical, but in flexible systems the side reactions
are normally ignored. Lastly, temperature affects some catalysts more strongly than others.
Delayed catalysts are commonly used in moulded foams to give fast demould times without
shortening the time to fill the mould. These become active only after the reaction exotherm
increases the temperature.

Many organometallic compounds are effective gel catalysts, the most common of which
are stannous octoate and dibutyl tin dilaurate. Recent toxicity concerns have reduced
organotin usage in Europe. Trialkyl amines such as triethylene diamine are also used as
gel catalysts although they are less selective than the organotins. Delayed gel catalysts
are usually trialkyl amine salts that will unblock at higher temperatures [14].

Blow catalysts are tertiary amines that have two carbons separating the catalytic amine
from another tertiary amine or an ether group. This structure is believed to form a complex
with water molecules that enhances their reactivity with isocyanate [15]. Bis (N, N,

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dimethylaminoethyl) ether and the structurally similar pentamethyl diethylene triamine


are widely used as strong blow catalysts. Morpholine and piperazine structures are
generally weaker and more balanced.

Successful foaming requires a balance between the gel and blow reactions. It is not possible
to make a universal balanced catalyst, but a number of catalysts are available that are
balanced for a particular system. These can be a single compound or a blend of gel and
blow components. In practice, most manufacturers use a catalyst system that somewhat
favours the blow reaction and then add minor amounts of a strong gel catalyst to allow
for daily adjustments. This is also useful for manufacturers that make several different
grades of foam because they only need a few catalysts to make many types of foam.

Reactive catalysts are frequently used to avoid volatile amine emissions. These have
reactive hydroxyl groups that enable them to become part of the chemical network.
Dimethyl ethanolamine (DMEA) is an inexpensive gel catalyst, while methyl hydroxyethyl
piperazine is a weak blowing catalyst. Triethanolamine is commonly used as a catalyst
and crosslinker in moulded foams.

5.3.6 Colorants

Natural polyurethane foam is an off-white colour that yellows over time with exposure
to air and light. Colorants are added to improve the aesthetic appeal, hide the natural
yellowing and give an easy way to tell different foam grades apart. Both pigment and
dye-based colorants are available for any type of polyurethane foam. These are usually
supplied as a concentrated liquid or paste in a low molecular weight polyol carrier.
Colorants with polyester carriers can be used for any type of foam, but polyether carriers
can cause pinholes in polyester foams. Carbon black is widely used to make different
gray and charcoal grades of foam. Most colours can be made by mixing different ratios
from a palette of 3-4 primary colours. White or blue-white pigments are sometimes used
to make white foam appear brighter and resist yellowing with age.

5.3.7 Antioxidants

Antioxidants are added to protect the colour of a slabstock foam during processing. The
foaming reactions are extremely exothermic, and the centre of a large block of foam can
reach 170 °C [16] and remain hot for many hours. Under these conditions, thermal
oxidation can yellow or ‘scorch’ the foam in the centre. Antioxidants can reduce scorch,
but if the block remains too hot for too long, any antioxidant will be overwhelmed and
scorch will still be visible. Recent work in exotherm management shows that additives

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Flexible Polyurethane Foam

can significantly reduce scorch by lowering core temperature by 25 °C [17]. At the very
least, it is important to allow space between curing foam blocks so they can cool as
quickly as possible.

5.3.8 Light Stabilisers

Most antioxidants provide only a slight benefit in keeping the foam from yellowing over
time. Light stabilisers are more effective in reducing long-term yellowing, but again they
will slow the process but not prevent it. The only sure ways to make non-discolouring
foam is to either make it black or to use an aliphatic isocyanate.

5.3.9 Flame Retardants

Some of the largest markets for flexible polyurethane foam are for furniture, bedding
and automotive parts. In these applications, the foam is required to meet strict flammability
specifications that limit the speed and extent of combustion. To meet these requirements,
the manufacturer adds flame retardants that inhibit the combustion process [18]. There
are several types of flame retardants, and each has its own benefits and drawbacks.
Further, all tend to increase density and reduce the durability and mechanical properties
of the foam. The most widely used materials are chlorinated phosphate esters such as tris
dichloro isopropyl phosphate (TDCP) and tris monochloro isopropyl phosphate (TCPP).
These are very effective in many grades of foam, but their health effects have been
questioned, and they contribute to foam discolouration (scorching) [19]. Pentabromo
diphenyl oxide gives much less scorch and is widely used in North America but is facing
a ban in some European countries because its structural similarity to polychlorinated
biphenyls may indicate long-term environmental issues [20]. Other brominated materials
are now being introduced that should have a more favourable profile [21]. Powdered
melamine is synergistic with chlorinated phosphate esters and brominated materials and
is frequently used to improve the performance of flame retarded foams, particularly to
meet Cal TB 133 [22] and BS 5852, CRIB 5 Test [23] requirements [24]. Melamine has
a favourable toxicological and environmental profile, but doesn’t work universally [25].
It requires high amounts of additive that can make the foam difficult to process [26] and
can negatively affect mechanical properties [27]. There are other flame retardant chemicals
that are used in minor amounts in FPF. These include aluminium trihydrate, ammonium
polyphosphate, antimony trioxide, barium sulfate, graphite and tribromo neopentyl glycol.

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5.3.10 Adhesion Promoters

Automotive parts are often made of vinyl with a moulded foam filling. Polyester foams
have excellent adhesion to vinyl but insufficient flow properties for this application.
Polyether foams have good flow but poor adhesion. To overcome the inadequacies of
each system, the moulder can use a polyol blend that contains small quantities of ester
polyol as an adhesion promoter to a polyether moulded foam. In this way, both flow and
bond strength are acceptable. In a similar manner, ester-ether hybrids are sometimes
used for slabstock foams designed for textile lamination. These foams are bonded to
textiles to give the strength and aesthetic appeal of the fabric with a padded feel. The
lamination process involves passing a thin sheet of foam over a flame and quickly pressing
the melted foam against the fabric. Polyester foams give a much better bond, but cannot
be used for some applications because of their long-term hydrolytic degradation. It has
been found that the lamination properties of polyether foams can be significantly improved
by adding small quantities of polyester polyols to the formula. It has been proposed that
small quantities of acid in the foam favourably affect flame bonding [28].

5.3.11 Other Additives

Polyurethane foam is naturally non-conductive, and it can build up static electricity in


certain environments. Anti-static additives help static dissipation for foams that are used
in the aircraft of electronics industries. Biocides can be added to protect foam from
bacterial or fungal attack if the foam is used where microbial growth is likely. Cell
modifiers can be used to make the foam coarser or to give the ‘double cell’ appearance of
a natural sponge. Plasticisers can be used to make softer foam. Clickability additives
allow the fabricator to cut the foam with a razor edge die without pinching the edges.
Mineral fillers increase density which can improve sound absorption, but may reduce
durability. Melamine and mineral flame retardant additives act as fillers, while phosphate
esters and brominated compounds can plasticise the foam.

5.4 The Foaming Process

FPF starts as a mixture of liquid chemicals and within a few minutes becomes a matrix of
solid polymer with a uniform, flexible, cellular structure. There are five discrete stages to
the foaming process: raw material conditioning, mixing, growth, cell opening and cure.
Distinctly different chemical and physical changes occur in each stage, and all affect the
final product.

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5.4.1 Raw Material Conditioning

A polyurethane foam manufacturer controls many of the chemical and mechanical inputs
to the process, but once the liquid leaves the mix head, chemistry and physics determine
the fate of the foaming mass. The only way to produce consistent foam is to start with
consistent raw materials. The ingredients arriving at the mix head must be at the right
temperature and should also have a certain amount of dissolved gas. If these properties
vary outside the normal range, defects may result.

The main reason for controlling temperature is that some chemical reactions are more
thermosensitive than others. The temperature affects the overall rate of reaction, and even
the relative rates. This can lead to an imbalance that changes the properties of the final
product. Viscosity also changes with temperature, and this affects flowability and mixing.

Gas molecules dissolve in polyol and isocyanate as it comes in contact with air during
transportation and storage. Dissolved gas is essential for cell nucleation in the mix head.
If raw materials are too fresh (not enough dissolved gas) insufficient nucleation can
result in a cell structure that is too coarse; conversely, old raw materials can make the
cells too fine. Most manufacturers age the major ingredients before use, and some even
monitor dissolved gas in the raw materials. Manufacturers can use vacuum or pressurised
gas [29] to reduce or increase the dissolved gas in the raw materials, particularly TDI [30].

It is important to recognise that dissolved gas in the liquid ingredients is not the same as
bubbles which are undissolved gas. Bubbles can form when pumping viscous raw materials
such as polyester polyols, or they can come from air in the raw material lines. This can
occur when a filter is changed for example. If air bubbles get into the mix head, pinholes
and other defects may result. Occasionally air is intentionally added at the mix head to
provide additional nucleation sites. This is most common when an irregular cell structure
can be beneficial (high resilience foams), or when a large number of nucleating sites must
be present as the mixture leaves the chamber (liquid carbon dioxide blown systems) [31].

5.4.2 Mixing

The mix head is where the isocyanate is mixed with water, polyol and other ingredients.
Often, some raw material streams are blended prior to entering the mixing chamber, but
once the isocyanate, polyol and water are together, the chemistry begins. The mix head
serves two critical functions: mixing the ingredients and forming the bubble nuclei that
will become cells in the foam.

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Handbook of Polymer Foams

Since the residence time in the mixing chamber is normally much less than one second, it
must be highly efficient to ensure that the liquid leaving is completely homogeneous.
After the mixing stops, dissimilar components will naturally begin to phase separate.
However, if there are unmixed regions at the outset, they will lead to large scale defects
in the foam.

Cell nucleation occurs when dissolved air cavitates into tiny bubble seeds. Tremendous
amounts of energy are required to create surface in a bulk liquid and vapourise the
dissolved gas. The mix head is the only place where sufficient energy is available for
nucleation, so the action in the mix head directly affects the number of cells in the final
foam. The manufacturer controls cell size by encouraging or inhibiting nucleation. These
examples will describe how to change the manufacturing variables to produce a finer
foam. It is possible to make a coarser foam by making the opposite change.

The most reliable way to make a finer celled foam is to decrease the pressure in the mix
head itself. Cells only nucleate in the mix head, and a low chamber pressure will make it
easier to form gas bubbles from dissolved gas. Chamber pressure is normally controlled
by the raw material pump settings and the diameter of the outlet pipe. Another way to
make finer cells is to use raw materials that have a higher concentration of dissolved gas.
These have more gas available to form nuclei, and will result in a finer foam. Surfactants
also help create fine celled foam because the energy required to nucleate a bubble is
directly proportional to the surface tension of the liquid [32]. Another way the
manufacturer can nucleate more cells is to increase the energy input. This can be done by
mixing at a higher speed [33] or by increasing the pressure of the line feeding raw materials
to the mix head. Both of these changes will increase the pressure drop in the mix head,
making it easier to cavitate cell nuclei from the available dissolved gas.

5.4.3 Growth

Cell growth begins shortly after the liquid leaves the mix head as gas diffuses out of the
liquid and begins to fill the bubble nuclei. The ambient external pressure is much lower
than the mix head pressure so the bubbles can grow easily. In the early stages, bubbles
are only a small part of the overall volume of the mixture (exception: liquid CO2 foams).
They are far apart, and remain spherical. As they grow, the cells come in contact and
must distort as they pack in three dimensions. Eventually gas will fill up to 99% of the
total volume. Regions where two bubbles converge are called walls or membranes, while
the intersections of three or more bubbles are called struts.

Foam rises because the gases that are generated are trapped inside closed cells. The
pressure inside the cells equals the external pressure plus the overpressure needed to
maintain and grow the cells against the forces of gravity, friction, surface tension, viscosity

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Flexible Polyurethane Foam

and elasticity. The overall pressure in the cells drops significantly as the liquid leaves the
pressurised mix head and will remain slightly above ambient during the free rise portion
of the reaction. In a moulded foam, the pressure rises again as the mould is filled and the
foam can no longer expand. In a free rise slabstock foam, the pressure in the cells remains
slightly above atmospheric until the cell membranes rupture and gas vents to the
atmosphere. If the stress of the expansion is too great, a large tear called a split may form
inside the block.

There are two potential sources for the blowing gas: chemically produced CO2 from the
reaction of water and isocyanate, and volatile additives otherwise known as alternative
blowing agents (ABA). Traditional ABA are low boiling compounds such as
chlorofluorohydrocarbons (CFC), hydrofluorocarbons (HFC), methylene chloride,
acetone [34] and hydrocarbons that evaporate at ambient pressure as the heat of
exothermic isocyanate reactions causes the temperature to rise. More recently, machinery
has been developed which allows the manufacturer to use liquefied CO2 as an ABA [35].
Of course, CO2 is a gas at ambient temperature and pressure, so it begins to vapourise as
soon as the material leaves the mix head and external pressure drops to ambient. These
foams form a froth that does not flow like a liquid. Therefore, they are laid on a slab conveyor
as a ribbon that expands vertically with only slight growth in the horizontal direction.

Bubbles in a liquid are thermodynamically unstable because they have a lot of surface
area and therefore high surface energy. Further, the membranes are thinned by both cell
growth and surface tension which pulls liquid from membranes into the struts. These
factors destabilise the cell walls and make it more likely that they will rupture. It is
important that cells do rupture (see Section 5.4.4), but they must remain closed through
the growth phase because the pressure of the trapped gas supports the foam and makes
it expand. This temporary stability comes from the surfactants and emulsifiers and is
aided by the increase in viscosity as the polymer gels. Surfactants lower surface tension
and reduce the surface energy needed to maintain the film. Emulsifiers prevent phase
separation of dissimilar ingredients that could disrupt thinning membranes. Viscosity
makes it more difficult for the liquid to flow, so the membrane is less likely to thin. When
the destabilising factors finally overcome the stabilising influences the membranes rupture.
Although the blow reaction will produce gas molecules for several minutes, the rise stops
when the block vents to the atmosphere. Gas molecules produced after cell opening
merely escape out of the foam.

5.4.4 Cell Opening

In a flexible foam, cell opening is essential because closed cells lead to poor mechanical
properties, low resilience and an undesirable pneumatic feel. In extreme cases, a closed
cell flexible foam will shrink. At maximum rise, the cells are filled with hot gas, but as

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the foam cools, the pressure inside drops. The membranes allow carbon dioxide to diffuse
out faster than air diffuses in [36], so this further reduces pressure in cells that remain
unopened after curing. The overall result is that a flexible foam with too many closed
cells will shrink as it cools. To prevent shrinkage, some foams (notably moulded and
high resilience slabstock types) are mechanically crushed to burst any closed cells. Rigid
foams are strong enough to maintain a partial vacuum within each cell. These can have
closed cells without shrinkage.

Cell opening presents an interesting paradox. A microscope shows that cell membranes
are often completely missing, indicating that the material had sufficient time and fluidity
to flow completely into the strut. Yet at the time of cell opening, the polymer in the struts
must be strong enough to maintain the cellular geometry and support the foam against
the pull of gravity. Before cell opening, pressure in the cells supports the weight of the
foam, but when the foam vents, the support must come from the struts. The foam will
lose height (settle or sigh back) if the struts are not strong enough to support the weight
above them.

Over the years, several mechanisms of cell opening have been proposed, and it is likely
that the exact cause of cell opening may be different in different types of foam. Probably
the most comprehensive theory [37] begins with the precipitation of urea microdomains
that signals the end of membrane stability. As this phase separation occurs, the polymer
goes through a period where it exhibits extensional thinning behaviour [38]; that is, the
viscosity drops dramatically as stress increases. If the polymer in the membrane is under
higher stress, it can flow while the unstressed struts remain intact. There are two probable
causes of this stress that will preferentially affect the membranes. One is driven by a
pressure gradient known as the Laplace force that thins the membranes of all types of
foam. The second is unique to polyurethane foams, where the precipitation of urea
probably causes a sudden increase in density of the polymer. The polymer contracts, but
the block of foam stays the same size. This gives a uniform force across the foam, but
since stress is force per unit area, the membranes feel more stress because the cross-
sectional area is less.

5.4.5 Cure

Once the cells open, the gas pressure is vented to the atmosphere. The foam is no longer
supported by pneumatic means, yet gravity continues to pull the foam downward. At
this point, the struts must have sufficient strength to support the weight of the foam or it
will sag or settle under its own weight. As discussed in Section 5.4.4, it is important to
balance the strength in the struts and instability in the membranes to control cell opening
and ultimately determine the success of the foaming process.

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As the polymer cures, the urea groups that form are attracted to each other because of
their similar polarity and hydrogen bonding. Urea phase separation begins at cell opening
and continues during the curing process. Urethane groups also phase separate as the
polymer cures, so that the final polymer has distinct urea and urethane phases [39]
dispersed in a ‘soft segment’ comprised mostly of less polar polyol chains. The urea and
urethane phases contribute hardness and dimensional stability to the polymer because
they are highly crystalline and remain intact well above room temperature. The continuous
phase is the non-crystalline soft segment. When an FPF is compressed or elongated, the
polyol chains in the soft segment can rearrange in response to the stress. Polyurethane
elasticity is a result of the hard and soft segment morphology.

It is important to recognise that although the foam achieves mechanical support after
cell opening, it is far from having fully developed properties. The temperature continues
to rise for several minutes beyond the cell opening, showing that isocyanate groups are
still reacting. Both blow and gel reactions build molecular weight and add crosslinks to
the polymer backbone. Since the cells have vented, gaseous products from the blow
reaction simply escape to the atmosphere without contributing to any further foam rise.
The mechanical properties of the foam improve as the curing reactions link together
polymer chains and the temperature subsides. Large foam blocks are usually set aside for
several hours before further processing, and final quality assurance testing is often delayed
until the next day. Moulded foams can usually demould after a few minutes, but these
also require several hours, often at elevated temperatures, to fully cure.

5.5 Manufacturing Equipment

Over the years, FPF equipment and chemicals have evolved together. Current technology
allows manufacturers to produce higher quality foams with less environmental impact
and greater economy than ever before. New foam grades are now available that could
not be made only a few years before, and that statement is likely to remain true far into
the future.

There are two main types of manufacturing equipment: slabstock machines that produce
large, continuous blocks of foam (see Figure 5.4), and moulding machines that produce
discrete parts which are cured in the shape and size of the mould. Both of these have
three main systems. The first is the tanks, pumps, and pipes that store, meter and pump
the raw materials, the second is the mix head, and the third takes the liquid pre-foam
away from the mix head and provides the space for it to rise and cure.

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Figure 5.4 Typical block of slabstock FPF


Source: Beamech

5.5.1 Storage and Delivery

Moulded foam equipment is designed to accurately dispense relatively small amounts of


liquid into each mould, so the feed tanks and delivery system are normally smaller and
less complicated than those seen in a slabstock machine. A moulder may have dozens of
machines, with each one running a few formulations. Additives are usually pre-blended
and only 2-4 streams actually enter the mix head [40]. This is very different to slabstock
machines which pour many different grades of foam. These can have twenty or more
additive streams to accommodate the different formulas, each with its own storage,
metering and delivery systems as detailed in Figure 5.5.

POLYOL ISOCYANATE

REQUIRED OPTIONAL
water fillers
catalyst flame retardants
surfactant antioxidants
colorants etc.

Figure 5.5 Schematic of slabstock mix head

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5.5.2 Mixing

Years ago, slabstock and moulded foam machines both used a traditional mix head
configuration. This is a cylindrical chamber where raw materials are introduced through
ports along the sides and the liquid is mixed with a pin mixer on a rotating shaft. This
design is ideally suited for slabstock foams because they operate continuously, but most
moulded foams require a solvent flush after every shot. As environmental regulations have
tightened, the impingement mix head was developed. This design forces together opposing
jets of the raw materials and relies on turbulence to mix. Since there is no rotating shaft, the
solvent flush is replaced by a plunger that purges the mixing chamber between shots [41].

5.5.3 Foam Rise and Cure

The most obvious difference between moulded and slabstock machines is how they handle
the liquid after it leaves the mix head. A moulded foam machine usually has many
individual moulds that are attached to a carousel. Empty moulds are carried to the mix
head, filled, closed and clamped. Most times, the mould is heated to accelerate the cure
so that it can be opened sooner and readied for the next use. The foam parts need
reasonable strength to demould, but they are often baked to complete the cure.

In most slabstock machines, the liquid from the mix head is deposited on a paper covered
conveyor with moving sides and an open top. Conventional foam machines (Figure 5.6)
pour the liquid on the paper from above and allow it to spread across the conveyor

Figure 5.6 Conventional foam being poured


Source: Beamech

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before it begins to froth. The conveyor is lowered through a series of fall plates that help
to improve the foam profile. Foam from a conventional machine generally has a very
uniform cell structure, but the blocks can have a crown in the middle because less liquid
reaches the edges of the conveyor. Several innovations have been developed to eliminate
the crown because rectangular blocks can be processed with much less cutting waste.
Manufacturers can traverse the mix head to spread the liquid better. They can also use a
device to lift the side paper while the foam is rising to raise the shoulders. With these
improvements, good conventional foam is still limited to a size of approximately 2 metres
wide and 1 metre high. Conventional equipment can also make round blocks of foam by
using a conveyor with cylindrical side walls.

A Maxfoam machine pumps the liquid into a trough that is almost as wide as the conveyor.
As more liquid is pumped in, it spills out over the top so a uniform ribbon of froth is laid
on the conveyor. In this case, the foam has a flat top because it expands in the vertical
direction without spreading horizontally. As in conventional machines, the flattest blocks
are made when fall plates lower the conveyor to nearly match the rise profile. The
Maxfoam system can produce large blocks with a good rectangular shape, but the
turbulence in the trough adversely affects cell structure.

Recently, machines have been introduced that can quickly switch between conventional
and Maxfoam configurations to improve operational flexibility [42] (see Figure 5.7).

Figure 5.7 Schematic showing conventional and Maxfoam capabilities


Source: Beamech

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5.5.4 Innovations

Equipment for large-scale polyurethane foam manufacturing has become much more
automated and sophisticated over the years, but in most cases, the difference between
machines from the 1960s and today relate to computerisation rather than the engineering
principle. All parts of the system are now more precisely controlled by a centralised
computer that can store hundreds of different formulations and allows the manufacturer
to change between foam grades with a single command [43].

The most notable equipment inventions of the past decade are VPF, CO2 as a blowing
agent and ground foam recycling. VPF and CO2 are both aimed at production of lower
density slabstock foams without the use of regulated blowing agents. For many years,
soft, safe low density foams were made by adding CFC or methylene chloride to the
formulation, but environmental regulations severely restricted these additives. Chemical
companies developed less harmful blowing agents, but most are flammable or expensive
and can still have environmental concerns. Low density, all-water blown foams are not
as soft and may be dangerous to produce because the exotherm temperature can exceed
the fire point. Rapid cooling strategies were adopted [44, 45] to reduce the fire danger, and
more recently, the equipment industry developed two elegant solutions: VPF and CO2.

The entire foam conveyor of a VPF machine is enclosed in a large vacuum chamber [46].
Foams made at reduced pressure have a lower density because the same amount of blowing
gas will fill a larger volume. Therefore, VPF machines can produce soft, low density
foams with a moderate exotherm and without blowing agents [47]. Another advantage is
that they collect and treat the toxic gases before releasing them to the atmosphere. Some
VPF machines may be operated above ambient pressure to produce unique foam grades.

Carbon dioxide blown foam technology was developed at around the same time as VPF,
and has been used extensively to make both slabstock and moulded foams. Of course,
carbon dioxide is a gas at ambient conditions, and low temperature and high pressure
are used so that it can be introduced into the mix head as a liquid [48]. CO2 remains a
liquid in the pressurised mix head, but it will vapourise as soon as the mixture exits [49].
The successful implementation of this technology required significant effort to develop
hardware that would smoothly transition the pressure to ambient without stressing the
liquid [50]. The froth leaves the mix head through a precisely engineered, narrow slot
which is almost as long as the conveyor width. The froth flows poorly, so the most of the
foam expansion should be in the vertical direction as in a Maxfoam machine.

Another recent innovation allows the manufacturer to non-cryogenically grind foam


scrap from the manufacturing process. The ultrafine powder is then used to displace
more than 20% of the virgin chemicals in the manufacture of new foam. With minor

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formulation adjustment, the resulting foam has properties equal to the original foam, so
the economics are driven by the difference between the value of scrap and the price of
chemical raw materials. The declining use of scrap foam in North American carpet cushion
has improved the economic advantage and led to its rapid adoption. As this technology
becomes more widespread, it will also allow the recycling of significant amounts of post-
consumer foams that currently end up in landfills [51].

5.6 Foam Characterisation

There are many tests used to measure the properties of FPF. The most significant methods
are formalised under ASTM D3574 [52] and D3453 [53] and BS EN ISO 1798 [54]. In
1994, the Polyurethane Foam Association (USA) published the Joint Industry Foam
Standards and Guidelines [55] which relates the test data to foam performance and
value, particularly in the furniture industry. Of course, there are many tests that are
specific to a particular customer, manufacturer or application. Some of the more important
tests are summarised in the next section.

5.6.1 Density

Density and hardness are sometimes thought to be similar, but these are completely
different properties, and surprisingly, there is only a weak relationship between them
[56]. Adding water to reduce density also increases the amount of urea in the polymer
which makes it harder. Many flame retardants increase density while softening the foam,
and copolymer polyols will stiffen the foam without affecting density.

Density is important to the performance and economics of a foam because it measures


how much of a foam is air and how much is polymer. The density is simply the mass
divided by the volume and is commonly measured in kilograms per cubic meter (kg/m3)
[57]. Most conventional grades of slabstock foams range from about 12 to 40 kg/m3.
Foams with fillers, flame retardants and copolymer or polyester polyols usually have a
higher density and range from 25 to 100 kg/m3. Flexible moulded foams can be poured
in much higher densities, but they can also go down to about 25 kg/m3 [58].

5.6.2 Hardness

Hardness is very important because most foams are used in applications where they
provide at least some type of cushioning. Therefore it is important to know how much
force is required to give a particular deflection or how much weight it can support.

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Harder foams are produced by increasing the isocyanate index, using copolymer polyols
or adding fillers [59].

High density moulded foams can be measured with a hand held durometer which has a
small indenter foot attached to a deflection spring. It measures the force required to push
the foot into the foam a known depth. The base of the durometer is only a few centimetres
across, and the deflection is just a few millimetres so it is useful for small samples but
only marginally accurate on slabstock foams.

Larger foam samples are usually measured by either the indentation force method (IFD)
[60] or the compression force deflection (CFD) [61] methods. Both tests use a large foot
(normally 325 cm2). A CFD test uses a foam block smaller than the foot. This eliminates
friction effects and allows the foam to flatten horizontally. IFD uses a large 10 cm thick
block of foam so that the circular foot is smaller than the sample. In both tests, the force
is measured at various deflections. There are many variants of this test depending on the
application. For the furniture industry, the most commonly reported values are the 25%
IFD and 65% IFD (IFD measured at 25% or 65% compression), and furniture foam is
normally specified by density and IFD.

There are also other values derived from IFD. For example the guide factor is IFD divided
by density. Compression modulus is the ratio of 65% IFD to 25% IFD. In seating
applications compression modulus is called support factor because higher values indicate
that the foam feels soft yet can support more weight without bottoming out. A hysteresis
value is calculated after running 25% IFD, 65% IFD and then a second 25% IFD on the
same piece of foam. The loss of 25% IFD after the 65% compression is the hysteresis.

5.6.3 Resilience

Resilience is measured by dropping a steel ball on a foam sample and measuring the
height of the rebound [62]. The ball rebound test is different from the hardness tests
because it indicates the instantaneous feel of the foam. The FPF industry quickly recognised
that resilience was important for many applications, and high resilience (HR) foams
were defined under ASTM D3770 [63]. Special copolymer polyols for HR foams were
introduced in the 1960s [64], and these now constitute a significant part of the overall
FPF industry. EO capped polyether polyols with modified polyisocyanates are also used
[65, 66]. More recently, low resilience foams have also gained in importance [67, 68].
These are known as viscoelastic, slow recovery or energy absorbing foams and will give
a characteristically low value on a ball rebound test. There are many ways to formulate
viscoelastic foams, although most are made with MDI. The key is to reduce polymer
elasticity around room temperature. Some techniques known to produce viscoelastic

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foams include the use of low molecular weight crosslinkers, blends of incompatible polyols,
alkoxylated alcohols, foreign polymers, plasticisers, and variations of isocyanate index [9].

In any of these tests, one must realise that foam will soften as temperature and humidity
increase [70]. In slabstock foams, hardness also varies across the height and width of the
block, and is even affected by whether the sample was cut in the horizontal or vertical
direction relative to the rise.

5.6.4 Porosity

Filtering, acoustic and gasketing applications usually require that the foam either permits
or blocks the passage of air. End users of other types of foam are not usually concerned
about porosity per se, but foam manufacturers have long known that air flow is by far
the easiest way to approximate the amount of intact cell windows in the foam, and this
affects many other important properties. Increasing porosity normally leads to better
resiliency and mechanical properties, but it is more difficult to produce high porosity,
low density foam because cell opening occurs earlier in more porous foams, so more of the
blowing gas is lost to the atmosphere. The surest way to produce foams with very high air
flow is by chemically or physically destroying all residual membranes after the foam is
cured. These reticulated foams are excellent for applications such as filtration, or liquid
delivery where membranes will interfere with the flow of air or liquid through the foam.

The traditional way to determine porosity is to measure the air flow in m3/second needed
to maintain a pressure differential of 125 Pa on a standard sized 50 mm x 50 mm x
25 mm [71] piece of foam. It is also possible to measure the pressure drop that occurs
when pulling a known volume of air through a cross sectional area of the foam. Open
celled foams give high numbers in the first method and low numbers in the second. Like
hardness, porosity can be significantly different in the horizontal and vertical directions.

5.6.5 Strength Properties

Hardness indicates the force needed to compress a foam. Tensile and tear strength measure
the force required to stretch and tear a foam respectively. Therefore, hardness is important
in cushioning, and tensile and tear strength are important when the foam is stretched in
handling or use. Tensile, tear and elongation are usually mentioned together because
they are all run on an extensometer, and differ only in the sample preparation. This
device has two jaws which hold the specimen and measure the force while slowly pulling
it apart. In principle, these measurements are the same for foams as for any other material.
The difference is that foams are not regular on a small scale, so much larger specimens

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Flexible Polyurethane Foam

must be used to compensate for the irregularity. The tensile experiment uses a classic
‘dumbbell’ or ‘dog bone’ shaped sample and measures the force per unit area (at the
narrow part of the specimen) required to break the sample. The increase in length at this
point is the elongation and is reported as a percentage of initial length [72]. Sometimes,
the force at 100% elongation is also recorded as the 100% modulus. In the foam industry,
tear strength is normally measured on a ‘split tear’ specimen. This requires a rectangular
sample with a cut down the centre. The foam is torn apart by pulling opposite sides of
the cut apart. Tear strength is the force required to continue tearing the foam. It is measured
as force per linear centimetre of the cut [73].

5.6.6 Cell Structure

Technical applications often require foams with a particular cell size or structure. It is
easy to recognise the difference between large and small cells, but it is more difficult to
agree on an exact measurement because a close look reveals the difficulty in measuring a
three dimensional cell with a ruler. Further, most cells have a slightly elongated shape.
Today, the cell size of most foams is measured by eye using a linear cell count method.
Methods that compare images of the foam to circular standards are more accurate and
less dependent on the individual running the test, but require more sophisticated equipment
[74, 75].

Cell uniformity can be even more subjective than cell size. Customers normally expect
the cells in a piece of foam to all be about the same size. Contaminants or air holes can
cause obvious non-uniformity, and can immediately turn the block to scrap. Some
applications demand a very consistent structure, but if the foam is hidden, there is
considerably more leeway. Some types of foams are intentionally contaminated to give a
consistent non-regularity to imitate the appearance of natural sea sponge. As with other
appearance issues, the manufacturer and customer usually develop an informal
understanding about what good foam looks like.

5.6.7 Environmental Stability

Stability and resistance tests are designed to determine if the foam will continue to deliver
expected performance throughout its working life. Many foams are used in environments
that can degrade foam quality. Some examples would be exposure to water [76], micro-
organisms, oil, solvents, high temperatures [77], sunlight and so on. There are many
different stability tests depending on the type of foam and its intended use. In general
they involve measuring the properties of interest, (e.g., hardness, tear strength, colour,
size) on a foam sample before and after controlled exposure to the degradative element.

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By increasing temperature or severity, it is often possible to estimate the effect of years of


ageing in a few weeks [78].

5.6.8 Fatigue

Many types of foam, such as those used in carpet cushion and seating applications are
expected to provide excellent cushioning properties for years of continuous use. Fatigue
resistance is clearly important in carpet padding, upholstered furniture and automotive
seating, but the foam thickness, compressive force, and sliding motion in each application
is quite different. Literally dozens of fatigue methods have been developed over the years
that attempt to mimic a particular end use. All dynamic fatigue tests put a foam sample
through thousands of compression cycles and measure softening and thickness loss. Some
also add a sliding or rolling element to simulate the other forces that a cushion will see in
normal use. ASTM D3574 [52] lists three fatigue methods [79]. One is a static test that
measures the decrease in force needed to maintain a constant deflection over time. The
other two are dynamic tests which either use a constant force pounding or a constant
force compression with a rolling component [80]. Generally, higher density foams perform
better in dynamic fatigue tests [81].

5.6.9 Compression Set

Compression set tests are similar to static fatigue methods except that they normally run
at much higher temperatures and can also include humidity, either as a preconditioning
step or during the test [82]. Foams can be permanently compressed to a fraction of their
original height if the temperature is high enough. These ‘felted’ foams are useful in certain
filtration or liquid delivery applications.

5.6.10 Flammability

Numerous disclaimers should precede this discussion of FPF flammability. As a general


summary, it is meant to offer an insight into the topic. The information presented herein
is believed to be factual, but the reader is warned that regulations and methods change
regularly and may not apply in a particular marketplace or geographical region. It is
presented without warranty and should only serve to direct interested readers to more
definitive sources of information. Flammability testing regulations are exceedingly
complex, with numerous governmental and private agencies imposing standards for foams
which fall under their auspices.

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Polyurethane foam flammability has been studied in great detail [83, 84]. While much
has been learned since the early days of the industry, fire is almost always accidental, so
it is impossible to predict how it will start or how it will spread. The best we can do is
come up with tests that are expected to model most likely scenarios. These include different
ignition sources, foam sizes and orientations, and may or may not include other materials
such as fabric in composite structures [25, 85]. As the industry becomes more global, a
few tests have emerged that have broad acceptance. Automotive foams are almost always
certified to MVSS 302 [86] or its near equivalent DIN or JIS standards. Furniture foams
are usually tested by California TB-117 (residential, component testing) [87] and Cal
TB-133 (public occupancy, composite testing) [21] in North America or BS 5852
(furniture) [23] and BS 7177 (mattresses) [88] in Europe [89]. It is likely that Cal TB-117
will move toward composite testing in the near future [87] to harmonise it with the
British Standard test. Other regional specifications also exist [90] including the Boston
Chair, New York Subway, and Italian Railway tests. Aircraft and other military foams
sometimes require a Military Specification (Mil Spec) test, and packaging foam normally
falls under UL94HF1 [91, 92]. As a last word, the reader is reminded that no test is
completely reliable at predicting fire performance under a particular set of conditions.

5.7 FPF Markets

The global market for FPF is estimated at over 3 million tonnes, roughly divided between
the Americas, Europe-Africa and Asia-Pacific. Of these, Asia-Pacific has shown the highest
growth rate [93]. Table 5.2 breaks down production by foam type and geography. There
are thousands of uses for FPF ranging from commodity cushioning products to highly
specialised technical foams. The transportation and furniture industries are the two largest

Table 5.2 Estimated foam production in 2001


Tonnes foam Asia-Pacific Europe-Africa Americas Global
Polyether 530,000 620,000 880,000 2,030,000
HR 90,000 180,000 140,000 410,000
Polyester 60,000 120,000 60,000 240,000
Total Slab 680,000 920,000 1,080,000 2,680,000
Moulded 270,000 380,000 330,000 980,000
Total FPF 950,000 1,300,000 1,410,000 3,660,000
Source: IAL Consultants

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consumers for FPF, and carpet cushion and packaging are also major markets [94]. While
all other foam applications only comprise approximately 10% of the foam produced,
these cover a broad range of specialty products that tend to have more stringent
requirements, and come with concomitantly higher profitability.

5.7.1 Transportation

Automotive and other transportation applications are clearly the largest markets for
moulded foam, and also use considerable amounts of slabstock foam. Automotive foams
use a higher percentage of MDI than the other markets. Within this segment, FPF is used
for seating, components (such as head and arm rests), textile lamination, gasketing,
filtration, sound absorption, and energy management. As a group, automotive foams
tend to require durability, high and low temperature resistance and hydrolytic stability.
Volatile compounds such as the antioxidant butylated hydroxy toluene (BHT) must be
eliminated from automotive foams because they can condense on the glass and cause a
hard-to-clean fog on windows [95]. These foams are often required to meet the fire
resistance of MVSS-302 [85] or other similar worldwide standards.

5.7.2 Comfort

The combined furniture and bedding industries are the largest user of slabstock foams
and also consume considerable amounts of HR foam. These industries are highly
dependent on the economy and its effect on disposable income [96]. The foams tend be
the lowest density products that give adequate support and fatigue resistance. Polymer
polyols are important here as they increase hardness and resilience without changing
density [97]. Depending on the location of the cushion, different factors contribute to
the overall perception of comfort. For example thick seat cushions and back cushions
tend to be softer, while thin seat cushions and bedding foams are usually harder. The
bedding industry is now becoming a major user of viscoelastic foams that conform to the
weight of the body and offer more uniform support [98]. Flammability is also a major
issue in furniture and bedding foams, and a number of appropriate standards may apply.

5.7.3 Carpet Cushion

Carpet cushioning foams are a North American phenomenon, as this application is almost
non-existent in the rest of the world. These can be high density prime or rebond foam. In
North America, most manufacturing remnants are recycled into carpet cushion. This

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Flexible Polyurethane Foam

process entails shredding the foam and bonding the bits together with an isocyanate
binder. This high density composite gives excellent durability, improves comfort and
reduces noise and carpet wear [99].

5.7.4 Packaging

In an industry dominated by paper products, cloth, natural materials and other foamed
polymers, FPF maintains an important position in the packaging industry. Foam is often
considered a high-end choice because it can be shaped to the contours of delicate parts
and gives good aesthetics, excellent protection and light weight. Foam hardness, resilience,
air flow [100] and sample geometry [101] all affect the cushioning properties of FPF. A
packaging engineer will choose an appropriate foam by considering the fragility of the
object, anticipated loads, weight and space requirements [102].

5.7.5 Specialty Applications

There are thousands of niche FPF products with higher technical requirements and lower
production volumes that are grouped together as the technical foams. These often require
very specific cell size or cell structure, porosity, hardness, solvent or water resistance,
diffusion properties, elongation, strength or compatibility with specific chemicals.
Technical foams are more likely to use polyester polyols because they give a uniform cell
structure and the cell size is easier to control. They are also stronger and give better
solvent resistance. They often go through one or more post processing steps to enhance
one or more of these properties. Reticulation refers to the chemical or thermal opening
of cell membranes to leave a network of polymer which will pass air with very little
resistance. Reticulated foams are commonly used in filtration. Felting is a process which
permanently compresses the foam with heat and pressure to give a densified foam that is
particularly good at wicking and transporting liquids.

5.8 Environmental Issues

In today’s world, most industries have had to answer questions about the environmental
impact of their products. The FPF industry is no exception, and despite a long history of
significant gains, there is still room for improvement. In fact, more than half of the
papers presented at the Polyurethane Foam Association (PFA) meetings since 2000 have
dealt with safety or environmental issues [103]. Many fair concerns have been raised,
while other claims are based on perception rather than science and the critics aim to try

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the industry in the court of public opinion. Often, spurious claims do more harm than
good because they distract the industry and the public from meaningful issues that could
be improved. In all, the environmental stakeholders can be divided into four groups:
plant workers, neighbours, consumers and the general public. Today, many companies
in the FPF industry adhere to Responsible Care® (registered trademark of the American
Chemistry Council) guidelines that make safety and environmental considerations an
integral part of the decision making process [104].

Plant workers are mainly concerned about the dangers they face during their working
lives. This includes acute and chronic effects of the chemicals that are used in the
manufacturing process as well as potential hazards from physical dangers such as falling
objects, cutting saws, falls, fires and other aspects of the manufacturing environment.
Workplace safety is primarily the responsibility of owners, management, and the workers
themselves. Organisations such as the Occupational Health and Safety Association,
(OSHA) in the USA, establish national safety standards for the workplace. These tend to
be stricter in developed nations. Any manufacturing site has unanticipated dangers, but
as the industry matures, the hazards become clearer and safer procedures and equipment
protect workers better. None of this is unique to the FPF industry.

The main specific hazard to FPF workers and people living near factories comes from the
vapours of isocyanates and other chemicals used in the process. In the USA, emission
standards are established by the Environmental Protection Agency (EPA) [105].
Toxicological information on any chemical should be obtained from a Materials Safety
Data Sheet (MSDS), but the industry has generally been most concerned with TDI , and
continues to study its properties [106]. A recent study in the USA showed that TDI
vapours close to the rising and curing foam occasionally exceed American Conference of
Governmental Industrial Hygienists (ACGIH)/OSHA limits, but respiratory protection
makes actual worker exposure rare [107]. New technologies more efficiently collect and
treat process gases [108-110], and a number of non-fugitive additives have been developed
[111-113]. Despite the continuing improvement in air quality both inside manufacturing
plants and in nearby areas, neighbourhood complaints have arisen. In 1997, these led to
the closure of the Trinity American Corporation’s facility in North Carolina, USA. Later,
the diisocyanate panel of the American Chemistry Council reviewed the data and
concluded that there was no scientific or legal basis for closing the plant [114].

Consumers expect products to be safe. FPF is lightweight and soft so it does not present
any physical hazards. Flammability is certainly a legitimate issue, and was discussed
earlier in Sections 5.3.9 and 5.6.10. The industry has extensively studied the potential
for toxic chemical exposure through contact with FPF. TDI has not been found in the
product, and none of the other emissions occur at concentrations that pose significant
health risks to humans under normal use conditions [115]. There is no positive evidence

112
Flexible Polyurethane Foam

that chemicals emanating from FPF harm consumers, yet advocacy groups occasionally
raise concerns. Over the past decade, use of BHT, butyl tin catalysts, volatile amines,
nonylphenol ethoxylates and various flame retardant chemicals have all been questioned,
and in all cases, the industry has found alternatives. A widely publicised report that the
suspected carcinogen toluene diamine is found in aged foam samples [116, 117] has
been shown to be the result of an analytical error [118, 119].

The FPF community has continued to develop technologies that reduce the impact of
manufacturing on the global environment. In 1987, the Montreal Protocol called for
CFC elimination by the year 2000, and this work was completed well ahead of schedule.
Other harmful ABA have also been reduced by chemical and mechanical innovations
[120]. Nearly all manufacturing trimmings are recycled into rebonded carpet cushion
foams [121].

The vast majority of foams that end up in the environment come from consumers. There
are many possible fates including litter, landfill, incineration, or recycling. Alliance for
the Polyurethane Industry (API) has shown that foams are safe in landfills. Degradation
is minimal, and they do not contaminate groundwater [122]. A study by Polyurethane
Recycle and Recovery Council (PURRC) demonstrated that municipal incineration is
also a safe and viable option for energy recovery [123]. Incineration is also recommended
by the European Isocyanate Producers Association (ISOPA) [124].

Recycling is the best option as it uses foam wastes to make new products. There is
already a large market for scrap foam as a raw material for rebonded products in North
America. European legislation is expected that will preclude disposal of FPF in landfills
and mandate recycling, particularly in automotive applications. If enacted, the amount
of scrap should significantly outpace demand for rebond. One possibility is to recycle
scrap foam by glycolysis which chemically reconstitutes it into new raw materials [125].
Another method grinds the scrap into a fine powder that can be reintroduced into foam
production, reducing the need for virgin raw materials. This technology is already used
to recycle manufacturing trimmings, and it is likely to be applied to post consumer scraps
as the equipment becomes more widespread [53].

5.9 Organisations

Four industry trade organisations are specifically dedicated to FPF. The PFA (www.pfa.org)
and the Alliance for Flexible Polyurethane Foams (AFPF), (www.afpf.com) are based in
North America. Many European countries have national FPF organisations, and the
national groups together make up Europur (www.europur.com). The fourth FPF
organisation is the Japan Urethane Foam Association (JUFA). Other trade associations

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Handbook of Polymer Foams

are involved in the FPF community as part of their broader scope, including ISOPA, API,
PURRC and International Isocyanate Institute (III).

References

1. O. Bayer, Angewandte Chemie, 1947, 59, 257.

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Flexible Polyurethane Foam

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21. T. Geran, Proceedings of the Polyurethane Foam Association Technical Program,


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22. Technical Bulletin No.133, Flammability Test Procedure for Seating Furniture for
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23. BS 5852, Methods of Test for Assessment of the Ignitability of Upholstered


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24. M. Barker, M.P. Hannaby and F.J. Lockwood, Proceedings of the SPI
Polyurethanes World Congress, Nice, France, 1991, p.628.

25. Personal discussions with Dave Kelly of William T. Burnett and Dimitri Dounis of
Hickory Springs, 2003.

26. H. Stone, Overview of the Combustibility and Testing of Filling Materials and
Fabrics for Upholstered Furniture, 1998, PFA, Wayne, NJ, USA.

27. M. Kageoka, Y. Tairaka and K. Kodama, Proceedings of the SPI Polyurethanes


World Congress, Chicago, IL, USA, 1995, p.62.

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Handbook of Polymer Foams

28. G. Howard, Proceedings of the Polyurethane Foam Association Technical


Program, Scottsdale, AZ, USA, October 1996, Paper No.1.

29. A.B. Lehnert, Proceedings of the SPI Polyurethanes World Congress, Las Vegas,
NV, USA, 1996, p.98.

30. L. Jung, Proceedings of the SPI Polyurethanes World Congress, Nice, France,
1991, p.169.

31. Personal discussion with Rob Borgogelli of Goldschmidt, 1999.

32. T. Housel, Proceedings of the Polyurethane Foam Association Technical


Program, San Diego, CA, USA, October 1999, Paper No.4.

33. R. Baumhäkel, Journal of Cellular Plastics, 1972, 8, 6, 304.

34. Hickory Springs Manufacturing Company, Proceedings of the SPI Polyurethanes


World Congress, Amsterdam, The Netherlands, 1997, p.740.

35. C. Fiorentini, M. Taverna, B. Collins, C. Greaves and T. Griffiths, Proceedings of


the Polyurethane Foam Association Technical Program, Newport, RI, USA,
October 1994, Paper No.10.

36. M. Olsson, Long-term Thermal Performance of Polyurethane Insulated District


Heating Pipes, Chalmers University of Technology, Gothenburg, Sweden, 2001,
p.33. [PhD Thesis]

37. T. Housel, Urethanes Technology, 2001, 18, 5, 40.

38. X.D. Zhang, H.T. Davis and C.W. Macosko, Journal of Cellular Plastics, 1999,
35, 5, 458.

39. J. Mertes, H. Stutz, W. Schrepp and M. Kreyenschmidt, Proceedings of the SPI


Polyurethanes World Congress, Amsterdam, The Netherlands, 1997, p.46.

40. Mixing Heads, Linden-EMB Technical sales literature, Linden Industries, Inc./
EMB, Cuyahoga Falls, OH, USA, 2002.

41. Introduction to Polyurethane Equipment, Cannon seminar, Mars, PA, USA,


1993.

42. Ultima Felxible Slabstock Foam Equipment, Beamech Ultima literature, Beamech,
Manchester, UK, 2000.

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Flexible Polyurethane Foam

43. J. Rayner, Proceedings of UTECH Asia, Suntec City, Singapore, 1999, Paper
No.2.

44. M.A. Ricciardi and D.G. Dai, Proceedings of the Polyurethane Foam Association
Technical Program, Point Clear, AL, USA, 1992, Paper No.6.

45. H. Stone, E. Reinink, S. Lichvar, G. Rusenko, W. Carlson, and C. Sikorski,


Proceedings of the Polyurethane Foam Association Technical Program, Point
Clear, AL, USA, 1992, Paper No.8.

46. R. Triolo, Proceedings of the Polyurethane Foam Association Technical Program,


Quebec City, Quebec, Canada, 1993, Paper No.10.

47. D. Ramazzotti and S. Carson, Proceedings of the SPI Polyurethanes Conference,


Boston, MA, USA, 1994, p.8.

48. M. Taverna, Proceedings of the SPI Polyurethane Expo, Las Vegas, NV, USA,
1996, p.370.

49. B. Blackwell, G. Buckley and W. Blackwell, Proceedings of UTECH Asia, Suntec


City, Singapore, 1997, Paper No.48.

50. T. Griffiths, Proceedings of the Polyurethane Foam Association Technical


Program, Salt Lake City, UT, USA, 2002, Paper No.3.

51. Personal communication with Martin Dawson of Mobius Technologies, 2003.

52. ASTM D3574, Test Methods for Flexible Cellular Materials – Slab, Bonded and
Molded Urethane Foams, 2001.

53. ASTM D3453, Standard Specification for Flexible Cellular Materials – Urethane
for Furniture and Automotive Cushioning, Bedding and Similar Applications,
2001.

54. BS EN ISO 1798, Flexible Cellular Polymeric Materials – Determination of


Tensile Strength and Elongation at Break, 2000.

55. Joint Industry Foam Standards and Guidelines, PFA, Knoxville, TN, USA, 1994.

56. Joint Industry Foam Standards and Guidelines, Section 1.0, Density Standards
and Guidelines, Polyurethane Foam Association, Knoxville, TN, 1994.

57. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test A: Density Test, 2001.

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Handbook of Polymer Foams

58. K. Usaka, M. Isobe, H. Utsumi and K. Ohkubo, Proceedings of the API


Polyurethanes World Congress, Salt Lake City, UT, 2002, p.75.

59. D.R. Gier, R.E. O’Neill, M.R. Adams, R.D. Priester, W.A. Lidy, C.G. Barnes, E.G.
Rightor and B.L. Davis, Proceedings of the SPI Polyurethanes World Congress,
Dallas, TX, 1998, p.227.

60. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test B1:Indentation Force Deflection Test –
Specified Deflection, and Test B2: Indentation residual Gage Load Test –
Specified Force, 2001.

61. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test C: Compression Force Deflection Test, 2001.

62. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test H: Resilience (Ball Rebound) Test, 2001.

63. The Furniture Industry’s Guide to Today’s Flexible Polyurethane Foam, AFPF,
USA, 1996, p.13.

64. W.C. Kuryla, F.E. Critchfield, L.W. Platt and P. Stamberger, Journal of Cellular
Plastics, 1966, 2, 2, 84.

65. D. Hicks, G. Davies, S. Spertini and P. Chaffanjon, Proceedings of UTECH 2000,


The Hague, The Netherlands, 2000, Innovations: Flexible Foam Development
Session, Paper No.3.

66. S. Murakami, K. Saiki, M. Hayashi, T. Satou and T. Fukami, Proceedings of the


API Polyurethanes Conference, Boston, MA, USA, 2000, p.281.

67. S. Narayan and A. Berube, Proceedings of the API Polyurethanes Expo,


Columbus, OH, USA, 2001, p.201.

68. P. Farkas, R. Stanciu, and L. Mendoza, Proceedings of the API Polyurethanes


Expo, Columbus, OH, USA, 2001, p.143.

69. A. Parfondry in The Polyurethanes Book, Ed. D. Randall and S. Lee, John Wiley
& Sons, New York, NY, USA, 2002, Chapter 14, p.220.

70. Joint Industry Foam Standards and Guidelines, Appendix A3.0, Temperature and
Humidity Effects on IFD, Polyurethane Foam Association, Knoxville, TN, 1994,
Section 3.1.

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Flexible Polyurethane Foam

71. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test G: Air Flow Test, 2001.

72. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test E: Tensile Test, 2001.

73. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test F: Tear Resistance Test, 2001.

74. Visiocell – A New Method to Measure the Cell Diameter of Polyuretahne Foam,
Recticel Visiocell Technical literature, Recticel, Wetteren, Belgium, 1999.

75. K.M. Lewis, I. Kijak, K.B. Reuter and J.B. Szabat, Proceedings of the SPI
Polyurethanes World Congress, Vancouver, BC, Canada, 1993, p.517.

76. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test L: Wet Heat Aging, 2001.

77. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test K: Dry Heat Aging, 2001.

78. J.T. McEvoy and R. Yamasaki, Proceedings of the API Polyurethanes Expo,
Columbus, OH, USA, 2001, p.281.

79. ASTM D3574, Standard Test Methods for Flexible Cellular Materials – Slab,
Bonded and Molded Urethane Foams, 2001.

80. Joint Industry Foam Standards and Guidelines, Section 9.0, Standards and
Guidelines for Dimensional Tolerances of Polyurethane Foam, Polyurethane
Foam Association, Knoxville, TN, 1994.

81. J.E. Knight, Proceedings of the SPI 30th Annual Technical/Marketing


Conference, Toronto, Canada, 1986, p.48

82. D3574-01, Standard Test Methods for Flexible Cellular Materials—Slab, Bonded,
and Molded Urethane Foams, Test D: Constant Deflection Compression Set Test,
2001.

83. E. Bleuel, P. Boehme, U. Rotermund, M. Reichelt and C. Seitz, Proceedings of the


API Polyurethane Conference, Salt Lake City, UT, USA, 2002, p.234.

84. B. Bastin, R. Paleja and J. Lefebvre, Proceedings of the Polyurethane Foam


Association Technical Program, Salt Lake City, UT, USA, October 2002, Paper
No.15.

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Handbook of Polymer Foams

85. J. David, Assessing the Need for a Federal Small Open Flame/Cigarette Ignition
Upholstered Furniture Flammability Standard, National Economic Research
Associates, San Francisco, CA, USA, 2001.

86. MVSS 302, Flammability of Interior Material – Passenger Cars, Multipurpose


Passenger Vehicles, Trucks and Buses, 1972.

87. Technical Bulletin No. 117, Requirements, Test Procedure and Apparatus for
Testing the Flame Retardance of Resilient Filling Materials Used in Upholstered
Furniture, California Bureau of Home Furnishings and Thermal Insulation,
North Highlands, CA, USA, 2000.

88. BS 7177, Specification for Resistance to Ignition of Mattresses, Divans and Bed
Bases, 1996.

89. InTouch, 1999, 7, 1, 4.

90. International Association of Fire Fighters & The National Association of State
Fire Marshals, Safety Alert Bulletin, 1999, 1, 1, 1.

91. UL 94HFI, Standard for Tests for Flammability of Plastic Materials for Parts in
Devices and Appliances, 1996.

92. Personal discussion with Richard Rose of Great Lakes Chemical, 2003.

93. Data provided by IAL Consultants, London, 2002.

94. End-Use Market Survey on the Polyurethane Industry in the USA, Canada and
Mexico in 2000, API, Arlington, VA, USA, 2001.

95. D.J. Grillo, T.L. Housel and F.A. Landis, Proceedings of the Polyurethane Foam
Association Technical Program, Newport, RI, October 1994, Paper No.1.

96. B. Poole, Proceedings of UTECH, 2000, The Hague, The Netherlands,


Furnishings Session, Paper No.1.

97. InTouch, 1995, 5, 1, 3.

98. L. White, Urethanes Technology, 2001, 18, 6, 22.

99. W. Wald, Proceedings of the Polyurethane Foam Association Technical Program,


Arlington, VA, USA, May 1998, Paper No.6.

100. G.L.A. Sims and D. Pentrakoon, Cellular Polymers, 1997, 16, 6, 431.

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Flexible Polyurethane Foam

101. G.L.A. Sims and J.A. Bennett, Polymer Engineering and Science, 1998, 38, 1,
134.

102. InTouch, 1996, 5, 2, 2.

103. Polyurethane Foam Association Technical Program Abstracts, May 2000 to


October 2002.

104. American Chemistry Council, Responsible Care, http://


www.americanchemistry.com/prodserv.nsf/s?readform&cbes-5hx2vj

105. Code of Federal Regulations Title 40, Parts 9 and 63, Environmental Protection
Agency, Washington, DC, USA.

106. P. Conner, Proceedings of the Polyurethane Foam Association Technical Program,


Arlington, VA, USA, May 2000, Paper No.2.

107. B. Cummings, Proceedings of the Polyurethane Foam Association Technical


Program, Salt Lake City, UT, USA, October 2002, Paper No.6.

108. R. Sack, Proceedings of the Polyurethane Foam Association Technical Program,


Salt Lake City, UT, USA, October 2002, Paper No.4.

109. C. Ecob, Proceedings of the Polyurethane Foam Association Technical Program,


Salt Lake City, UT, USA, October 2002, Paper No.5.

110. B. Blackwell, Proceedings of UTECH, 2000, The Hague, The Netherlands,


Innovations: Flexible Foam Development Session, Paper No.1.

111. R. Milian, Proceedings of the Polyurethane Foam Association Technical


Program, New Orleans, LA, USA, October 2001, Paper No.1.

112. J.G. Kniss, L.A. Mercando and M.L. Listemann, Proceedings of the Polyurethane
Foam Association Technical Program, Newport, RI, USA, October 2000, Paper
No.1.

113. E. Rister, Proceedings of the Polyurethane Foam Association Technical Program,


Arlington, VA, USA, May 2002, Paper No.3.

114. S.P. Levine, Proceedings of the Polyurethane Foam Association Technical


Program, Arlington, VA, USA, May 2001, Paper No.5.

115. L. Peters, Europur Presentation, Helsingor, Denmark, June 1996, Slides 17


and18.

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Handbook of Polymer Foams

116. E. Okumus, Arbetarskydd, February 19th, 1999, 6.

117. M. Dalene, G. Skarping and P. Lind, American Industrial Hygiene Association


Journal, 1997, 58, 8, 587.

118. K. Hall, F.A.L. van Parys and R.J. Young, Plastics, Rubber and Composites,
2001, 30, 9, 426.

119. K. Hillier, D. King, A. Kronborg-Hansen and T. Schupp, Cellular Polymers,


2001, 20, 4, 279.

120. InTouch, 1997, 6, 2, 2.

121. InTouch, 1994, 4, 1, 3.

122. F. Lichtenberg, Proceedings of the Polyurethane Foam Association Technical


Program, May 2002, Arlington, VA, USA, Paper No.2.

123. Sustainability, PURRC Pamphlet, PURRC, New York, NY, USA, 1997. http://
www.utm.edu/~moo/purrc/advanced.html

124. There are a Variety of Ways to Recycle Polyurethane, API Pamphlet, Arlington,
VA, USA. http://www.polyurethane.org/polyurethane_recycling/
how_poly_recycled/purrc2.html

125. S.H. Shin, J.H. Chun and B.S. Tae, Proceedings of the SPI Polyurethanes World
Congress, Las Vegas, NV, USA, 1996, p.77.

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Rigid PVC Foam

6
Rigid PVC Foam

Noreen L. Thomas

6.1 Introduction

Rigid polyvinyl chloride (PVC) foam (flexible PVC Foam is covered in Chapter 7 of this
book) was first produced some thirty years ago, when it was heralded as ‘the wood of
the future’ [1, 2]. Now this material has a well-established market in Western Europe of
about 300 ktonnes. The product range covers diverse applications such as window sills,
sewer pipes and advertising boards. The reasons for the success of this material are its
ability to compete with wood and also the benefits that it offers over solid PVC.

Many of the applications for extruded PVC foam profile (in the density range 500 to
800 kg/m3) are for wood-replacement products. It can be sawn, nailed or screwed without
splitting or cracking, thus allowing use of woodworking methods. Foamed extrudates
can be produced to resemble wood in terms of structure, colour and appearance. Hence
rigid PVC foam profile is often used as a direct substitute for wood. This is being driven
[3] by environmental pressure to protect forests, the rising price of timber and the
advantages of a maintenance-free product. On a cost/volume basis PVC foam is more
expensive than wood but becomes more cost effective when wood finishing operations
are taken into account. PVC foam can be extruded into complex shapes (some of which
are not possible with wood) without the finishing operations and scrap associated with
the manufacture of wood trim.

In addition PVC foam offers the following advantages over wood [4, 5]: chemical
resistance, good weatherability, (i.e., does not rot), good fire retardancy (Class B1, based
on DIN 4102 [6]), and resistance to infestation by vermin. The main obstacles to its use
are its reduced toughness and higher cost compared with wood.

Apart from its success as a replacement for wood, rigid PVC foam is also being used to
replace solid PVC. This is because foamed PVC provides a number of advantages over
the solid polymer. Firstly, foaming gives a lower cost per unit volume of product, which
in today’s highly competitive and cost conscious environment is a very important
consideration. The economics of extruding foamed versus solid PVC are examined by

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Handbook of Polymer Foams

Patterson and Hughes [7] and also by Dobrowsky [8]. Other benefits of foaming [4, 9]
are lower thermal conductivity (hence improved insulation), reduced thermal expansion,
improved acoustic damping properties, higher stiffness (due to increased cross-sectional
area for a given weight) and improved resistance to wind-load.

There are three major markets for rigid PVC foam: profile, sheet and pipe. Within Western
Europe the current sizes of these sectors are estimated to be 60, 50 and 180 ktonnes,
respectively. These markets are regional, reflecting the disparate preferences in building
design and differences in building regulations throughout Europe. For example, the UK
is by far the largest market for foam profile, whereas foam sheet is predominantly produced
in Germany, with additional production in Switzerland, UK and Eire. The most important
market for foam pipe has always been France, although now significant quantities are
also manufactured and used in Germany, the Netherlands and Spain, with some production
in Switzerland and the UK.

As discussed previously, rigid PVC foam profile is mainly produced for wood-replacement
products [5]. These are used in both weathering (exterior) and non-weathering (interior)
applications. Examples of weathering applications include cladding, soffit boards, roofing
products, windowsills and door-frames. Examples of non-weathering applications are
skirting boards, cornices, wall and ceiling panelling, curtain rails, guide rails for shutters,
coving and furniture profiles.

PVC foam sheet is used in a variety of applications [5, 10] including display panels,
signs, advertising boards, partition panels, building panels, garage door panels, table
tops and shelves. It is used as the core material of sandwich structures in boat building,
and for tanks and refrigerated vehicle bodies. PVC foam sheet is suitable for printing,
painting and silk-screening. Sheets can be thermoformed, even after printing, and this
opens up an even wider range of possible applications.

Foam core pipe is used in applications in which there is no internal pressure [5, 11].
Products include drain pipes, sewer pipes, effluent discharge pipes, ventilation ducts,
cable conduits and winding cores for textiles and paper. Apart from its considerable
market share in Europe, it also enjoys widespread use in other countries, such as the
USA, Australia and China [8].

6.2 Foam Extrusion

The principal method for the production of PVC foam profile, sheet and pipe is extrusion.
The cellular structure is generated by the decomposition of chemical blowing agents
(CBA), which are organic or inorganic compounds that decompose on heating to evolve

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Rigid PVC Foam

one or more gases. Physical blowing agents (PBA), which are gases or low boiling point
liquids, are not widely used in the production of rigid PVC foam.

6.2.1 Basic Principles

The basic principles for the extrusion of polymer foams were first elucidated by Hansen
[12, 13] and have also been discussed by Han [14] and Gale [15].

Gas is introduced into the molten polymer in the extruder barrel either by thermal
decomposition of CBA or by direct injection of PBA. The principles involved are similar
for both types of blowing agent because the gaseous decomposition products from the
CBA are generated within the extruder barrel and dissolve in the molten polymer.
Dissolution is possible because of the high melt pressure within the extruder.

To achieve an optimum foaming operation it is essential that bubble nucleation is delayed


until the polymer melt emerges from the die. Hence high pressure must be maintained
throughout the barrel and die to keep the gas in solution. This requires appropriate
screw and die design, as well as good temperature control. By lowering the die temperature
both melt viscosity and pressure are raised, and this will suppress any undesirable,
premature foaming.

When the melt exits the die, the rapid drop in pressure causes the polymer to become
supersaturated with gas. Phase separation occurs and almost instantaneous nucleation
of bubbles takes place. Bubbles will nucleate at irregularities in the polymer melt such as
CBA solid residues, pigments, fillers, etc. The growth rate of the bubbles is rapid at first
and then decreases as the pressure within them diminishes. Bubble growth is also retarded
as the polymer cools down and its viscosity increases. To prevent the foam structure
from collapsing, it is essential to cool the material very rapidly. This is done by passing
the foam through a chilled calibration unit so that the cellular structure is rapidly ‘frozen’
into place. The surface quality, density and thickness of the outer skin are all influenced by
the distance between the die and the calibration unit as well as the intensity of the cooling.

Many aspects of the foam morphology are controlled by the formulation used. These are
discussed in detail in Section 6.3. Cell size and uniformity depend critically on the amount
and type of chemical blowing agent. A uniform, closed, fine cell structure is desirable for
most applications. Cell size is also a function of the rheological properties of the polymer. If
the polymer viscosity is too high, then the bubbles will not be able to expand fully, and it will
not be possible to achieve a low density foam. If the polymer viscosity and melt strength are
too low, the cells will rupture and/or collapse. In the case of PVC, melt strength is determined
by the molecular weight of the polymer and by the use of acrylic processing aids.

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Handbook of Polymer Foams

6.2.2 Extrusion Processes

Rigid PVC foam is processed from dry blend on parallel or conical, contra-rotating,
twin-screw extruders. These are basically the same machines as used for producing solid
product with some differences in screw design [5]. The big difference in foam extrusion
is in the die and calibration systems used.

There are essentially two methods of foaming [5, 9, 11, 16], described as the free-foaming
and Celuka methods. The free-foaming method is illustrated in Figure 6.1. The polymer
melt is allowed to expand freely after exiting the die, prior to entering the calibration
system, which is situated a short distance away. The extrudate has an even foam density
distribution across its thickness and a thin higher density skin (Figure 6.2). This process
can be used to produce pipe, sheet and simple profiles.

The free-foam method is the preferred process for the extrusion of rigid PVC foam sheet
[17]. Product thicknesses can be obtained between 2 and 20 mm and widths from 1 to
2 metres. Typical throughput rates are in the range 200 to 600 kg/h. Special temperature
controlled die lips can be used to give different processing temperatures for the upper
and lower lips of the die. A 3-roll polishing stack is used for calibration and cooling. The
free-foam process offers several advantages over the Celuka method for sheet extrusion.
The lines are more flexible and do not require new dies and calibrator modifications
every time that the sheet thickness is changed. This gives a simpler production process
with less investment cost.

Figure 6.3 is a scanning electron micrograph of a cross-section through the thickness of


a sample of PVC foam sheet made by the free-foam process. This foam has an average
density of 600 kg/m3 and shows a fine, even, closed cell morphology.

Figure 6.1 Schematic diagram of free-foaming method


Redrawn with permission from G. Beckmann, Proceedings of the PRI PVC ’87
Conference, Brighton, UK, 1987, Paper No.13, Figure 1. Copyright 1987, Institute of
Materials

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Rigid PVC Foam

Figure 6.2 Density distribution across thickness of free-foam product


Redrawn with permission from G. Beckmann, Proceedings of the PRI PVC ’87
Conference, Brighton, UK, 1987, Paper No.13, Figure 3. Copyright 1987, Institute of
Materials

Figure 6.3 Scanning electron micrograph of cross-section through free-foam sheet

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The Celuka process is also known as the inward-foaming method. The calibration unit
is situated adjacent to the die and has the same dimensions as the die, thus controlling
foam expansion. This set-up gives very rapid cooling. Bubble formation is quenched in
the surface of the product and a solid outer skin is produced. The die contains a mandrel
[18], which controls melt pressure decay and allows the melt to foam freely inside the
profile (Figure 6.4).

The density distribution across the thickness of the Celuka foam profile (see Figure 6.5)
is quite different from that produced from the free-foaming process. There is a solid
outer skin, usually about 0.5 mm thick, and a lower density core. The outer surfaces of
Celuka products are the same as those of solid extrusions, whereas free-foam products
have a rougher, more textured surface finish. The Celuka method is used for making
pipes, sheet and profiles of complex geometries.

Figure 6.6 is a scanning electron micrograph of a cross-section through a Celuka foam


profile. This foam has the same average density as that pictured in Figure 6.3, (i.e.,
600 kg/m3) but has a coarser cell structure because of differences in formulation (see
Section 6.3). The solid Celuka skin, which is formed by quenching of the melt against
the chilled calibrator surface, can be seen on the right hand side of this micrograph. Also
to the left of the centre of the picture is a vertical line corresponding to the join between
the two melt streams that have been separated by the mandrel in the die. This line lies
midway through the thickness of the profile and corresponds to the dip in density shown
at the centre of Figure 6.5. It is very important that the two melt streams become properly
fused: otherwise a plane of weakness will exist at the centre of the profile.

Figure 6.4 Schematic diagram of Celuka method


Redrawn with permission from G. Beckmann, Proceedings of the PRI PVC ’87
Conference, Brighton, UK, 1987, Paper No.13, Figure 2. Copyright 1987, Institute of
Materials

128
Rigid PVC Foam

Figure 6.5 Density distribution across thickness of Celuka product


Redrawn with permission from G. Beckmann, Proceedings of the PRI PVC ’87 Conference,
Brighton, UK, 1987, Paper No.13, Figure 4. Copyright 1987, Institute of Materials

Figure 6.6 Scanning electron micrograph of a cross section through a Celuka profile

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Handbook of Polymer Foams

The advantages of the Celuka process are that the solid skin gives a product with a
harder surface, better appearance, improved impact properties and higher stiffness. Also
this process can be used for making profiles with complex shapes, which would be very
difficult by the free-foam method.

Another important process, which is now widely used, is co-extrusion of a surface layer
of solid PVC over the foamed product. This can be used to produce harder, glossier
surfaces or different colours. It also has the advantage that unpigmented and/or recycled
material can be used in the foamed core. The co-extruder, which can be single or twin-
screw, feeds material to form the compact outer skin to an outer die with the same shape
as the desired profile [5]. Co-extrusion can be used in conjunction with either Celuka or
free-foam processes.

An example of a profile produced by co-extruding a skin over a Celuka foam profile is


illustrated schematically in Figure 6.7. This is co-extruded foam cladding with a skin
covering the top surface. Obviously the co-extruded skin is only required on the surface
exposed when the product is in use. Figure 6.8 is a scanning electron micrograph showing a
cross-section through co-extruded foam profile, which has an overall density of 500 kg/m3.

In the production of foam core pipe, co-extrusion is used to produce the solid skin on
both exterior and interior surfaces [8, 19]. Either one or two co-extruders may be used
[20, 21]. When only one co-extruder is used, the gelled skin material is fed into the die
where it is divided into two concentric layers between which the core material is supplied
[21, 22]. Other systems involve the use of two co-extruders to feed inner and outer skins
[21]. Proponents of the latter, while acknowledging the additional capital outlay required,
claim that there is better control over outer and inner skin thicknesses and improved
weld line strength between the layers [20, 21]. No special downstream equipment is

Figure 6.7 Schematic diagram of co-extruded foam cladding

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Rigid PVC Foam

Figure 6.8 Scanning electron micrograph of a section through a co-extruded foam


profile

required, but because foam core pipe is a better thermal insulator than solid PVC (and is
therefore harder to cool), it may be necessary to install longer water tanks than those
normally used for cooling solid PVC pipes.

6.2.3 Effect of Processing Conditions

The choice of processing conditions plays a critical role in determining foam morphology
and density - and hence the physical and mechanical properties of the product. The heat
and shear imparted to the material will determine the rate of decomposition of the blowing
agent, melt viscosity of the polymer and the degree of gelation of the polymer.

Kim and co-workers [23] have shown that foam density generally decreases with increasing
extrusion temperature up to a certain optimum temperature and thereafter begins to
rise. Similar observations have been made by Rabinovitch and co-workers [24]. The
explanation is that at low temperatures the foaming process is inefficient because of high
polymer melt viscosity coupled with low gas pressure. Foaming efficiency improves with
increasing temperature but above the optimum temperature range density begins to rise
because too low a melt viscosity causes cell rupture and collapse.

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The effect of volumetric flow rate has also been studied by Kim and co-workers [23], who
found that foam density decreased with increasing extrusion rate. This was attributed to
better mixing and reduced viscosity. Thomas and co-workers [25] have also investigated
how foam density is affected by extrusion screw speed. They reported that foam density
decreased by 24% as the screw speed was increased from 6 to 14 rpm and thereafter
remained constant (see Figure 6.9). At the highest screw speed investigated (18 rpm) there
was evidence of cell collapse and so an intermediate screw speed was recommended.
Rabinovitch and co-workers [24] also found that for very high screw speeds there is a
substantial increase in foam density due to cell collapse and attributed this to shear heating.

Brenis [26] investigated a number of processing variables and concluded that the most
influential in controlling foam density were the front cylinder zone temperatures, screw
temperature and screw speed. Other variables such as adapter, flange and die temperatures
had less effect on density but were more influential over surface finish: running with
these temperatures lower produced a smoother surface skin. Work by Thomas and co-
workers [25] has also confirmed that the front barrel zone temperatures have the greatest
effect on foam density.

Figure 6.9 Effect of screw speed on foam density [25]

6.3 Foam Formulation Technology

As in all PVC applications, the formulations for the production of foamed PVC are a
complex mixture of thermal stabilisers, lubricants, processing aid, pigment and filler, in
addition to the blowing agents required to produce the cellular structure. The type of

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Rigid PVC Foam

PVC and formulation ingredients control the thermal stability, gelation behaviour, powder
flow characteristics, melt viscosity and melt strength of the material during the production
process. Hence all the components of the formulation will influence the subsequent foam
density, surface finish and overall properties of the foam [3] and there may be interactions
between individual ingredients.

6.3.1 Blowing Agents

6.3.1.1 Chemical Blowing Agents

There are many criteria for the choice of a suitable chemical blowing agent [27]. Obviously
it is essential that decomposition takes place within the processing temperature range of
the polymer. In the case of rigid PVC foam, this processing window is between 160 °C
and 190 °C. The blowing agent should not decompose too quickly, but should have a
high gas yield and be economical to use. It requires good long-term storage stability and
ease of incorporation and dispersion in the polymer. It should have the ability to produce
a fine, even cell structure and a stable foam that is not prone to collapse. The decomposition
products should be compatible with the polymer and not have an adverse effect on its
processing characteristics or thermal stability. Furthermore, both the blowing agent and
its decomposition products should be non-toxic and ‘environmentally friendly’.
Unfortunately there is no perfect candidate that can meet all these requirements. The
blowing agents most commonly used in the production of rigid PVC foam are
azodicarbonamide (ADC) and sodium bicarbonate (SBC), and they are often used together
because of synergism.

ADC is widely used in the plastics industry, particularly in the production of PVC plastisol
foams. It has the structure H2N-CO-N=N-CO-NH2 and decomposes exothermically at
about 215 °C to give a gas yield of 220 cm3 [5]. The major gaseous decomposition
product is nitrogen, which constitutes about 60% by volume of the gases evolved. Other
gaseous products are CO2, CO and NH3. The relative amounts of these depends on the
decomposition mechanism of ADC, which varies as a function of environmental factors,
such as pH [27, 28, 29]. Although the decomposition temperature of ADC lies outside
the processing window of rigid PVC foam, there are numerous activators or kickers [30]
that can lower the decomposition temperature into the required range. Some examples
of these are zinc and lead salts, which are also added as thermal stabilisers for PVC [29,
31]. A blowing agent that is sometimes mixed with ADC to act as a kicker is
oxybisbenzenesulfonyl hydrazide (OBSH) [32]. It decomposes in the temperature range
150 to 160 °C and evolves nitrogen and water vapour. The extent to which the
decomposition temperature of ADC is reduced depends on the ratio of ADC to OBSH in

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Handbook of Polymer Foams

the mixture. Work is still underway to find new kickers for ADC and thereby obtain
better control of the foaming process [33].

One of the main advantages of using ADC is that it is a very efficient blowing agent. This
is illustrated in Figure 6.10 [34], which shows how the foam density of an extruded free-
foam strip varies with the concentration of ADC in the formulation. There is a sharp
decrease in density from 1400 to 500 kg/m3 as the ADC level is increased from zero to
about 0.5 parts per hundred parts of PVC (phr). The density then stays constant and
eventually begins to rise as the ADC concentration is further increased. The explanation
for this phenomenon is that with increasing levels of blowing agent above an optimum
amount the cells begin to collapse and coalesce [3, 35].

In summary, ADC is a highly efficient exothermic blowing agent, which gives a high rate
of gas expansion and a fine, uniform cell structure [34, 36] - as illustrated in Figure 6.3.
Its disadvantages are that it can cause cell collapse if used in too high a concentration
and may give yellowish foams. Also it is classed as an irritant and may cause allergic
respiratory reactions.

SBC is a well-known blowing agent because of its use in baking powder. Its decomposition
is endothermic and reversible and takes place over a wide temperature range, which
fortunately coincides with the processing window for rigid PVC foam. The decomposition

Figure 6.10 Effect of ADC concentration on foam density [34]

134
Rigid PVC Foam

products are CO2, H2O and Na2CO3 and the gas yield is 125 cm3. Compared with ADC,
its decomposition has been described as slow and erratic [36].

SBC is a less efficient blowing agent than ADC. The effect of increasing levels of SBC on
the density of extruded free-foam strip was investigated [34] and the results are shown in
Figure 6.11. There is an almost linear relationship between increasing SBC concentration
and decreasing foam density: cell collapse was not detected in these experiments. To
produce a foam with a density of 500 kg/m3 it was necessary to use 2 phr of SBC,
compared with 0.5 phr of ADC (Figure 6.10). Also the foams produced using SBC had a
coarse, irregular cell structure [34, 37].

In summary, SBC decomposes over a wide temperature range, the reaction does not go
to completion and the gas yield and pressure are relatively low compared with those of
ADC. The cell structure tends to be coarse and irregular, which can lead to inferior
impact properties (see Section 6.4). However, previous problems of variable gas yields
and poor dispersion, caused by the hygroscopic nature of SBC, have largely been overcome
with current products, which are coated with oil or wax [30]. The advantages of SBC are
that it is easier to handle than ADC, produces a whiter foam and is less prone to give
problems with cell collapse.

Figure 6.11 Effect of SBC concentration on foam density [34]

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Handbook of Polymer Foams

Bearing in mind the complementary properties of the two blowing agents, it is not
surprising to find synergistic effects when they are used together. Combined use of ADC
and SBC has been reported to give better control of extrudate density, product colour
and processability [36]. Overall it is possible to obtain a lower density foam which is less
prone to cell collapse. This is illustrated in Figure 6.12, which shows a 3-D plot of foam
density as a function of the levels of ADC and SBC in the formulation. It can be seen that
the lowest density foams are produced using a combination of the two blowing agents.

Another advantage of using a combination of ADC and SBC is that a finer cell structure
is achieved than can be obtained with SBC alone [38]. It seems that nitrogen produced
from the decomposition of ADC readily nucleates bubbles and these act as nucleation
sites for CO2 bubbles from the decomposition of SBC. The propensity for nitrogen bubbles
to form more readily than carbon dioxide may be explained by the fact that the solubility
of nitrogen in PVC is 20 times lower than that of carbon dioxide [39].

The optimum ratio of ADC:SBC depends on the application and the processing method
used [40]. For rigid PVC profiles, which are generally produced by the Celuka process, a
high level of SBC is used with a low level of ADC, which acts as a ‘nucleating agent’ to
ensure a reasonably fine cell structure. Foam sheet is largely produced by the free-foam
process and here it is found that formulations with a high concentration of SBC give a
poor surface finish. Hence the best systems for this application are mixtures of exothermic
blowing agents either without SBC or with a low level. Similarly for foam core pipe the
blowing agent is mainly exothermic with a small amount of SBC, if any.

Figure 6.12 Effect of combined use of ADC and SBC on foam density [34]

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Rigid PVC Foam

6.3.1.2 Physical Blowing Agents

Physical blowing agents are rarely used in the extrusion of foamed PVC. However, the
question arises as to why not use direct gassing of carbon dioxide and nitrogen to replace
chemical blowing agents: these gases are said to be a factor of ten cheaper when used
from cylinders than when obtained from CBA [15].

In fact there was a widespread attempt to use CO2 in thermoplastic foam extrusion [41],
but it is difficult to get the same product quality as achieved with other blowing agents -
both in terms of surface finish and foam consistency. There are problems in delivering
the gas to the extruder and sealing the extruder to prevent gas leaking back through the
hopper. Nitrogen gas is also used as a blowing agent, but to a lesser extent than carbon
dioxide: it is said to be more difficult to work with than CO2. However, in the longer
term, the use of inert gases may be the way forward for physical blowing agents in foam
extrusion.

Gale [15] has described experiments using carbon dioxide, nitrogen and argon as blowing
agents for foam extrusion. Carbon dioxide was found to give the best results and was
used in further trials of both commodity and engineering polymers [42]. A standard
extruder was used with retrofitted parts, including a cavity transfer mixer to mix the
CO2 as a supercritical fluid into the polymer melt. The experiments were successful and
it was concluded that the commercialisation of direct gas injection of CO2 may depend
on capital costs and plant responsibilities for handling high pressure gas as much as any
other technical issue.

In terms of PVC extrusion, Dey and co-workers [43] have reported a novel method of
extruding high density, rigid PVC foam using a commercial PVC compound with inert
gas PBA (CO2 or argon). The process was developed on a segmented single screw extruder
with L/D ratio of 40. Gas was injected into the barrel through a nozzle in a Dynisco type
port. An electronic gas-pressure controller was used to regulate the gas injection pressure,
and the mass flow rate of the blowing agent was monitored with a Matheson gas flow
meter. Using this set-up they were able to produce free foam rods with densities of the
same order as currently produced by conventional technology using chemical blowing
agents. It was difficult to get a fine foam structure with CO2 but there was an improvement
when talc was added as a nucleating agent.

Direct gas injection of CO2 and N2 is also being used in the emerging technology of
microcellular foam extrusion [44, 45] - see Section 6.5.2.

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6.3.2 Processing Aids

Processing aids, based on acrylic copolymers of relatively high molecular weight, are
widely used in PVC extrusion processes to promote fusion, enhance surface finish, and
increase melt extensibility and strength [46, 47]. In formulations for rigid PVC foam
there is no doubt that processing aid is a key ingredient [10, 48, 49]: the improvement
conferred in both melt elasticity and strength prevents collapse of the cellular structure.

The importance of the molecular weight of the processing aid was first demonstrated by
the work of Ide and Okano [50]. They showed that the tendency for foam density to
increase at high concentrations of blowing agent was arrested if a high molecular weight
processing aid was used. With increasing molecular weight, it was possible to achieve
progressively lower foam densities before cell collapse took place. This result was
confirmed by Pfennig and Ross [35]. Choice of higher molecular weight processing aid
also gives foams with improved surface appearance [47].

The effect of processing aid concentration on foam density has been examined by
Szamborski and Pfennig [10]. They found that for both tin and lead stabilised PVC foam
sheet formulations, increasing the concentration of processing aid up to 8 phr gave
significant density reductions. Surface finish was also improved.

The influences of both concentration and molecular weight of processing aid on the
density of extruded free-foam strip are shown in Figure 6.13 [51]. It can be seen that for
all processing aids there is a reduction in foam density as the addition level is increased
from 4 to 8 phr, although the effect is less evident at high molecular weights. The corollary
is that a desired improvement in melt strength may be achieved either by use of high
molecular weight or by high level of processing aid.

Measurements carried out using an elongational rheometer have confirmed that melt
extensibility and rupture stress are increased with increasing addition level and/or
molecular weight of processing aid [51].

The important relationship between processing aid and blowing agent, established by
the work of Ide and Okano [50] and Pfennig and Ross [35], is a key factor in the
formulation technology of PVC foam. It is important to get the right balance between
these ingredients to avoid cell collapse on the one hand and unnecessary use of too much
processing aid on the other. This relationship is illustrated in the 2-D contour plot of
Figure 6.14 [34], which shows foam density as a function of the level of both blowing
agent and processing aid. At processing aid levels of 3 phr and below, the lines of constant
foam density run parallel to the blowing agent axis. Hence, increasing blowing agent has
no effect on foam density because cell collapse takes place. However, in the bottom right

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Rigid PVC Foam

Figure 6.13 Effect of processing aid molecular weight and level on foam density [51]

Figure 6.14 Two dimensional contour plot showing effect of concentration of blowing
agent and processing aid on foam density [34]

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Handbook of Polymer Foams

hand corner of the plot the lines of constant foam density run parallel to the processing
aid axis, showing that density reduction cannot be achieved with high levels of processing
aid if there is insufficient blowing agent.

6.3.3 Type of PVC

The molecular weight of PVC is usually expressed in terms of K-value, which is a measure
of the solution viscosity of the polymer. This is the most important parameter determining
the suitability of PVC for foam extrusion. Too low a K-value gives a low melt strength,
so that the foam will easily rupture and/or collapse. Too high a K-value gives a highly
viscous melt, so that bubbles are unable to expand fully. In both cases the result is a high
density foam.

Patterson and Szamborski [3] have examined the effect of PVC K-value on foam density.
They compared resins of K-values 51, 57, 60, 66 and 68, and found that the lowest foam
densities were produced with K57 and K60 resins.

It is generally recognised that the best PVC for rigid foam is suspension or mass polymer
with a K-value in the range K56 - K62. Higher K-value resins (in the range K65 to K68)
are sometimes used for the production of foam core pipe [8]. In this case, melt extensibility
is improved by the use of processing aid.

6.3.4 Stabilisers

Stabilisers perform a dual role in PVC foam formulations: they prevent thermal
degradation of the polymer and function as activators for the decomposition of ADC
[29, 30, 31]. Lead and zinc stearates are particularly effective in the latter respect. Lead
stabilisers are widely used in foam formulations in Western Europe for both profiles and
pipes. They are relatively cheap, have a lubricating effect and give a wide processing
window. Calcium/zinc formulations have a small share of the foam profile market. They
offer advantages over lead because of their lower toxicity, but they are more expensive
and provide a smaller processing window.

Organotin stabilisers can be divided into two types: mercaptides and carboxylates. The
majority of tin stabilisers used are mercaptides. They are excellent heat stabilisers but
give poor weatherability and do not have a kicking action on ADC. Hence formulations
based on tin mercaptide, which are used for the majority of non-weathering foam sheet
products, require ‘kickers’ for ADC decomposition: otherwise a low gas yield will result
[3, 9, 31].

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Rigid PVC Foam

Tin carboxylates are more expensive than tin mercaptides but offer excellent weathering
properties and do act as ‘kickers’ for ADC decomposition [52]. These stabilisers are a
good choice for free-foam sheets for outdoor applications, (e.g., advertising boards or
garage door panels).

6.3.5 Lubricants

Lubricants are essential ingredients in any PVC formulation because of their role in controlling
gelation, melt viscosity, flow and surface finish. In the foaming process it is important that
the PVC blend gels early enough in the extruder so that gaseous decomposition products
from the CBA can dissolve in the melt and are not drawn off in the vent or even lost back up
the hopper. Also it is essential to generate enough shear to decompose the blowing agent.
However, too much shear heating will cause cell collapse. Hence a balance of internal
(compatible) and external (incompatible) lubricants is required [5, 9]. Decker [53] has
demonstrated that the type of lubricant not only affects the ease of processing, but also
determines the effectiveness of the blowing agent and hence the final density of the product.

6.3.6 Typical Formulations

The majority of the rigid PVC foam profile produced in Western Europe is lead-stabilised
and a typical formulation is given in Table 6.1 [25]. This formulation serves as a guide:
it requires tailoring for the particular extruder and product in question. Levels and/or

Table 6.1 Guideline lead-stabilised formulation for rigid PVC foam profile
[25]
Ingredient Parts per hundred parts of polymer (phr)
PVC resin - K57 100
Lead stabiliser 3-4
Lead co-stabiliser and lubricant 0.4-0.6
Lubricants (internal and external) 1.0-2.0
Acrylic processing aid 5-8
Blowing agent (SBC and ADC) 1.5-2.5
Titanium dioxide pigment 1-5
Filler (calcium carbonate) 4-8

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type of stabiliser, pigment and filler should be adjusted depending on whether the foam
is co-extruded and whether the product is intended for outdoor use.

Table 6.2 shows a typical formulation for PVC free-foam sheet [5, 10, 49]. The same
considerations as discussed previously apply in terms of adjustment of the formulation
to the process and product. In particular, the choice of tin stabiliser as well as the level
and type of pigment should be governed by the weathering properties required of the
finished product.

A typical formulation for foam core pipe is given in Table 6.3 [5, 8]. To reduce costs, the
maximum amount of filler and minimum amount of processing aid are used commensurate
with the properties required in the final product.

Table 6.2 Guideline tin-stabilised formulation for rigid PVC foam sheet
Ingredient Parts per hundred parts of polymer (phr)
PVC - resin (K57 - K60) 100
Tin stabiliser 1.0-2.0
Epoxy compound (co-stabiliser) 1.0-2.0
Lubricants (internal and external) 1.5-2.5
Acrylic processing aid 6-10
Blowing agent (ADC) 0.4-0.8
Titanium dioxide pigment 1-5
Filler (calcium carbonate) 4-8

Table 6.3 Guideline lead-stabilised formulation for PVC foam core pipe
Ingredient Parts per hundred parts of polymer (phr)
PVC - resin (K65 - K68) 10 0
Lead stabiliser and co-stabiliser 2-3
Lubricants (internal and external) 0.8-1.5
Processing aid 3-6
Blowing agent (ADC) 0.5-0.7
Filler (calcium carbonate) 5-12

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Rigid PVC Foam

6.4 Properties

The rapid growth in the market for rigid PVC foam products in recent years has been
due to the benefits that these materials offer over both wood and solid PVC. Some obvious
advantages of foamed PVC over wood are good weatherability, improved chemical
resistance, good fire retardancy and excellent resistance to attack by vermin [4, 5]. Over
solid PVC, the advantages of foaming are a lower cost per unit volume of product,
higher stiffness for the same weight of material, better acoustic damping properties,
improved resistance to wind load, lower thermal conductivity and lower thermal
expansion [7, 8, 9]. A comparison of the thermal expansion and thermal conductivity
coefficients of PVC foam versus solid PVC are given in Table 6.4, showing the reduction
produced on foaming.

Also included in Table 6.4 is a comparison of the mechanical properties of foamed and
solid unplasticised (PVC-U), together with the test methods used for their measurement.
It is found that, in common with all other materials, the mechanical properties of the
foamed products are reduced in comparison with their solid counterparts. However, it is
clear that the method of foaming influences the properties of the material produced. For
example, although the Celuka profile has a lower density than the free-foam board, it
has a considerably higher impact strength and hardness, due to the integral skin generated
in the Celuka process.

The characteristics of a foam that determine its mechanical properties [62] are: foam
density (including density distribution through the product thickness), skin integrity and
thickness, surface texture, and cell morphology, (i.e., cell size and uniformity). However,
according to studies of a large number of different polymer foams over a wide range of
densities [63], the single most important factor controlling the mechanical properties of
foamed materials is the relative density (Ø), i.e., the ratio of the average foam density to
the density of the solid material.

Throne [64] has reported results of mechanical properties of a number of thermoplastic


structural foams (which did not include PVC) over a relative density range of 1.0 to 0.5.
Many properties, such as tensile strength, compressive modulus, shear modulus, fatigue
strength and creep strength, were found to obey an empirical square law relationship
with relative foam density as expressed by the equation:

X = Xo.Ø2 (6.1)

where X is the mechanical property of the foamed product and Xo is the mechanical
property of the unfoamed material. Young’s modulus of thermoplastic foams [62] has
also been shown to depend on the square of the relative density (Equation 6.1).

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144
Table 6.4 Comparison of properties of foamed and solid PVC (Reproduced from [16] with permission)
Property Test method Units Values
Free foam Celuka profile Solid
profile 120 x 3 140 x 10 mm
mm skin = 0.5 mm
Handbook of Polymer Foams

Density @ 23 °C DIN 53420 [54] kg/m3 600 550 1,400


Coefficient of linear VDE 0304 K-1 0.50 x 10-4 0.54 x 10-4 0.70 x 10-4
thermal expansion @ 20 °C
Thermal conductivity DIN 52612 [55] W/mK 0.062 0.062 0.16
Impact strength @ 23 °C DIN EN ISO 179 [56] kJ/m2 12 25 no failure
Foamed Solid PVC

Tensile stress at yield DIN EN ISO 527-1 and MPa 17.5 17 58


527-2 [57, 58]
Tensile stress at break DIN EN ISO 527-1 and MPa 16 15 35
527-2 [57, 58]
Elongation to break % 40 30 27.5
Shore D hardness DIN 53505 [59] - 50 80 80
Modulus of elasticity ISO 178 [60] MPa 1,200 1,200 3,050
Vicat softening temperature DIN EN ISO 306 [61] °C 63 67 78
Rigid PVC Foam

Flexural properties [64] were found to fit the expression:

X = Xo.Ø3/2 (6.2)

or for samples with carefully controlled skin thicknesses and high foam density the linear
law of mixtures gave the best fit, as shown in Equation 6.3.

X = Xo.Ø (6.3)

Data [11, 16, 65] for the mechanical properties of rigid PVC foams do not appear to
follow the square law relationship. Tensile strength data more nearly fit a law of mixtures
(Equation 6.3), whereas flexural properties gave a better fit to Equation 6.2. Yield stress
and Young’s modulus data fall somewhere between the values predicted from Equations 6.2
and 6.3, presumably depending on other morphological features in addition to average
foam density. For example, density distribution and skin thickness are particularly important
in determining flexural properties, Young’s modulus and creep behaviour [62].

Impact behaviour is an important feature of rigid PVC foams. However, there appears to
be no theoretical or empirical relationship to describe adequately the impact characteristics
of thermoplastic structural foams. The main factors affecting impact properties are overall
thickness, foam density and skin thickness [62]. The solid skin is important to eliminate
crack-initiation caused by bubbles acting as stress raisers in the surface. A fine, even cell
structure will improve impact properties. With this type of foam morphology, surface
texture is minimised and the risk of crack initiation from coarse bubbles at the surface is
reduced: where crack propagation does occur, it will be much more localised. Hence the
method of fabrication and choice of blowing agent level and type are all key factors in
determining the impact strength of the foamed product.

6.5 Novel Processes and Applications

6.5.1 Recycling

PVC has been the subject of much environmental debate and scrutiny over recent decades,
covering many aspects of its lifecycle. One particular criticism is that PVC cannot be
recycled. However, this is not the case: PVC is a thermoplastic polymer and like other
thermoplastics it can be reground and reprocessed into new products.

One of the advantages of producing co-extruded foam profile or pipe is the opportunity
that it provides to use recycled material in the foamed core. The recyclate may be industrial

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scrap recovered from pipe production [7] or foam production processes, or it may be
material recovered after consumer use.

There have been a number of initiatives to use post-consumer PVC recyclate in co-extruded
foamed products [66]. For example, in 1990 the PVC pipe manufacturers in the Netherlands,
under the auspices of the FKS (the Dutch Federation of Plastic Pipe System Manufacturers),
addressed the problem of collecting and using waste PVC pipes and fittings [67]. These
materials are now used in the co-extrusion of non-pressure sewage pipe. The skin layers
are of virgin PVC and the middle layer consists of recycled material from the collected
waste. The middle layer may be compact or foamed depending on the end-use of the pipe.
Another successful initiative has been the collection of PVC bottles in France for use in the
foamed core of three-layer pipe [68]. It has also been demonstrated that recycled PVC
packaging is suitable for use as the foamed core in co-extruded cellular profiles [69, 70].

6.5.2 Microcellular Foam

Microcellular foams are dealt with in detail in Chapter 10 of this book. Development of
this technology with respect to rigid PVC is discussed below.

Microcellular foams are a novel type of thermoplastic foam with an average cell size of
about 10 μm. Relative densities can vary from 0.1 to 0.95 and the bubble density from
108 to 1011 bubbles per cm3 [71]. The concept of microcellular foams was devised by Suh
of the Massachusetts Institute of Technology in the early 1980s [72] with a view to
reducing material costs of mass produced plastic items. The idea was that if bubbles with
a smaller diameter than the critical flaws already present in the polymer could be
introduced in sufficient numbers, it would be possible to reduce the density without
sacrificing mechanical properties. These novel materials were believed to have the potential
to revolutionise the way that thermoplastics are used.

The key feature about microcellular foams is that homogeneous nucleation is required to
produce the very large number of small cells. Homogeneous nucleation will occur when
there is a large thermodynamic instability due to a sudden drop in gas solubility: this is
induced by creating a rapid pressure drop during processing [73]. Commercial production of
microcellular foams is now underway. The technology is known as the MuCell process and
is available for both injection moulding and extrusion [74, 75]. The gas is delivered to the
system in the form of a supercritical fluid. The process consists of essentially three stages:

(i) Production of a polymer/supercritical fluid mixture,

(ii) Formation of a single phase polymer/supercritical fluid solution, and

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Rigid PVC Foam

(iii) Inducement of thermodynamic instability to produce homogeneous nucleation and


hence a foamed material with a large number of micro-voids.

The MuCell process for PVC [44] has been successfully demonstrated on a variety of
different extruders: single screw, counter-rotating twin screw and a tandem arrangement
in which a counter-rotating twin screw feeds a single screw extruder. At present all the
extrusion applications under development have very low wall thicknesses. High output
extrusion processes producing profiles of small cross-sectional area are preferred because
under these conditions there is a large pressure drop at the die exit, which is an essential
criterion to achieve the very small cell size. Standard PVC formulations can be run [44,
45, 76], although some adjustment to the lubrication is necessary to improve the gloss.

6.5.3 Foamed Composites

Linear and crosslinked low density PVC foams are used as core materials in composite
sandwich structures [77, 78]. These composites are made for applications such as the
hulls of catamarans and door assembly units for recreational vehicles. The structure
must be optimised for stiffness, strength, weight and cost. The properties that dominate
the choice of the foamed core are shear strength and shear modulus. Compressive strength
is also important. Although crosslinked PVC has better mechanical properties than linear
PVC for a given density, linear PVC foam has excellent thermoforming properties and is
the preferred material for fabrication into complex shapes.

6.6 Summary

There is growing demand for rigid PVC foam in both Europe and the USA in the three
market sectors of profile, sheet and foam core pipe. Many of the applications for PVC
foam profile are for wood-replacement products because of its ease of fabrication and
the advantages of a maintenance-free product. Foam core pipe is taking a growing share
of the non-pressure pipe market because of its cost effectiveness, higher stiffness for a
given weight and facility for the incorporation of recycled material.

In order to make a product with the minimum weight for the required stiffness, strength and
impact performance, it is necessary to control several aspects of the foam morphology. The
most significant properties are foam density and skin thickness, although cell size distribution
and surface finish are also influential. The means of controlling these factors are threefold.
Firstly, there is the choice of processing method, which can be either free-foam or Celuka
with the option of co-extrusion. Secondly, the processing conditions play an important role
in determining foam morphology and density. The third element is the formulation.

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Perhaps more so than for other thermoplastic structural foams, there is a complex
formulation technology involved in the production of rigid PVC foam products.
Formulations contain a mixture of processing aid, thermal stabilisers, lubricants, pigment
and filler in addition to the blowing agents required to produce the foamed structure.
The type of PVC and other ingredients in the formulation control the powder flow,
gelation behaviour, thermal stability, melt rheology and melt strength of the material
during the production process, and have an important effect on the properties of the
end-product.

The formulation and process technology of rigid PVC foam have been well researched.
These materials offer the attraction of providing optimum stiffness and strength for the
minimum weight of material. Hence, there is a constant drive towards novel applications
for PVC foam and also towards new ways of foaming solid products to improve cost
effectiveness.

References

1. R.J. Nightingale, Europlastics Monthly, 1974, 47, 14.

2. Plastics, Rubber and Textiles, 1970, 1, 485.

3. J. Patterson and G. Szamborski, Journal of Vinyl and Additive Technology, 1995,


1, 148.

4. E.C. Szamborski and T.E. Buterbaugh, Plastics in Building Construction, 1993,


18, 7.

5. H.P. Schneider in Plastics Extrusion Technology, 2nd Edition, Ed., F. Hensen,


Hanser Publishers, Munich, Germany, 1997, Chapter 13, 435.

6. DIN 4102, Fire Behaviour of Building Materials and Components.

7. J. Patterson and R. Hughes, Proceedings of Vinyl Retec ‘97: Plastic Systems for
the Building Industry, Atlanta, GA, USA, 1997, 91.

8. J. Dobrowsky, Kunststoffe Plast Europe, 1998, 88, 5, 15.

9. P.S. Schipper, J. Black and T. Dymek, Journal of Vinyl and Additive Technology,
1996, 2, 304.

10. G. Szamborski and J-L. Pfennig, Journal of Vinyl Technology, 1992, 14, 105.

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11. R. Brathun and P. Zingsheim in Handbook of Polymeric Foams and Foam


Technology, Eds., D. Klempner and K.C. Frisch, Hanser Publishers, Munich,
Germany, 1991, Chapter 10, 243.

12. R.H. Hansen and W.M. Martin, Journal of Polymer Science, Part B, 1965, 3,
325.

13. R.H. Hansen, SPE Journal, 1962, 18, 77.

14. C.D. Han, Y.W. Kim and K.D. Malhotra, Journal of Applied Polymer Science,
1976, 20, 1583.

15. M. Gale, Proceedings of Blowing Agent Systems: Formulations and Processes,


Rapra Technology Ltd., Shrewsbury, UK, 1998, Paper No.6.

16. G. Beckmann, Proceedings of the PRI PVC ’87 Conference, Brighton, UK, 1987,
Paper No.13.

17. Plastics News International, March 1998, 8.

18. P.E. Boutillier, inventor; Kuhlmann Ets, assignee; FP 1,498,620, 1967.

19. Plastics News International, March 1998, 16.

20. M. O’Neill, Modern Plastics International, 1997, 27, 1, 54.

21. A. Odell, Jr, Proceedings of Vinyl Retec ’91, Applying 90s Technology to Vinyl,
Fort Michell, KY, USA, 1991, 113.

22. M. Doucat, inventor; Societe Generale de Canalisations (SOGECAN), assignee;


EP 19564, 1980.

23. B.C. Kim, K.U. Kim and S.I. Hong, Polymer (Korea), 1986, 10, 215.

24. E.B. Rabinovitch, J.D. Isner, J.A. Sidor and D.J. Wiedl, Proceedings of SPE
ANTEC ’97, Toronto, Canada, 1997, Volume III, 3554.

25. N.L. Thomas, R.P. Eastup and T. Roberts, Plastics and Rubber and Composites
Processing and Applications, 1994, 22, 115.

26. K.L. Brenis, Proceedings of the 32nd SPE Annual Technical Conference, ANTEC
’74, San Francisco, CA, USA, 1974, 692.

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27. H. Hurnik in Plastics Additives Handbook: Stabilisers, Processing Aids,


Plasticisers, Fillers, Reinforcements, Colorants for Thermoplastics, Ed., R.
Gächter and H. Müller, Hanser Publishers, Munich, Germany, 1985, 619.

28. R.A. Marshall, Journal of Vinyl Technology, 1991, 13, 144.

29. R.J. Shute, Proceedings of SPE RETEC PVC Primer, Atlanta, GA, USA, 1985,
99.

30. K. Collington, Proceedings of Cellular Polymers I, Rapra Technology Ltd.,


Shrewsbury, UK, 1991, Paper No.22.

31. C.F. Tu, Proceedings of SPE ANTEC ’77, Montreal, Canada, 1977, 211.

32. G.L.A. Sims and C.O’Connor, Proceedings of Blowing Agent Systems:


Formulations and Processes, Rapra Technology Ltd., Shrewsbury, UK, 1998,
Paper No.2.

33. S. Girois and C.A. Bertelo, Proceedings of SPE Vinyl Retec ‘97: Plastic Systems
for the Building Industry, Atlanta, GA, USA, 1997, 107.

34. N.L. Thomas, R.P. Eastup and J.P. Quirk, Plastics, Rubber and Composites:
Processing and Applications, 1997, 26, 47.

35. J-L. Pfennig and M. Ross, Proceedings of PVC ‘90, PRI, Brighton, UK, 1990,
Paper No.21.

36. K.U. Kim, T.S. Park and B.C. Kim, Journal of Polymer Engineering, 1986, 7, 1.

37. B.C. Kim, K.U. Kim and S.I. Hong, Polymer (Korea), 1986, 10, 143.

38. N.L. Thomas and R.J. Harvey, Journal of Vinyl and Additive Technology, 1999,
5, 63.

39. D.W.V. Krevelen, Properties of Polymers: their Correlation with Chemical


Structure; their Numerical Estimation and Prediction from Additive Group
Contributors, 3rd Edition, Elsevier, Amsterdam, 1990, Chapter 18.

40. G. Luebke, Proceedings of Blowing Agent Systems: Formulations and Processes,


Rapra Technology Ltd., Shrewsbury, UK, 1998, Paper No.11.

41. D. Stover, Plastics World, 1994, 52, 7, 33.

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Rigid PVC Foam

42. M. Gale, British Plastics and Rubber, 2000, May, 4.

43. S.K. Dey, C. Jacob and M. Xanthos, Journal of Vinyl and Additive Technology,
1996, 2, 48.

44. K. Blizard, L. Chen, R. Straff, M. Deweerdt and D. Mullie, Proceedings of AMI


Profiles Conference 2000, Düsseldorf, Germany, 2000, Paper No.12.

45. M.R. Holl, M. Ma, V. Kumar and R.R. Kwapisz, Cellular Polymers, 1998, 17,
271.

46. F.N. Cogswell, Pure & Applied Chemistry, 1983, 55, 178.

47. K. Kitai, P. Holsopple and K. Okano, Journal of Vinyl Technology, 1992, 14,
211.

48. J. Patterson in Plastics Additives: An A-Z Reference, Ed., G. Pritchard, Chapman


and Hall, London, UK, 1998, 526.

49. P.S. Schipper and D. Tanjala, Proceedings of APE Vinyl Retec ‘97: Plastic Systems
for the Building Industry, Atlanta, GA, USA, 1997, 137.

50. F. Ide and K. Okano, Pure & Applied Chemistry, 1981, 53, 489.

51. B. Haworth, L. Chua and N.L. Thomas, Plastics and Rubber and Composites
Processing and Applications, 1994, 22, 159.

52. M. Cuilleret, Proceedings of Addcon World ‘98, RAPRA, London, UK, 1998,
Paper No.11.

53. R.W. Decker, Journal of Vinyl and Additive Technology, 1996, 2, 121.

54. DIN 53420, Testing of Cellular Materials; Determination of Apparent Density,


1978.

55. DIN 52612, Testing of Thermal Insulating Materials.

56. DIN EN ISO 179, Plastics - Determination of Charpy Impact Strength, 1997.

57. DIN EN ISO 527-1, Plastics - Determination of Tensile Properties - Part 1:


General Principles, 1996.

58. DIN EN ISO 527-2, Plastics - Determination of Tensile Properties - Part 2: Test
Conditions for Moulding and Extrusion Plastics, 1996.

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59. DIN 53505, Testing Of Rubber - Shore A and Shore D Hardness Test, 2000.

60. ISO 178, Plastics - Determination of Flexural Properties, 2001.

61. DIN EN ISO 306, Plastics; Thermoplastic Materials; Determination of Vicat


Softening Temperature, 1997.

62. P.R. Hornsby, Materials in Engineering, 1982, 3, 443.

63. M.F. Ashby, Metallurgical and Materials Transactions A, 1983, 14A, 1755.

64. J.L. Throne, Plastics Design and Processing, 1976, 16, 20.

65. J. Patterson, Journal of Vinyl and Additive Technology, 1998, 4, 26.

66. K.H. Steinbruck, Proceedings of SPE RETEC ARC ‘97: Information to Grow the
Plastics Recycling Industry, Chicago, IL, USA, 1997, 219.

67. R.L.J. Pots and P. Benjamin, Proceedings of Plastic Pipes IX, Edinburgh, UK,
1995, 442.

68. S. Dupont, C. Dehennau, P. Benjamin, B. Rijpkema and G. Voituron, Proceedings


of Recycle ’91 Conference, Davos, Switzerland, 1991, Paper No.34.

69. N.L. Thomas and J.P. Quirk, Plastics and Rubber and Composites Processing and
Applications, 1995, 25, 89.

70. N.L. Thomas, J.P. Quirk and H. Cretney, Progress in Rubber and Plastics
Technology, 1997, 13, 56.

71. V. Kumar, Cellular Polymers, 1993, 12, 207.

72. J.E. Martini, F.A. Waldman and N.P. Suh, Proceedings of SPE ANTEC’ 82, San
Francisco, CA, USA, 1982, 28, 674.

73. D.F. Baldwin, C.B. Park and N.P. Suh, Polymer Engineering and Science, 1996,
36, 35.

74. European Plastics News, 1998, 25, 8, 107.

75. European Plastics News, 1999, 26, 9, 27.

76. V. Kumar, J.E. Weller, M. Ma, R. Montecillo and R.R. Kwapisz, Cellular
Polymers, 1998, 17, 351.

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77. M. Glaskin, Advanced Composites Engineering, 1990, 5, 5, 16.

78. G. Dohn and R. O’Meara, Reinforced Plastics, 1999, 43, 5, 22.

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7
Flexible PVC Foams

Christopher J. Howick

7.1 Introduction

Chapter 6 of this handbook gives a detailed description of the formulations and techniques
involved in the production of rigid polyvinyl chloride (PVC) foams. As far as the end
product is concerned, the only difference between a rigid PVC foam and a flexible one is
the presence of a plasticising species in the latter. However, this simple chemical difference
hides a major difference in the production technologies available to produce flexible
foams. The majority of flexible PVC foams are produced via a plastisol route, that is, the
products are spread as a liquid dispersion of a speciality PVC resin in liquid plasticiser
and gelled and fused in ovens rather than produced via the rigid foam route of extrusion
and injection moulding. Additionally there is a large range of plasticising species available
on the open market, each with the potential of altering the foaming characteristics of the
formulation. All of these will be discussed in detail in this review.

7.2 Flexible Foam Types and PVC Types

7.2.1 Flexible Foams Based on Suspension PVC

In order to differentiate further, it should be stated that flexible foams can be formed
from PVC resins produced by two distinct technologies. Suspension PVC resins (S-PVC),
as used in rigid foams, can be used to form both rigid and flexible articles. For flexible
articles, a plasticiser, usually a liquid (see next Section), is added in the dry blend stage of
production and this remains in the final product to give flexibility to the resin. The
processing technology of the dry blend is the same as those for rigid systems although
due account needs to be given to the lower melt viscosity and reduced fusion temperatures
of the plasticised formulation. In principle any rigid foam application can be made flexible
by this route although applications for flexible foam via this route are somewhat rare.
The products themselves tend to have a low melt strength.

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7.2.2 Flexible Foams Based on Dispersion or Paste Resins

A very high proportion of flexible PVC foams are based on dispersion or paste resins.
These are materials produced from a wide variety of speciality PVC resins - emulsion,
seeded emulsion, microsuspension, mini-emulsion - which have the capability of forming a
liquid dispersion or plastisol when mixed with a liquid plasticiser. These resins, compared
to their S-PVC counterparts, are very fine particle size powders produced by the spray
drying and milling of a PVC latex. Plastisols formed from these resins can be spread,
rotationally cast, sprayed or have other substrates dipped into them. The wet plastisol is
then gelled by various routes but usually this is done thermally with a conventional oven.
In simple terms the incorporation of a blowing agent, usually azodicarbonamide (ADC),
during the plastisol mixing stage, will produce a foamed article in the oven. The higher the
level of blowing agent used the greater the level of expansion in the final product and
consequently the lower the density of the final product. This is the production of chemically
foamed flexible PVC but the production of mechanically foamed flexible PVC is also
possible. This is formed by the deliberate incorporation of air into the plastisol in the
mixing stage and if this ‘wet foam’ can be maintained during the fusion stage a foamed
product will result. The production of foam by this route is particularly enabled by dispersion
resins since in general they contain residual surfactant which can act to stabilise the wet
cells, although the deliberate addition of further surfactant is also commonplace. This
process is described in more detail in the application sections (Sections 7.3.1 and 7.3.4).

7.2.3 Chemically Blown Foams from PVC Plastisols: Fundamentals

Details of applications for plastisol foams are given in Section 7.3 and references [1-3] of
this review but all applications of chemically foamed plastisols are governed by the same
general principles.

The chemical blowing agent is introduced into the formulation during the plastisol mixing
stage along with other ingredients. A typical foamed plastisol formulation will contain
the following:

• PVC Dispersion resin


• Mineral filler (chalk)
• Pigment
• Liquid plasticiser
• Blowing agent
• Stabiliser/kicker (activator)
• Viscosity depressant
• Speciality additives

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Flexible PVC Foams

Each of these in turn has a pronounced effect on foam formation and are discussed
individually below, but first a description of the normal gelation and fusion processes
involved in the formation of a plastisol-based PVC foam is given.

7.2.3.1 Plastisol Foam Formation

The formation, gelation and foaming of a plastisol can be divided into a number of key
steps:

• Plastisol Formation

The PVC resin and other additives (including chemical blowing agent) are mixed in a
planetary or impellor type mixer to form an even dispersion of all the solid ingredients in
the liquid phase. For low viscosity pastes it may be necessary to instigate a two fold mix
cycle with a reduced amount of liquids in the first cycle to ensure a higher viscosity mix
to give adequate dispersion of solid particles in the mix. This is particularly important
when the blowing agent in use is in solid form since uneven dispersion of blowing agent
will result in uneven expansion in the foam. Chemically foamable plastisols are then
usually evacuated to remove excess air.

The plastisol may be stored or used immediately.

• Coating

The plastisol is coated onto a substrate or poured into a mould. By far the most common
means of application is onto a substrate (for floorings, wallcoverings, coated fabrics,
synthetic leathers). Application of the plastisol to the substrate is made by using reverse
roll, knife coating or screen coating, each of which place a different viscosity and rheology
requirement on the plastisol. A good review of these techniques in the wallcovering
sector is given by Niven [4] and the general rheology of PVC plastisols by Sarvetnick [5].

• Semi-gelation

The coated substrate may then be semi-gelled if subsequent coats and print designs are
to be applied. This involves heating of the plastisol to above the glass transition
temperature of the PVC polymer (70-85 °C) so that the polymer chains become fully
mobile and the plasticiser and other liquid additives can be absorbed into the polymer.
This results in a rapid rise in viscosity as the plastisol solidifies and for a typical mid-
molecular weight resin this state continues until the temperature reaches approximately
140 °C. This is a typical semi-gel temperature although the range varies from 125 °C to
160 °C depending on both polymer and formulation. The state of the semi-gel is a solid

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but as complete fusion of the polymer and all the additives has not yet occurred the
material has little strength and flexibility. However if the semi-gel has been produced by
passing the plastisol around a heated drum, as is frequently the case, the semi-gel has a
very smooth surface which is ideal for printing of designs or the laying down of further
plastisol coatings.

One key point for semi-gelled plastisol foams is that the semi-gel temperature must be
below both the true decomposition temperature and the catalysed decomposition
temperature of the blowing agent to prevent foaming and surface texturing of the semi-gel.

• Gelation, Fusion and Expansion

After semi-gel printing and storage the material is then fused by passing through another
heating stage. This stage is normally performed using conventional thermal ovens. During
fusion the polymer enters the melt and full mixing of formulation ingredients occurs at a
molecular level. The result of the melting of the polymer is for a reduction in viscosity to
take place. The overall viscosity versus temperature profile for a typical plastisol in shown
in Figure 7.1. On cooling from the fused state the product re-establishes the polymer
network but with plasticiser molecules intimately mixed. These molecules prevent the
establishment of all of the chain - chain interactions that characterise rigid PVC so the
flexibility of the final product is greatly enhanced (for detailed descriptions of the
plasticisation mechanism see [6-11]).

Figure 7.1 Effect of plasticiser level of plastisol gelation and fusion

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Flexible PVC foam

Flexible PVC Foams

For the purpose of flexible PVC foams, the key point about the gelation and fusion
process is that the temperature of the blowing agent decomposition will be reached and
exceeded during this stage. The resulting generation of gas will give rise to the foaming
of the melt and this structure will be retained in the final product if cell walls have
sufficient strength to survive the thermal treatment after they have formed. The amount
of foam expansion depends on a number of factors but in simple terms is governed by
the volume of gas generated and the viscosity of the polymer melt at the point of blowing
agent decomposition, higher viscosity melts giving a greater level of resistance to the
expanding gas. There are many good detailed descriptions of the foaming of PVC plastisols
given in the literature [1-3] and the reader is encouraged to read these to gain an in-
depth understanding.

7.2.3.2 Blowing Agents and Foam Formation

A chemical blowing agent is a substance that can be added to a material such that the
substance decomposes at a given temperature to release a volume of gas that causes the
material to expand. As with rigid foams by far the most common chemical blowing
agent is ADC which has a decomposition temperature in the range 200-230 °C. This
temperature can be reduced by the incorporation of catalysts or ‘kickers.’ These are
typically metal salts or complexes and have chemical features so much in common with
the range of metal thermal stabilisers for PVC that the two properties are frequently
combined in a ‘stabiliser - kicker’ system. These can be used either separately from the
blowing agent or they can be compounded with the blowing agent by the blowing agent
manufacturer. Thus in theory it is possible to tailor a blowing agent-kicker combination
for an individual formulation and set of processing conditions to give the degree of gas
yield and expansion required. In addition to the temperature of blowing agent
decomposition the rate of gas generation is also critical and depending on the processing
conditions (length of oven, rate of air changes, etc.), a choice of kicker will need to be
made. Four basic types are:

1. Low temperature action with rapid gas generation

2. Low temperature action with slow gas generation

3. High temperature action with rapid gas generation

4. High temperature action with slow gas generation

and there are also intermediate types available from suppliers. The effect of these various
kickers is shown in Figure 7.2. For example a high speed wallcovering formulation based

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Figure 7.2 Effect of different kickers on foam expansion

on a low molecular weight resin would require a low temperature, rapid gas generation
type since the low molecular weight of the resin would establish the correct melt viscosity
conditions rapidly. In a product which has additional requirements of mechanical strength
a higher molecular weight of PVC resin will be specified with the proviso to delay the
decomposition of the blowing agent until the plastisol melt viscosity has reduced
sufficiently to give the expansion level required. This may result in the need for a high
temperature, more controlled gas generation kicker/catalyst type. However raising the
molecular weight of the PVC resin can be of limited effect in an attempt to improve the
mechanical strength of the foam: greater benefit in mechanical strength can often be
obtained by improvements in the structure and uniformity of the foam produced and in
many cases this may mean the use of low molecular weight PVC homopolymers.

7.2.3.3 Cell Types

Flexible PVC foams are generally described by their cell nature, i.e., closed or open cell.
Closed cells tend to give good resistance to compression but if compression occurs they
will recover slowly. Open cells, whilst offering very low resistance to compression, will
recover quickly from any compressive force. These factors are important where these

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Flexible PVC Foams

properties form part of a specification. Generally an open cell structure will result if a large
amount of the foam structure has formed before maximum gelation of the plastisol has
occurred. When further heat is applied and melt viscosity falls, the pressure within an
individual cell increases so that the cell walls break to form an open cell structure. Thus for
open cell structure a fast gelling system is desired and this can be made through formulation
development and resin choice. Although some statements with regard to preferred resin
choice for open and closed cell have been made [1] exceptions to these statements can be
found. In addition to the type of cell, i.e., whether open or closed type, the quality of the
cell will also need consideration. Cells can range from exceedingly fine to very coarse and
this is controlled by a number of factors. Of key importance are the gelation rate, the gas
evolution rate of the blowing agents involved and also the surfactant present from the PVC
resin manufacturing process. The PVC particles will contain a layer of surfactant on their
surface and when the blowing agent decomposes these layers stretch so the surface tension
of this surfactant plays an important role in determining the quality of the cell (as defined
by structure (open or closed), size and uniformity), as does the solubility of this surfactant
in the plasticiser and the ease at which the plastisol can release entrapped air (for chemical
foaming formulations) or retain air (for mechanical foam formulations). PVC resin
manufacturers will generally develop resin systems for chemical foam formulations of given
families of surfactants known to impart good cell structural quality.

7.2.4 PVC Resins used in Plastisol Foam Formation

The choice of PVC resin in the chemically foamed formulation has long been a subject
which arouses great amounts of discussion and debate. Since these resins are spray dried
they tend to have a unique particle size distribution associated with the drying process,
which is difficult to match on a different spray drier. Consequently, different resins have
different particle size distributions and hence different gelation properties which in turn
affect the foam properties. Although end users may deem one resin as an acceptable
alternative to another resin, it is rare to find two resins which are indistinguishable.
Resins available are made by a variety of routes.

7.2.4.1 Microsuspension Resin

Made in a method similar to the suspension resin (in which monomer droplets are
suspended in water and then polymerised using a monomer soluble initiator) with the
exception that the vinyl chloride:water mixture is mechanically homogenised to produce
very fine droplets of monomer in water. These droplets are then stabilised using a surfactant
and the system polymerised. This results in a broad particle size PVC latex which is then
spray dried and milled.

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7.2.4.2 Emulsion Resins

In this case the polymerising medium contains very small droplets of monomer in water
which are formed by the use of surfactants. The polymerisation is carried out using
water soluble initiators and the resulting PVC latex contains very small PVC particles
with a very narrow particle size distribution. This latex can then be spray dried and
milled. A number of variants of the process are also available such as seeded emulsion,
continuous emulsion and mini-emulsion. The last of these shows similarities to
microsuspension polymers in that a broad range of monomer droplet sizes are formed
through the use of surfactants. Emulsion and seeded emulsion polymers may be
differentiated from mini-emulsion polymers in that for the latter a homogenised mix of
vinyl chloride monomer and water is produced prior to polymerisation through the use
of surfactants. This combined surfactant system (where surfactants act to both homogenise
the monomer:water mixture and to take part in polymerisation) generally leads to
polymers possessing relatively high residual surfactant levels and these can play a part in
the foaming process since they can lead to a differing surface tension of the expanding
cell walls during the formation of the foam. In general terms such polymers exhibit
faster gelation properties and a tendency to open cell formation, a property that can be
enhanced by careful selection of blowing agents and kickers.

The drying and milling phases of the processes - common to all of the polymerisation
technologies listed above - play a critical part in the foaming performance of the grade of
polymer. The spray drying process forms agglomerates of the primary particles present
in the PVC latex. These can range from a few microns in size up to about 50 μm. These
agglomerates can be broken down by milling although it is rare for large proportions of
them to be broken down entirely. As a result, the final polymer as supplied to the foam
processor contains a range of particles from sub-micron primaries to persistent large
agglomerates up to 50 μm. The proportion of agglomerates to primaries is set by the
precise drying conditions and the severity of the milling used. Essentially the smaller
particles melt more quickly on the application of heat which then results in the plastisol
entering the true melt phase more rapidly.

7.2.5 Mineral Fillers

Fillers such as chalk are used in a formulation for cost reasons since they are normally
available at significantly lower costs than the other primary formulation ingredients.
The level used is a balance between the cost advantages and the potentially detrimental
effects on foaming and viscosity of the plastisol. High filler levels will lead to an increased
melt viscosity which will in turn provide more resistance to the evolved gas from the
blowing agent decomposition. In turn this will lead to reduced foam expansion. High

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filler levels will also result in higher densities of the foam (filler density is significantly
higher than other formulation ingredients) and result in a deterioration in mechanical
properties. At high levels, filler will also have an effect on the cell structure.

7.2.6 Pigments

These have a similar effect to fillers but, owing to their significantly higher price and the
fact that they have the potential to cause increased plastisol viscosity, their concentration
in the final formulation is significantly lower than that of a filler and in normal cases
their effect on foaming is negligible.

7.2.7 Liquid Plasticiser

This has a pronounced effect on the foaming process, both in terms of type and levels used.
Since foaming properties are dependent on the melt viscosity of the plastisol, plasticisers
play an important part in the foaming process since they can, by nature of their polarity
and concentration, affect the melt viscosity obtained during the fusion process. It needs to
be stressed that a conventional viscosity versus temperature plot as recorded using dynamic
temperature viscometry, records the change in viscosity with temperature over a period of
up to 30 minutes whereas conventional plastisol fusion ovens subject the plastisol to a high
temperature, e.g., 200 °C, for a short time period (1-2 minutes). Thus, the time taken for a
plastisol to reach a given melt viscosity will be controlled by the fusion characteristics of
the formulation. In general, faster fusing formulations will give faster expansion owing to
their ability to reach lower melt viscosities during the plastisol fusion stage. In terms of
plasticiser types, the effects are summarised next:

• ‘Active’ plasticisers: these produce fast fusing systems and are generally based on
polar, relatively low molecular weight plasticiser esters such as butylbenzyl phthalate
and benzoates. Whilst these produce fast fusion and relatively fast expansion it should
be noted that the higher polarity can cause relatively rapid rates of plastisol viscosity
increase with time and may lead to undesirable migration and exudation properties
in the final product.

• Dialkyl phthalate esters: these include the industry standards di-2-ethylhexyl phthalate,
di-isononyl phthalate and di-isodecyl phthalate (DIDP). Such esters also includes di-
isoheptyl phthalate.

The effect of these plasticiser types on the foam properties are given in Table 7.1.

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Table 7.1 Effect of plasticiser type on fusion and foaming characteristics


Phthalate ester No of carbon atoms in Fusion and foam
alkyl chain characteristics
Butylbenzyl phthalate 4 and 6 Very fast
Dipropylene glycoldibenzoate 3 Very fast
Di-isoheptyl phthalate 7 Fast
Di-2-ethylhexyl phthalate 8 Medium
Di-isononyl phthalate 9 Medium
Di-isodecyl phthalate 10 Slow
Linear 9,11 phthalate 9 and 11 Slow
Di-undecyl phthalate 11 Slow
Di-isotridecyl phthalate 13 Very slow

The plots shown in Figures 7.1 and 7.3 record the changes in viscosity of the plastisol
with temperature and this can be used to find the optimum range of melt viscosity for a
given blowing agent system. The key parameter is the precise value for the viscosity of
the plastisol melt at the temperature of decomposition of the blowing agent. Figure 7.1
shows the effect of increasing the level of plasticiser on the gelation characteristics with
progressive additions resulting in progressive reductions in melt viscosity which in turn
will produce greater foam expansion when the blowing agent decomposes. Similar effects
can be obtained from increasing mineral fillers (increasing melt viscosity) and decreasing
the molecular weight of the resin (K Value) which leads to significant reductions in melt
viscosity and therefore greater foam expansion during blowing agent decomposition.

Figure 7.3 shows the effect of different plasticiser type on the gelation characteristics
with the very active butyl benzyl phthalate giving rapid gelation through to the relatively
slow progress of the C10 phthalate ester DIDP. Also shown here is the plot of Tan delta
with temperature. This is the ratio of the loss (or viscous) modulus to the storage (or
elastic) modulus of the plastisol. Since a PVC plastisol is neither purely viscous (dissipating
all energy as heat during flow and not recovering to any degree from the deformation),
nor purely elastic (storing all energy input and recovering completely from the applied
deformation) this value gives a measure of the change in state of the plastisol as the
temperature is raised. In turn this gives a measure of the elasticity of the plastisol at a
given temperature as the plastisol is heated and this can give an insight into its ability to

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Flexible PVC Foams

Figure 7.3 Effect of plasticiser type on plastisol gelation and fusion

be used satisfactorily in certain processes in which the material may be subject to


deformation at various temperatures. Figure 7.3 shows the expected increase in Tan delta
(increasing viscous behaviour) as the plastisol enters the melt.

7.2.8 Blowing Agent Type and Level

Naturally this is a critical feature of foam formation. Whilst the level of foam increases
proportionately with the level of blowing agent, higher levels of blowing agent may lead
to a disruption in the texture of the foam surface. Birch [12] showed the relationship
between blowing agent particle size and speed of expansion: as expected a finer particle
size of the blowing agent results in a more rapid decomposition that a corresponding
large particle size blowing agent. ADC continues to be the standard for the flexible PVC
industry since it is relatively easily activated with foam catalysts (or ‘kickers, see
Section 7.2.3.2) so that the decomposition occurs in the melt range for the majority of
PVC resins. Where lower plastisol gelation temperatures are used other lower temperature
blowing agents such as 4,4´-oxy bis(benzenesulfohydrazide) can be used. Additionally,
inorganic hydrogen carbonates can also be used. These are seldom used alone but may
be used to augment ADC and in some cases can produce desirable surface effects in
fashion goods.

There has recently been a move towards very matt finishes for foam surfaces as a desired
fashion effect and producers have faced a technical challenge in ensuring that technology
and additives available to provide surface disruption on a microscopic level have not led
to a deterioration in foam quality.

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7.3 Products Utilising Foamed Plastisols

A number of industries utilise flexible PVC foam technology. The principal ones are:

1. Floorings and carpet backings

2. Wallcoverings

3. Synthetic Leather

4. General Foams

7.3.1 Floorings and Carpet Backings

Whilst these can be made through a calendered route the foamed products are generally
made through a plastisol route.

The spread (plastisol) flooring market can be divided into two distinct sectors - domestic
and contract. The former places a major emphasis on design and new designs both instigate
and follow fashion trends within the sector. There are regular new product launches and
the foam can play an important part in the achievement of these design requirements.

A typical cushion vinyl flooring consists of four layers (see Figure 7.4). At the top is a
wear layer of clear PVC which provides the necessary wear and mechanical resistance.
Beneath this there is generally a printed foam layer which utilises chemical inhibition.
Both of these layers are spread onto a fibreglass layer impregnated with a solid PVC
plastisol. The whole assembly can then be turned and have a backing layer applied and
the whole flooring can then be fully fused during which time expansion of the blowing
agent occurs.

Figure 7.4 Typical cushion vinyl flooring: 1 = Impregnated fibreglass; 2 = printable foam
layer; 3 = clear wear layer and 4 = foamed backing layer (chemical or mechanical)

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Flexible PVC Foams

The aim of the process of chemical inhibition is to nullify the effect of the blowing agent.
The printable foam coating is spread onto the solidified coated fibreglass and this new
layer is then gelled at a temperature below the decomposition temperature of the blowing
agent. This stage is performed frequently using a heated metal drum. This solid product is
then printed with inks, some or all of which can contain a chemical inhibitor, which either
interacts with the blowing agent to prevent its decomposition, (e.g., thiourea), or interacts
with the kicker to prevent it from ‘kicking’ the blowing agent (trimellitic anhydride,
benztriazole). Whichever route is used the effect is the same - selective prevention of foaming
in the layer to give a contour effect, (i.e., areas of foam and areas of no foaming), throughout
the flooring. Since these inhibitors may be dispersed or dissolved in selected inks only, this
leads to certain colours in the design possessing differential relief to other colours when the
remaining PVC layers have been applied and the final product is expanded by fusion - a
potentially striking visual effect. An alternative method can involve the inclusion of kickers
in the ink so that foaming is generated only in printed areas - again the overall effect is the
same. The inks are then dried and other layers applied.

The original technology was patented by the Congoleum Corporation [13] although the
primary patents have expired and the technique is now used throughout the cushion
vinyl flooring industry. Traditional inhibitors were based on trimellitic anhydride although
concerns with regard to the toxicity of this material have encouraged the use of
benztriazole. More recently technology has moved towards water-based printing systems
and derivatised benztriazole and thiourea systems have been studied. Today a number of
proprietary inhibition systems are sold.

It may be noted that the mechanism of inhibition requires migration of the inhibiting
species into the printable vinyl layer. The rate of this migration will depend on both the
migration rate of the ink solvent and the thickness of the foam layer. It is possible to dry
these inks too rapidly before full penetration has occurred (especially in the case of the
generally less polar, water-based systems) and also there is a danger of excessive migration
if the unfoamed, semi-finished product is stored for prolonged periods. This is due to the
migration of the ink continuing under pressure in the rolled flooring through other layers
and into the foamed areas that are not intended to be inhibited. This phenomenon is
generally referred to as ‘ghosting’ [4].

The backing layer is frequently foamed, either by a chemical or mechanical means. In


this layer foam structure is important since it is this layer which is a major contributor to
the ‘cushion’ effect.

Contract vinyl flooring possesses many of the features of cushion vinyl flooring. Whilst
design and fashion are important, a major consideration is meeting the key technical
standards specified by authorities or architects for installation in hotels, schools, hospitals,

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etc. Key areas in which PVC foam has a major contribution are the acoustic properties
and the compression and indentation resistance and recovery. The products used in this
area have a variety of structures, e.g., printed inhibition type foams, flat printed layers,
thick or thin wear layers, compact or highly foamed backings selected to obtain the
overall properties required to meet these tests. The foam contributes thickness and a
cellular structure, with thick, closed cell foams preferred for sound absorption. For good
compression properties, closed cell foams offer better compression resistance although
open cell foams perform better on compression recovery. The exact requirements are
generally met by a suitable combination of resin type, expansion ratio, fusion conditions
and foam thickness. Standards of relevance are EN 424 [14], EN 425 [15] and EN 433
[16]. Acoustic properties of building materials form one of the six essential requirements
of the European Construction Products Directive (89/106/EEC) [17].

The production of foamed PVC backings for carpets also takes place although the volumes
involved are much lower than that for cushion vinyl floorings. Application technologies
are relatively straightforward knife coating technologies and are based on free foaming
formulations, (i.e., no inhibition requirement). A range of blowing agents is used. ADC
is the most common although lower temperature systems can also be used when either
carpet fibres or printing inks used in the carpets are particularly thermally sensitive.
Some products in this sector are sold into contract applications and here acoustic and
compression recovery is also important although the carpet itself has a major influence
on these properties.

7.3.2 Wallcoverings

Foamed wallcoverings show many of the foaming technologies described for floorings
although the foaming in wallcoverings is almost exclusively through a chemical rather
than mechanical means. A variety of foamed wallcoverings are available:

1. Inhibited foamed wallcoverings

2. Free blow foams with flat surface

3. Free blow foams with a textured surface

Inhibited foamed wallcoverings are made using the same methodology as described for the
inhibition layer of cushion vinyl flooring. In wallcoverings this produces a relief effect and
gives the ability for the wallcovering producer to mimic a tile design (hence this particular
product being named ‘tiling on a roll’). The technology was again based on the Congoleum
patent [13]. This product may also contain a clear PVC coating on top.

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Flexible PVC Foams

Relief designs in wallcoverings can also be made by printing foamable plastisols onto
paper in a specific design through screen printing. The versatility of PVC resins available
on the market enables all types of rheology to be obtained and this includes the highly
pseudoplastic rheology, required for high speed screen printing of intricate designs. With
good shear recovery plastisol can be laid down onto paper without flowing out of design
so that the plastisol is fused with blowing agent decomposition in specific areas to create
the desired design effect. With numerous screen printing stations available, each printing
a plastisol with a different formulation (often containing a different level of blowing
agent), complex designs are possible with different areas having different levels of
expansion. Many of these designs have areas of high expansion but with characteristic
flat surfaces - an effect requiring complicated PVC formulating involving resin, plasticiser,
blowing agent and kicker development. The surface texture can be altered by precise
changes in the melt viscosity profile in order to find the optimum melt viscosity at the
temperature at which the blowing agent decomposes.

Similar designs can also be produced with a textured surface. In this case the surface of
the foam is deliberately disrupted through a combination of ‘pre-blow’, caused by the
incorporation of low temperature blowing agents, and by the incorporation of a volatile
species - frequently iso-propanol - to allow for boiling off during the foam gelation
stage. This textured surface is a traditional design feature for certain markets.

7.3.3 Synthetic Leather

This is a large market for plastisol-based PVC resins and the foaming of plastisols is an
integral part of the technology.

The product itself is made up of a number of layers (see Figure 7.5).

A plastisol is applied to a backing substrate such as a silicone release paper and gelled.
The foam layer is then applied and gelled below the decomposition temperature of the

Figure 7.5 Schematic of PVC leathercloth; 1 = fabric backing; 2 = foam layer; 3 = solid
top coat; 4 = release paper or other substrate

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blowing agent. A lamination plastisol is then applied and finally a fabric (either natural
or synthetic) is applied and ‘squeezed’ into the lamination plastisol. The whole assembly
is then fused in an oven and the blowing agent allowed to decompose. In some cases the
lamination stage may be omitted and the adhesion of the fabric simply made into the
foam coat. The general aim of the product is to have a relatively high expansion ratio to
simulate the lightweight leather ‘feel’ - indeed, in many of the fashion leather sectors this
‘feel’ or ‘touch’ is the main selling point and is difficult to quantify in terms of mechanical
testing. The lightness is also enhanced by relatively high levels of plasticiser and here
resin choice is important since a resin which is capable of giving a workable paste with
high levels of plasticiser is required.

In technically demanding sectors such as automotive leather, additional requirements


exist. Many systems omit the fabric stage and these products are known as unsupported
expanded vinyl (UEV) and in this case the PVC must possess additional strength since it
cannot rely on the fabric for strength in the many vacuum forming processes that exist in
the automotive industry. This places the additional challenge to the PVC formulator
since the additional mechanical strength is generally obtained through the use of higher
molecular weight resins which traditionally possess poorer foaming characteristics. Hence
a formulation requiring higher foaming temperatures and later blowing agent
decomposition (see above) may be appropriate. Additionally this product must possess
low fogging properties and have excellent long term thermal stability.

7.3.4 General Foams

In addition to those products described previously, foams are also produced and sold as
foams. These products are generally highly expanded and subsequently low density
chemical foams or low density mechanical foams produced by speciality processes. These
products sell into markets such as the automotive and indoor application markets for
sealing foams and products such as draft excluders. They are technically demanding
since the general requirement is to obtain very thick foams (in comparison to the products
described previously) but still retain a fine cell structure which is free from foam collapse
and possesses a flat foam surface. Such foams are also made through simple plastisol
coating technology and differ only in the significantly higher levels of blowing agents
used. Foams are generally sold according to density and indentation resistance and
recovery specifications and in some cases the proportion of open to closed cells.

Some speciality foams are produced through mechanical means involving the
pressurisation of a PVC plastisol with a liquid blowing agent which will evaporate to
produce a foamed plastisol which can then be gelled. The foam is normally produced in
very thick slabs which can then be cut into thinner sections as required. Again these find

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use in automotive applications but also in stationery goods and sports matting and medical
applications such as surgical collars.

References

1. R. Brathum and P. Zingsheim in Polymeric Foams, Eds., D. Klempner and K.


Frisch, Hanser Publishers, Munich, Germany, 1991, Chapter 10.

2. D.A. Boscott and S. Coulson, Proceedings of PVC ‘93, Brighton, UK, 1993,
Paper No.36.

3. P. Bergounhon and B. Ernst, Proceedings of PVC ‘99, Brighton, UK, 1999, p.258.

4. W.G. Niven in Plastics: Surface and Finish, 2nd Edition, Ed., W.G. Simpson,
Royal Society of Chemistry, Cambridge, UK, 1993, Chapter 15, p.281-305.

5. Plastisols and Organosols, Ed., H.A. Sarvetnick, Van Nostrand Reinhold, New
York, NY, USA, 1972.

6. J.K. Sears and J.R. Darby, The Technology of Plasticizers, Wiley Interscience,
New York, NY, USA, 1982.

7. A. Wilson, Plasticisers: Principles and Practice, Institute of Materials, London,


UK, 1995.

8. D.F. Cadaogan and C.J. Howick in Ullmann’s Encyclopedia of Industrial


Chemistry, 5th Edition, VCH-Wiley Publishers, New York, NY, USA, 1992,
Volume A20, p.439.

9. D.F. Cadogan and C.J. Howick in Kirk-Othmer Encyclopedia of Chemical


Technology, 4th Edition, John Wiley and Sons, New York, USA, 1996, Volume
17, p.258.

10. C.J. Howick, Proceedings of PVC ‘93, Brighton, UK, 1993, Paper No.38.

11. N.J. Clayden and C.J. Howick, Polymer, 1993, 34, 12, 2508.

12. S.J. Birch, Proceedings of PVC ‘93, Brighton, UK, 1993, Paper No.35.

13. J.C. Harkins, Jr., R.R. Nairn, H. Tarlow and F.E. Ehrenfeld, inventors;
Congoleum Nairn Inc., assignee; US 3293094, 1966.

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14. EN 424, Resilient Floor Coverings – Determination of the Effect of the Simulated
Movement of a Furniture Leg, 2001.

15. EN 425, Resilient Floor Coverings – Determination of the Effect of a Caster


Chair, 2002.

16. EN 433, Resilient Floor Coverings – Determination of Residual Indentation After


Static Loading, 1994.

17. 89/106/EEC, Council Directive of 21st December 1988 on the Approximation of


Laws, Regulations and Administrative Provisions of the Member States Relating
to Construction Products, 1988.

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Polyolefin Foams

8
Polyolefin Foams

David Eaves

8.1 Introduction

Although polyolefin foams are relatively recent additions to the range of polymeric foam
materials, having been first marketed in the early sixties, they have found a use in almost
every industry. Areas of application include packaging, sports and leisure, toys, insulation,
automotive, military, aircraft, buoyancy, cushioning and others. This wide range results
from the scope to vary properties from hard and tough through to soft and resilient.
Hard (though not brittle) foams are obtained using polypropylene or high density
polyethylene as the basic polymer, whilst softer materials are obtained using ethylene or
propylene co-polymers such as ethylene vinyl acetate (EVA). This ability to vary foam
properties by changes in the polymer is similar to that seen in polyurethane foams, although
the technologies are very different since almost all polyurethane foams result from liquid
technology with in situ polymerisation and blowing whilst polyolefin foams are all
produced starting with the basic thermoplastic polymer.

No single foaming method dominates polyolefin foam manufacture and both continuous
and batch processes are operated. The manufacturing process is a factor determining
both the form of the foam (sheet, block, bead) and foam properties since the process
determines the foam structure, degree of crosslinking (if any) and level of residual by-
products, e.g., from the blowing agent.

Polyolefin foams are normally closed cell, though open cell products can be made by a
post manufacture processing operation. The foams may be crosslinked or non-crosslinked,
different processes being used for each type. Crosslinked foams retain their basic foam
structure at temperatures above the polymer melting point and hence lend themselves to
heat moulding methods for the manufacture of shaped products from foam sheet. Most
polyolefin foam products involve further operations on the foam following manufacture.

Whilst there has been for some time a wide choice of materials for polyolefin foam
manufacture encompassing most of the homo and copolymers of ethylene and propylene,
the range has recently been increased further by the introduction of polyolefins made

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using metallocene catalysts. These catalysts enable a high degree of control of polymer
structure and polymers are available having enhanced properties including higher tensile
strength and elongation and greater flexibility. Some manufacturers have introduced
foams based on metallocene catalysed polymers and claim significant property advantages
for such foams. It is reported however, that metallocene polymers are more difficult to
process and hence increase the costs of foam manufacture.

The blowing agents used for polyolefin foams include chemicals such as azodicarbonamide
(ADC), liquids (such as chloroflurocarbons (CFC) or more recently
hydrochloroflurocarbons (HCFC) and hydrocarbons) and gases (such as CO2 or N2).
Since the foams are closed cell, the blowing agent remains in the foam for significant,
sometimes quite extended, periods and can affect foam properties and post manufacturing
forming operations.

8.2 Manufacturing Processes and Materials

8.2.1 Extruded Non-Crosslinked Foam

8.2.1.1 Process

The manufacturing concept is comparatively simple, a physical blowing agent, originally


CFC-11, is injected at the end of the melt homogenisation section of a single stage extruder.
At this point all additives, which may include nucleating agents and pigments (often
added as masterbatches), have been incorporated. The blowing agent is dispersed in the
melt, reducing the melt viscosity and allowing efficient cooling and temperature control
so that the melt temperature is reduced to a point close to the polymer melting point.
The extruder barrel and die design are such as to withstand the high pressures generated
(typically 15-20 MPa) where the liquid blowing agent is present. On exit from the die,
the polymer immediately expands by virtue of the pressure from the contained blowing
agent. Nucleation takes place in the die as the pressure decreases towards the die exit
and may be enhanced by the presence of nucleating agents such as talc. Adiabatic cooling
effects help to stabilise the polymer by reduction of extrudate temperature below the
polymer melting point.

A preferred process is a tandem extrusion system. This, whilst more capital intensive,
allows separation of the initial melt homogenisation step from the subsequent mixing of
blowing agent for which a higher screw speed may be necessary. A co-rotating twin

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Polyolefin Foams

screw extruder is sometimes used for the primary mixing to give superior dispersion of
additives. The tandem arrangement is particularly advantageous at high extrusion rates
(above 200 kg/h) and allows a wider range of formulations to be processed. The high
pressure generated in the down stream extruder must be contained by a suitable seal
between extruders and manufacturers have their own patented solutions to this problem.

After manufacture, the blowing agent within the foam can cause dimensional instability
due to the different rates of diffusion of air into the foam and blowing agent out.
Manufacturers therefore institute a maturing period to allow the foam to stabilise before
dispatch to customers. This can take several weeks, depending on foam thickness and
the temperature used to accelerate maturing. Vapour released is collected and recovered
or exhausted.

The use of CFC-11 has been discontinued in developed countries in line with the Montreal
Protocol, and alternatives evaluated have included HCFC, HFC, various hydrocarbons
such as pentane and isobutane, and gases such as CO2 and N2. Although HCFC have
been adopted for the manufacture of some non-polyolefin foams, they are interim
substances due for phase out themselves. HFC are acceptable but expensive, and the
gases are difficult to use requiring very high containment pressures to achieve useful
expansion levels. Hence, hydrocarbons have been generally adopted for the manufacture
of non-crosslinked extruded polyolefin foam. Although technically acceptable in that
the expansion process can, with some adjustment to material and process parameters, be
made to operate satisfactorily, hydrocarbons are inherently flammable and (in mixtures
with air) explosive. This gives rise to safety considerations in both manufacture and use,
for instance if there is any residual vapour left in the foam after manufacture it will
slowly diffuse out and, in confined storage, build up to a dangerous level. For this reason
it is necessary to control the maturing stage to the extent of ensuring no significant traces
of hydrocarbon blowing agent are left in the foam.

Processes using an inert blowing agent do not, of course, have the flammability problems
associated with hydrocarbons. Nitrogen has been in use for many years to produce
crosslinked foams by the autoclave process (see later) but an extrusion process has not
been developed owing to the high pressures necessary to achieve significant incorporation
of gas in the polymer. Carbon dioxide however has considerably greater solubility and
maintains the advantage of low cost and zero ozone depletion potential (ODP). Extrusion
processes using CO2 are available, the main problem being sealing in the extruder to
retain the necessary pressure. Foams however tend to have a poor cell structure with
large cell dimensions, and the high diffusion rate of CO2 out of the foam compared with
air into the foam results in the dimensional stability problem mentioned earlier. Extrusion
processes using CO2 tend to be sensitive to operating parameters.

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Technology for production of non-CFC blown polyolefin foams is available from extruder
manufacturers such as Reifenhauser GmbH (RElcell lines) and Berstorff GmbH (Schaumex
and Schaumtandex lines). A typical Schaumtandex line comprises [1]:

• Silos for raw materials (polymer and reclaim).

• Pre-dryer.

• Mixing and metering unit for polymers and any additives.

• Blowing agent storage vessel and metering unit.

• Tandem extruder system with gear pump and extrusion die, e.g., for board sheet.
Blowing agent is metered in towards the end of the first extruder with a patented
‘active melt seal’ to prevent back up of pressure from the blowing agent.

• Thickness calibrator following the die.

• Take off roller train.

• Cooling section.

• Take off unit.

• Longitudinal cutter.

• Cross cutter.

• Conveyor belt to stacking unit.

Depending on precise design and equipment, this type of line is suitable for both polyolefins
and other polymers such as polystyrene. Blowing agents can include CO2 and hydrocarbons.

MuCell technology, which aims to produce foams with very small cells having dimensions
comparable to or smaller than the critical flow size in polymers, also claims to produce
CO2 blown polyolefin foams by an extrusion process. Foam densities however are
relatively high. This recent technology is available for license from Trexel and is reviewed
in Chapter 10 of this Handbook.

8.2.1.2 Materials

The polymer most used is low density polyethylene (LDPE), that is, polyethylene produced
by high pressure reactor technology and having a polymer density about 920 g/l. This

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material has good processing characteristics and a suitable polymer melting point.
Polymers such as linear low density polyethylene (LLDPE) and high density polyethylene
(HDPE) have higher melting points with a narrower melting range, and more critical
processing characteristics including lower melt strength, making these materials less
suitable for the process.

Polypropylene, like HDPE, also normally has a sharp melting transition and low melt
strength, but some variants introduced by Montell (Higran) and Borealis (Daploy HMC
130D) introduce long chain branching into the normally linear chain structure. These
products exhibit high melt strength and strain hardening which enables the production
of polypropylene foams. The cell walls stabilise without rupture within the short time
required to allow expansion to low densities [2].

These materials can also be used for the manufacture of expanded polypropylene beads
(EPP) by extrusion (see later).

An interesting material’s variant is the use of thermoplastic elastomers (TPE). Mack and
Meyke (Berstorff) [3] have described a process, introduced in 1995, which uses a single
extruder having an L/D of 30 with the injection point for blowing agent mid-barrel. At
this stage the melt temperature is 220 ºC, reducing to 195 ºC at the die exit by virtue of
the provision of barrel cooling. The profile is quenched with spray nozzles over a belt
conveyor. Water is used as the blowing agent, and the polymer used is Santoprene. No
nucleating additives are necessary - it is surmised that the dispersed rubber phase of the
TPE is sufficient to cause bubble nucleation and a fine cell structure is produced. Foam
densities are fairly high - about 300 kg/m3. The product is seen as an alternative to vulcanised
ethylene-propylene diene terpolymer (EPDM) foam profiles with the advantages of:

• no curing,

• no harmful emissions,

• recyclable,

• full colour matching possible,

• lower densities compared with EPDM.

8.2.2 Expanded (Non-Crosslinked) Polyolefin Beads

An expanded polymer bead process was first developed by BASF in the 1950s for
polystyrene. In the 1970s the process was extended to polyethylene and, more recently,

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to polypropylene copolymers. The production process involves converting the polymer


to micropellets which are transferred to a process tank as an aqueous slurry. Here the
pellets are impregnated with a hydrocarbon blowing agent such as propane at elevated
temperature and pressure. After the hydrocarbon is fully absorbed, pressure is released
and the particles allowed to expand to form low density beads some 4-5 mm in diameter.
The blowing agent is contained and recovered for further use. Since the bead size is small
and the polymer, whilst being below its melt temperature is above its glass transition,
diffusion of blowing agent out of the beads is rapid and is said to be essentially complete
within a few days following production. This contrasts with polystyrene which, as it is
below its glass transition at normal ambient temperatures, retains the blowing agent and
is transported for use in the unexpanded state. Polystyrene beads are expanded by the
producer of the final product using appropriate moulds. Polyethylene or polypropylene
beads are transported in the expanded state, and hence the moulding process is technically
different. It has been described by Cousins and Domas (BASF) [4] and essentially involves
the following stages:

1. Mould closed, locked and preheated.

2. Back pressure applied and mould filled with expanded particles. The back pressure
(0.06 – 0.40 MPa) compresses the expanded particles and hence controls the weight
of foam needed to fill the mould, and also the final moulded foam density. A high
back pressure results in a high density of moulded foam.

3. Mould sealed and back pressure reduced.

4. Steam passed through mould to fuse particles.

5. Water passed through mould to cool moulding and then drained off.

6. Air pressure applied to loosen moulding.

7. Mould opened and moulded part ejected.

8. Mouldings stored at elevated temperature, e.g., 80 ºC, to stabilise dimensions.

It will be realised that foam mouldings are inevitably denser than the nominal bulk
density of the expanded particles. Some data for Neopolen P (polypropylene bead foam
produced by BASF) [4] is shown in Table 8.1.

Since the low bulk density of EPP particles (and the requirement to transport in the
expanded state) results in high transport costs, development work has attempted to find

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bulk density Neopolen P moulded density Neopolen P

Polyolefin Foams

Table 8.1 Comparison of nominal bulk density and typical


moulded density for Neopolen P
Nominal bulk density, kg/m3 Typical moulded density, kg/m3
11 21-26
17 26-35
28 50-65

methods of moulding lower density foams from higher density beads. A method of
achieving this has been described by Cousins (BASF) [5] .

In this process particles are pre-pressurised with air (0.3-0.4 MPa) at elevated temperatures
(70-80 ºC) for a period of 4 to 6 hours. This technique essentially introduces air as a
post-manufacture blowing agent. The pre-pressurised particles are passed into the mould
as normal, but the additional blowing effect of the air allows significantly greater
expansion within the mould, resulting in moulded densities comparable with the initial
bulk density of the particles, as low as 11 kg/m3. Although the process is essentially a
batch method, it can be operated quasi-continuously by use of a large pre-pressurising
vessel in which particle levels are maintained by a small dosing feed tank and from
which pressurised particles are taken as required to feed moulds. Tank volumes need to
be large enough to achieve an average residence time of the required 4-6 hours. The
method is described as the Pressure and Temperature System (PAT) or, in its quasi-
continuous form, C-PAT.

Production of EPP beads is also possible by extrusion, and in 1996 Montell introduced
Higran F, an EPP bead grade based on extrusion foaming of their high melt strength Higran
polypropylene. Technology is available from Berstorff and essentially involves cutting the
extrudate directly at the die plate by means of a rotary knife [1]. The pellets expand due to
the pressure decrease and are then cooled in a water flow prior to drying and bagging. The
process can be used for both polyethylene and polypropylene bead production.

8.2.3 Extruded Crosslinked Foam - Processes

There are essentially two processes for the manufacture of crosslinked polyolefin foam by
extrusion. Both use a chemical blowing agent but are distinguished by the crosslinking method:

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• Irradiation crosslinking, in which crosslinking and expansion are separate making it


easier to balance the two stages of reaction

• Chemical crosslinking, in which crosslinking chemicals are compounded into the


mix at an early stage, with crosslinking taking place at the same stage as expansion.
This process is more sensitive to operate owing to the additional heat input at the
compounding stage and the requirement to balance crosslinking and blowing agent
decomposition at the expansion stage.

Both processes were originally developed in Japan and have subsequently been
commercialised worldwide. The chemical crosslinked process is the more common as it
obviates the requirement of costly irradiation equipment.

8.2.3.1 Irradiation Crosslinked Extruded Sheet

The process, originally developed by Sekisui Electrical Co., Japan, involves three stages;
sheet extrusion, irradiation crosslinking, and expansion.

In the first stage, powder grades of LDPE or EVA copolymers or blends are fed into a
high length:diameter ratio (L/D) extruder, e.g., 30:1, together with a chemical blowing
agent and activators, lubricants, pigments as required. A powder polymer feed is necessary
to ensure good mixing and uniform feed ratio with the chemical blowing agent, which is
added at typical levels of 10-20 phr. An essential requirement is to keep the melt
temperature below the decomposition point of the blowing agent to prevent premature
expansion in the extruder, and melt temperatures normally are maintained at 130-145
ºC which is adequate for melt fluidity without pre-decomposition. The extruder is designed
to provide good mixing whilst giving good temperature control, and feeds a sheet die
providing extruded sheet up to 1.5 m wide and 4 mm thick.

At the end of the extruder line, the sheet is exposed to radiation. Although technically
this could be from a gamma ray source (Cobalt 60), in practice electron beam radiation
is used owing to the greater control, freedom from gradual decay, and no requirement
for permanent heavy shielding (though some shielding is necessary). However, electron
beam radiation equipment of the type which can be safely used in a normal factory
environment is not as penetrating as gamma radiation and this imposes a thickness
limitation on the extruded sheet (and hence expanded foam).

Ideally, the induced crosslinking should be uniform through the sheet and this may be
better achieved with thicker sheet by passing twice through the beam, the second time

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Polyolefin Foams

the sheet being turned over. This does however interfere with process continuity and
adds to cost. Radiation doses are in the range 1000-200000 Gy, depending on formulation
- EVA is more sensitive to radiation requiring a lower dose for crosslinking and is usually
present in the mix for this reason. Crosslink levels are substantially lower than, for
example, rubber vulcanisation, with solvent extractable levels around 30-40%.

Although the process is generally thought of as continuous, in practice the crosslinked


sheet is stored in take up rolls until needed and then expanded as required. Extrusion
crosslinking stages do not then have to match the linear throughput rate of the expansion
stage and storage space requirements are reduced.

Expansion is carried out in an infra red (IR) hot air oven generally arranged vertically so
as to minimise the degree of contact of the hot expanding sheet with guidance bars
which have to cope with the three dimensional expansion of the sheet. Temperatures are
in the range 220-230 ºC. The expanded sheet is taken up on rolls. It has a fine cell
structure and good surface quality, although the latter can deteriorate owing to degradation
from high irradiation doses with thicker sheet. This is another factor limiting sheet
thickness.

8.2.3.2 Chemically Crosslinked Extruded Sheet

This process was developed independently in Japan by Furukawa Electric Co. and Hitachi
Chemical Co. and, like the irradiation process, has subsequently been licensed for
operation worldwide. The Furukawa and Hitachi processes are similar in the initial
stages, differing at the expansion stage. The first stage involves melt compounding a
peroxide crosslinking agent and a chemical blowing agent with the chosen polymer.
Since both the crosslinking agent and the blowing agent will decompose or react if
compounding temperatures reach critical levels for any length of time, temperatures at
this stage are closely controlled and the crosslinker and blowing agent system are selected
so as to give a safe operating window.

The usual crosslinker is di-cumyl peroxide (DCP) which has a half life of l minute at
170 ºC and a melting point of 55-60 ºC. Dispersion is often aided by use of an inert
carrier which mitigates the screw slip resulting from the presence of melted peroxide.
The blowing agent is normally activated ADC formulated so no significant decomposition
occurs below 120-130 ºC. However, care has to be taken to eliminate ‘dead spots’ in the
mixer where material may be held up for an extended time since this can result in some
premature blowing. Decomposition of the blowing agent is also dependent to some extent
on particle size, and this is also controlled.

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Compounding methods include both internal Banbury type mixers feeding a pelletising
line, and twin screw compounding extruders. Good dispersion is essential in achieving
high quality expanded sheet with uniform cell structure. Crosslinker and blowing agent
may be compounded together or as separate mixes.

Compounded pellets are then fed to a sheet extruder having good mixing characteristics
whilst minimising heat build up. Extruder design is critical in achieving this and more
recently co-rotating twin screw extruders are receiving consideration owing to their good
mixing characteristics combined with heat transfer for good cooling. Under these conditions
premature crosslinking and blowing can be eliminated. These reactions are time/temperature
dependent and the aim is to achieve good mixing whilst temperature does not exceed a
maximum determined by the residence time in the extruder and die. In practice, temperatures
are maintained at 110-120 ºC, and the main problem encountered is normally hang up of
mix at elevated temperature in the die or extruder such that the theoretical residence time
is significantly exceeded. This can result in crosslinked or even expanded particles in the
extruded sheet which give rise to defects when the sheet is expanded. Following from these
considerations, sheet die design is such as to minimise dead spots.

The extruded sheet is taken up on rolls and held at least 24 hours before proceeding to
the expansion stage. Some quality control tests may be carried out on the extruded sheet
but these are generally restricted to a check on thickness and an inspection for obvious
premature reaction of crosslinker or blowing agent.

At the expansion stage, differences in the two processes become apparent:

• Furukawa process: a continuous wire mesh conveyor is used to carry the sheet through
a three zone hot air oven. Heating is accomplished by hot air jets above and below
the conveyor which serve also to release the sheet from the conveyor after significant
crosslinking so as to allow expansion. Failure to release will result in tearing as the
sheet tries to expand, such tearing and poor release often being indicative of insufficient
crosslinking. Although the crosslinking step is arranged to occur at a lower temperature
than blowing agent decomposition, in the Furukawa process the two processes to
some extent go on concurrently. Oven temperatures are about 230 ºC. The expanded
sheet passes through an edge trimmer and then via a take off system to a take off roll.

• Hitachi process: the compounded sheet is taken by a silicone rubber/fibreglass


reinforced conveyor into an infra red preheating crosslinking oven where a high
degree of crosslinking is achieved prior to subsequent expansion. This level of
crosslinking enables the sheet to expand totally unrestricted in the next stage which
is a hot air oven. No mesh conveyor is needed. The separate crosslinking zone enables
a higher level of crosslinking and lower foam densities to be achieved compared with

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Polyolefin Foams

the Furukawa process. In addition, the higher melt strength which permits free
expansion also gives a smoother skin with finer cells and fewer cell irregularities
(voids or pinholes). A disadvantage is the necessity of maintaining tight control over
the balance of crosslinking and blowing; too great a level of crosslinking restricts
expansion and may cause excessive shrinkage of the expanded sheet, whilst a low
crosslink level will result in a low melt strength and consequent likelihood of sheet
tearing and/or cell collapse during expansion. As with the Furukawa process, expanded
sheet is trimmed and taken up on a roll.

Both the Hitachi and the Furukawa processes result in some surface oxidation/degradation
during the high temperature expansion stage. Process modifications to minimise this
have been described, e.g., use of a nitrogen blanket, but these are not known to be
operated. The same applies to processes using a high temperature liquid salt bath for
curing and expansion. Such a process is reported to give both good cell structure and
high surface quality [6].

8.2.3.3 Materials

• Polymers

Selection is made primarily on the basis of ensuring that melt processing temperatures
should not exceed 120 ºC during compounding and extrusion of unexpanded sheet.
Normally, LDPE and EVA, alone or as blends, are used, with melt flow indices in the
region of 2.0-4.0 g/min. These polymers, particularly EVA, crosslink reasonably efficiently
with peroxides and process at acceptably low temperatures. HDPE and LLDPE require
higher processing temperatures and are not used. Polypropylene, whilst a desirable polymer
to expand owing to its higher use temperature and generally lower cost, poses problems
for crosslinked foam production due firstly to the necessarily higher processing
temperature and secondly to the difficulty of crosslinking. Free radical crosslinking with
peroxide normally leads to chain scission and degradation of polypropylene rather than
crosslinking. Polypropylene sheet foams are therefore made using blends of suitable
polypropylene copolymers, which have a lower and broader melting point and hence
lower processing temperatures, together with an additive to enhance crosslinking. Various
possible additives have been described in the patent literature, many of them of dubious
acceptability for health and safety reasons, e.g., divinyl benzene, and manufacturers of
crosslinked polypropylene foam sheet use undisclosed proprietary systems.

More recently, metallocene catalysed polyethylenes (mPE) have become available. These
materials can have enhanced physical properties owing to the greater regularity of chain

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Borealis Exxon Phillips Elenac Dow Dex Plastomers Dupont Dow

Handbook of Polymer Foams

structure, and the catalysts allow a wide range of polymers to be produced having densities
from about 0.87 to 0.94 g/cm3. Polymer flexibilities vary in line with density and at the
lower end compare well with the flexibility of EVA copolymers. The availability of these
materials in Europe has been reviewed by Maier [7] and is summarised in Table 8.2.

Densities cover the range of medium density polyethylene (MDPE; 0.93-0.94 g/cm3),
LDPE (0.915-0.935 g/cm3) and LLDPE/very low density polyethylene (VLDPE; 0.90-
0.93 g/cm3), together with new materials having densities less than 0.90 g/cm3.

A differentiation is sometimes made between polyolefin plastomers (POP), which have


applications in the film and packaging area, and the newer lower density polyolefin
elastomers (POE) which are now competing with thermoplastic elastomers (TPE), flexible
polyvinylchloride (PVC), crosslinked elastomers, and ethylene copolymers [EVA and
ethylene methyl acrylate (EMA)].

Whilst having the potential to provide improved foam properties and also foam flexibilities
previously only achievable through use of copolymers such as EVA, the processing
problems of metallocene polyolefins, resulting in high heat build up at the sensitive mixing
and extrusion stages, has restricted the use of these materials for cross-linked foam
production. When used, they are always blended with something else, e.g., LDPE.

Table 8.2 Commercial availability of mPE (Europe)


Producer Product Co-monomer Density range, g/cm3
Borealis Borecene 1-hexene 0.934-0.94 0
Dow Elite 1-octene 0.916-0.935
Exxon Exceed 1-hexene 0.918
Phillips mPact 1-hexene 0.916-0.933
Elenac Luflexen 1-butene 0.903-0.917
Elenac Luflexen 1-hexene 0.918
Dow Affinity 1-octene 0.868-0.915
Dex Plastomers Exact 1-octene 0.90 2
Dupont Dow Engage 1-octene 0.8863-0.910
Source: [7]

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Polyolefin Foams

• Blowing Agents

ADC is used as the blowing agent of choice. Decomposition is controlled by the use of
activators such as zinc oxide or an organo zinc complex which may be incorporated in
the material as supplied, or compounded in later as part of the mix. A further factor
controlling decomposition rate and the temperature of decomposition is particle size.
Fine particles decompose preferentially and thereafter catalyse the decomposition of larger
particles. Manufacturers of ADC therefore use processes involving crystallisation control
and air grading, aiming to produce uniform coarse particles (diameter 3 μm or less).
Such materials reduce the possibility of premature decomposition during mixing and
extrusion.

Particle size distribution does vary between grades from different manufacturers and
foam producers tend to have preferences depending on the particular process being
operated. The electron beam process, which separates the crosslinking and expansion
stages, can tolerate a somewhat wider particle size distribution than the chemical
crosslinking processes.

• Crosslinking Agent

The requirement of the crosslinking agent is to remain inactive during compounding and
extrusion (some 5 minutes at 120 ºC), with rapid crosslinking triggered subsequently at
higher temperatures before any substantial decomposition of blowing agent. Alkyl
peroxides are most commonly used, usually dicumyl peroxide (half life 1 minute at
171 ºC). If a higher decomposition temperature is needed, then 1, 3-bis (t-butyl peroxy
iso propyl) benzene is an alternative (half life 1 minute at 182 ºC).

Silane crosslinking has been described [8] and is in limited commercial use. Silane groups
are grafted on to the polymer during compounding and crosslinking is effected after
extrusion by exposure to moisture (or steam). The process eliminates the possibility of
premature crosslinking in the extruder (provided polymers are dry) but imposes a thickness
limitation owing to the exposure time necessary to allow diffusion of moisture into the
foam, which increases as the square of extrudate thickness.

• Other Additives

Antioxidants and UV stabilisers are not normally added to formulations. LDPE grades
used are free from antioxidants (although EVA grades normally have low antioxidant
levels as supplied). Although such additives could reduce surface oxidation at the high

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temperature oven expansion stage, they interfere with peroxide crosslinking.


Microcrystalline additives such as talc have been mentioned in the literature as cell
nucleators but are not normally used. Process aids such as zinc stearate may be added,
but these are also activators for the blowing agent, which must be allowed for. Crosslinking
aids, in the form of small amounts of EVA or acrylate terpolymers, may be used but have
an effect on foam flexibility. Pigments are commonly added to produce coloured foams.
Pigment masterbatches aid dispersion with minimum shear (and heat build up) and give
a cleaner working environment. It should be noted that no pigments are needed to produce
white foams, since the multitudinous reflections from cell walls gives foams a naturally
white appearance. It may however be necessary to use white pigments (titanium dioxide)
in combination with coloured pigments if pale pastel colours are required.

Flame retardants are added to produce flame resistant foams, antimony trioxide/halogen
systems being the most effective. Like pigments, these are added as masterbatches.

Typical Formulations are, for 100 parts polymer:


5 phr ADC and 0.5 phr DCP to give foam density 100 kg/m3
10 phr ADC and 0.7 phr DCP to give foam density 60 kg/m3
17 phr ADC and 0.9 phr DCP to give foam density 30 kg/m3

Further information on the Sekisui, Furukawa and Hitachi processes can be found in
reference [6].

8.2.4 Press Moulded Crosslinked Foam Process

The semi-continuous nature of the crosslinked sheet foam process gives good production
efficiency but both the radiation and chemical crosslink routes have a limitation on the
maximum thickness of foam that can be produced. In the radiation process it is the
inability of the electron beam to achieve uniform crosslinking with thick extrusions,
whilst in chemically crosslinked foam the limitation is heat transfer at the crosslinking/
expansion stage. Normal maximum thickness of extruded crosslinked sheet foam is about
15 mm. (The nitrogen autoclave process described later can produce ‘thin blocks’ up to
about 50 mm).

Whilst thicker foams can be produced from thin sheet by heat lamination, problems can
arise due to surface degradation at the expansion stage and lamination quality is poor
unless a surface skin is removed beforehand.

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Polyolefin Foams

Hence, thick foams (up to 120 mm) are made by press moulding or injection moulding
methods whereby crosslinking and blowing agent decomposition are carried out in a
closed mould. Expansion occurs subsequently.

Note: injection moulding is generally limited to production of foam densities greater


than 100 kg/m3.

Several variations of the press moulded process are in commercial use, and are discussed
in Sections 8.2.4.1 and 8.2.4.2

8.2.4.1 Single Stage Process

Closely related to the methods used for the production of closed cell elastomeric and
flexible PVC foams, the process involves firstly compounding the polymer with crosslinker,
blowing agent and any required additives. As with crosslinked sheet foam, care must be
taken to minimise heat build up so as to avoid premature crosslinking and blowing.
Banbury batch mixers and twin screw compounding extruders are both used. A defined
weight of compound is then placed in a mould and press cured, typically for 45 minutes
at 150 – 170 ºC. Under these conditions curing is complete and the blowing agent is fully
decomposed. When the mould is opened the product expands directly, literally jumping
out of the mould. Moulds are designed to facilitate this.

Whilst having the advantage of simplicity, the single stage process has several
disadvantages, namely:

• High mould pressures are generated, particularly at low foam densities which use
formulations with greater amounts of blowing agent generating larger gas volumes
for greater expansion. This requires the use of heavy duty presses and high clamping
forces.

• Only a part of the platen area can be used so as to avoid contact of the expanding
foam with the guide pillars, with consequent foam distortion.

• High press opening speeds are necessary (> 10 cm/s) to accommodate the rapid foam
expansion.

Mould design is critical to avoid generation of internal stresses with the likelihood of
foam defects during expansion.

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Handbook of Polymer Foams

For these reasons foam density is restricted to a minimum of 70 kg/m3 with the single
stage process, higher degrees of expansion requiring a two stage process.

8.2.4.2 Two Stage Process

Compounding is carried out as for the single stage process, but at the press curing stage
crosslinking and gas evolution are controlled to ensure no or only partial expansion
occurs on release from the mould. Full expansion is carried out in a later second stage.
Several variants are operated, including:

• Press curing for some 40 minutes at 130 ºC. The product is essentially fully crosslinked
but there is only partial decomposition of the blowing agent and therefore only limited
expansion from the mould. The expansion is completed by transferring the product
to a hot air oven, typically for 50 minutes at 170 ºC.

• Press curing for some 20 minutes at 130 ºC, resulting in partial curing but no significant
decomposition of blowing agent. The product is taken from the mould and transferred
to a hot air oven as before to complete curing and enable expansion, typically
60 minutes at 165 ºC.

Press curing at 170 ºC followed by chilling. Curing is complete and most of the blowing
agent is decomposed. Chilling the product (before the mould is opened) gives the material
sufficient strength to prevent significant expansion after removal from the mould. Whilst
immediate transfer to an expansion oven is not necessary, there is a slow loss of the
blowing agent trapped at high pressure within the solid product, and final expansion is
generally carried out shortly after press curing, again in a hot air oven.

In all these two stage processes, product from the first stage can be transferred to an
expansion mould for the second stage, in which case heating can be carried out using
steam. An expansion mould allows final dimensions (and hence foam density) to be
closely defined.

Formulations for press moulding are not so critical as those for crosslinked extruded
foam since it is not so essential to achieve a balance between crosslinking and blowing
agent decomposition. However, the same requirements exist regarding choice of these
additives, and ADC together with DCP crosslinker are the agents of choice. Polymers are
LDPE/EVA blends with zinc oxide activator and stearic acid processing aid. A typical
formulation is shown in Table 8.3.

Pigments and flame retardants may be incorporated to give coloured or flame resistant
foams and generally also improve cell structure by also acting as nucleating agents.

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press moulding Polyolefin foams

Polyolefin Foams

Table 8.3 A typical formulation for press moulding


Ingredient Quantity
LDPE 100 phr
EVA 15 phr
DCP 2.1 phr
AZDC 6.0 phr
Zinc oxide 2.0 phr
Stearic acid 1.0 phr
Source: [9]

8.2.5 Injection Moulded Foam Process

Polymers are selected to have high melt fluidity in the range 100 – 120 ºC so as to permit
good mixing without predecomposition. Screws with high L/D ratio (25 – 30:1) are used
for mixing prior to injection, and formulations are similar to those used for press curing.
During moulding, similar constraints apply as for the single stage process since the product
expands directly from the mould, with mould design important in preventing undue
internal stress during expansion. Mould temperatures are about 200 ºC and insulation is
needed to maintain temperature uniformity (and hence uniformity of crosslinking and
expansion within the product). Foam densities are normally in the range 100 - 300 kg/m3.

Press curing processes have been reviewed by Puri and Collington [9].

8.2.6 The Nitrogen Autoclave Process

This is a unique process operated by only one company worldwide (Zotefoams plc,
Croydon, UK). The process was originally developed in the late 1950s and was
commercialised in the early 1960s. It comprises three stages, namely:

• Extrusion and crosslinking

• High pressure gassing

• Low pressure expansion

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8.2.6.1 Stage 1

At the first stage a polyolefin together with a crosslinking agent and any other desired
additives such as pigments and flame retardants is extruded using an extruder with good
mixing ability. Originally single screw extruders with high L/D (25 - 30:1) and appropriate
mixing sections were used; more recently co-rotating twin screw compounding extruders
have been introduced. The mix is fed to an extrusion die to produce sheet up to some
12 mm in thickness. Extruded sheet is carried on a conveyor belt (coated with
fluoropolymer for good heat resistance and to avoid sheet sticking) into a curing oven
where the temperature is held at some 160 ºC over a residence time of about 20 minutes
to achieve complete curing. Since there is no blowing agent incorporated at this stage the
problem of balancing crosslinking and blowing reactions is eliminated, though care must
be taken to avoid premature crosslinking. A peroxide crosslinker is used having a
somewhat higher decomposition temperature than DCP at levels very much lower than
those used in other chemically crosslinked foam systems. This reflects the higher molecular
weight polymers used (resulting in improved foam properties) and the lower crosslink
level needed to stabilise the foam during expansion. Polymers used are HDPE, LDPE,
EVA, EMA, polypropylene, metallocene polyolefins, and various blends of these materials.

After exiting the crosslinking oven, the extruded sheet is cooled and cut to precisely sized
polymer slabs. These are quite stable and may be stored indefinitely until required for expansion.

When first developed the process did not use chemical crosslinking. Cut slabs were
crosslinked after the extrusion stage by radiation in a separate operation. This option,
although more costly, is still used for polymers which have too high a processing
temperature to allow incorporation of peroxide without premature decomposition. This
includes HDPE, where slabs are cured off site either by cobalt 60 gamma radiation or
electron beam irradiation. The radiation sources are more penetrative than would be
possible in a normal factory environment and the thickness limitations of the Sekisui
process do not apply. An irradiation regime is used whereby slabs are turned and
interchanged to ensure uniform crosslinking through each slab.

Since slabs can be sampled after crosslinking, quality controls can be introduced to ensure
the process is operating within specified tolerances. As well as slab dimensions this check
includes measuring crosslink level which is not possible with other processes. Any
deviations can be corrected by minor adjustments of crosslinker at the extruder.

8.2.6.2 Stage 2

At the second stage the blowing agent is incorporated. This is pure nitrogen which is
dissolved in the slabs by exposure to the gas at high pressure (up to 70 MPa) and

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Polyolefin Foams

temperature (above the melting point of the polymer, typically 150 ºC. Under these
conditions, despite the low solubility of nitrogen in polyolefins, sufficient gas dissolves
to ensure subsequent expansion. The amount of gas dissolved, and hence the degree of
subsequent expansion depends on temperature and more particularly, pressure. Final
foam density is determined at this stage, and foams having densities over a wide range
(commercially 15 to 120 kg/m3) are made from a single formulation by varying the
pressure in the high pressure autoclave.

Temperature/pressure cycles must be sufficient to ensure complete dissolution of gas.


This is a diffusion process dependent on temperature, pressure and slab thickness, and
times are typically 6-8 hours to achieve saturation.

Foam quality can deteriorate if there is any oxygen present as an impurity in the nitrogen
and through any temperature non-uniformity. Measures are taken in gas supply and
autoclave design to minimise these factors.

After the slabs are saturated with nitrogen, gas pressure is reduced and the slabs cooled.
Gas comes out of solution causing cell nucleation but no significant expansion takes
place at this point. Cooling continues until the slabs have sufficient solid strength to
contain the trapped nitrogen without expansion, whereupon the pressure is reduced to
zero gauge and the slabs removed from the autoclave.

The pressure cycle in the autoclave controls cell size. A fast reduction in pressure after
saturation increases the cell nucleation rate, resulting in a greater number of cells in the
expanded foam with consequently smaller diameter. Slower rates of pressure reduction
result in larger cells. Cell diameters are controlled within the range 0.1-1.0 mm.

8.2.6.3 Stage 3

The final expansion stage is carried out within a few hours of gassing to avoid any
significant loss of gas from the slabs. Expansion is done in a low pressure autoclave of
sufficient size to accommodate full expansion of the foam blocks. Air pressure is applied
(approximately 1.5 MPa) and the temperature raised above the polymer softening point
to about 150 ºC. When the slabs have reached this temperature the pressure is released
to allow rapid expansion providing foam blocks up to 2 m x 1 m in length x width and
up to 50 mm in thickness.

Whilst it would be possible to expand in an air oven, the use of a pressurised vessel, by
preventing expansion until the slabs are at uniform temperature, enables controlled
expansion with no internal stress and hence improved foam quality.

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Capital cost of the autoclave process is substantially more than that of other processes,
due mainly to the cost of the high pressure autoclave and ancillary equipment. The design
of the autoclave, including the closure which allows for easy insertion and removal of
extruded slabs whilst maintaining the necessary high pressures during the process cycle,
is proprietary to Zotefoams as are the detailed operating parameters. Running costs can
nevertheless be lower than other processes owing to the high productivity of a high
pressure autoclave for the production of low density foam, and the absence of any costly
blowing agent.

Advantages of the autoclave process are:

• The blowing agent, pure nitrogen gas, leaves no solid residues in the foam. Such residues
can reach significant levels in foam expanded with chemical blowing agents and are a
major limitation in production of such foams at densities less than some 25 kg/m3. The
autoclave process does not have this limitation and foams are produced down to 15 kg/m3
commercially and 10 kg/m3 foams have been made in development work.

• Crosslinking and expansion are separated, simplifying production, enabling quality


control measures to be introduced at intermediate stages and widening the choice of
suitable polymers. The option of irradiation crosslinking enables manufacture of
foams using polymers having high processing temperatures such as HDPE.

• Cell size is under control at the high pressure second stage. Crosslinked slabs may be
expanded in a range of cell sizes and this choice does not have to be made until the
foam is expanded.

• Foam cell structure, i.e., the uniformity and integrity of the cells, is significantly
better than that found with other processes, leading to property benefits, particularly
in strength and compression set.

A disadvantage is the high capital cost and it is this, together with the undisclosed
proprietary operating parameters, which have prevented this technology from becoming
more widely adopted. However, Zotefoams have recently entered into a sales alliance
with Alveo (who produce extruded sheet and block foam), and are also building a
manufacturing plant in North America, so the technology may be starting to disseminate.
Interestingly, the North American plant will operate initially by expansion of gassed
slabs produced by the UK plant and shipped over in refrigerated containers. This reduces
the transport costs of shipping expanded foam and eliminates for a time the cost of a
high pressure autoclave at the new site.

Some further information on the autoclave process is given in references [10], [11] and [12].

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8.2.7 Recycling Processes

Non-crosslinked polyolefin foams can be readily recycled by granulation and extrusion.


The recycled product may be incorporated with virgin polymer at levels of 10 - 20% to
produce new foam with little effect on foam properties. The main difficulty, as with
many recycling operations, is that of segregation and collection of foam for recycling
without contamination, e.g., by other foams which may not be easy to identify. Within
the manufacturing operation this problem can be solved by careful control of reject
material and trimmings, but there is a considerable problem in ensuring foam consumer
waste is free from contamination. Some foam manufacturers in response, for instance, to
packaging waste legislation, have set up schemes whereby foam can be segregated,
collected and returned to the production unit for recovery.

Crosslinked foam cannot easily be recovered and used for new foam production since the
crosslinks interfere with melt flow. Other recycling methods have therefore been developed:

• Reuse is emphasised, the crosslinks being beneficial in establishing and maintaining


good properties. Crosslinked polyethylene foam is the material of choice for reusable
packaging, for example as in house transit packs for automotive parts.

• Coarsely chopped foam may be heat moulded to form, e.g., drainage liners for rooftop
gardens. The granules (10 - 20 mm in size) are transported on a conveyor through a
heating chamber and are then consolidated by shaped rollers or in a press.

• More finely chopped foam (5 - 10 mm in size) can be consolidated by equipment in


which foam granules are passed between a rotating and a stationary plate. Granules
become heated above the melt point by shear effects and the foam structure is
destroyed. The consolidated granules can be used as a coarse moulding powder
although the original objective of this process was density increase to reduce waste
volume. A foam of density 50 kg/m3 can increase in density to some 400 kg/m3.

• Many regard energy recovery as the best option for recycling plastics although this is
not encouraged by, for example, the European Packaging Regulations. Polyethylene
can be combusted to produce energy with an effectiveness some 3 times that of
cellulosic products, e.g., paper, cardboard, wood, with no possible evolution of noxious
halogen or nitrogen compounds. Domestic waste can be difficult to combust without
the presence of waste polyethylene.

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8.2.8 Post Manufacturing Operations

Polyolefin foam is normally an intermediate material which has to undergo further


processes to give a final product. Such processes may include:

Sawing Adhesive bonding


Splitting Routing
Die stamping Sanding
Hot wire cutting Drilling
Laminating Flocking
Butt welding Printing
Thermoforming

The surface of polyethylene foam is non-polar and has a low level of interaction with
surface treatments such as flocking, printing and adhesive bonding. Such treatment
generally requires special formulations or a surface pre-treatment to ensure success.
Copolymer foam such as EVA is more amenable to these processes as this is more polar.

Sheet lamination to build up thick blocks from two or more sheets does not require
adhesive as the surfaces will self-bond if heated above the polymer melting point. The
original sheet surface, which may be rough and degraded through oxidative reactions
during the high temperature stages of production, is often split off prior to lamination.
Surfaces are heated by hot air or, preferably, by passing over a heated blade (the latter
technique gives greater temperature uniformity) and then brought together immediately
after the hot zone. The bond formed is at least as strong as the foam. Laminates having
more than two sheets are preferably built up symmetrically to avoid distortion (curvature)
caused by minor differences in compression imposed by top and bottom feed rollers.

Butt welding is carried out using analogous techniques to heat lamination.

Several different methods are in use for thermoforming which, in contrast to heat
lamination, can only easily be carried out with crosslinked foams. Whilst thermoforming
of solid materials is precluded by the presence of crosslinks, in polyolefin foams a
small amount of crosslinking stabilises the cell structure in the hot state and the moulded
form is retained by the strength of the polymer below its softening point. The methods
in use are:

• Heat moulding: foam is placed in a mould with an overload of some 10%. The
mould is closed, heated to a temperature above the softening point of the polymer,
e.g., for polyethylene foams, 140-150 ºC, and then cooled. The moulded product is
removed from the cold mould.

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• Heat impression moulding: foam sheets cut to the appropriate size are placed in an
infra red oven for a time dependent on sheet thickness and density, e.g., for LDPE
foam of 45 kg/m3 density, Zotefoams recommend 10 seconds heating at 140 ºC per
1 mm thickness of foam. The hot sheet is transferred to a cold mould and pressed for
a similar time to that used for heating. The method is faster and cheaper than heat
moulding but makes considerable demands of foam hot strength for low density
foams and/or high draw ratios. Better thermoforming is found with higher density
foams having intrinsically greater hot strength.

• Vacuum forming: the foam is heated as for heat impression moulding and then
transferred to a one piece mould with provision for the application of vacuum to
draw the foam down to the mould shape.

• Body forming: in an interesting variant used for medical applications hot sheet is
wrapped around the human body to produce wrist, ankle, knee and other supports
which conform precisely to the body shape. Although the foam is heated to 140 ºC,
the low heat content and thermal conductivity allow this to be carried out without
any discomfort to the patient.

8.3 Properties of Polyolefin Foams

As with all foams, properties depend on the following factors:

• Type of polymer

• Closed cell versus open cell content

• Foam density

• Presence of any modifying additives

• Cell structure and integrity

Polyolefin foams are almost wholly closed cell and modifying additives are mostly
restricted to small amounts of pigments, nucleating agents and processing aids, none of
which have any significant effect on properties. Flame retardants, however, are added at
levels up to 20% by weight and can affect physical properties in addition to conferring
flame resistance. Fillers are not normally used since they increase density without any
positive contribution to physical properties. In general, therefore, physical properties
depend on polymer, foam density and cell structure. The effect of foam density on
properties is shown in Table 8.4 for a range of LDPE based foams.

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Handbook of Polymer Foams

Table 8.4 Effect of foam density on properties (autoclave process)


Formulation
1 2 3 4 5
Foam density (kg/m3) 24 33 45 60 70
Compression strength 25% (kPa) 35 40 50 70 85
Compression set (%) 1 32 27 22 19 16
Tear strength (N/m) 410 690 1130 1490 1855
Tensile strength (kPa) 340 455 600 790 945
Elongation at break (%) 105 135 150 160 170
Flexural modulus (MPa) 0. 4 0.7 1.0 1.7 2.7
Note 1: 72 h at 50% compression, 0.5 h recovery
Source: Zotefoams plc, data sheets

As may be expected, all properties improve as foam density increases.

The effect that choice of polymer has on properties is shown in Table 8.5, comparing
foams of similar densities.

The increase in maximum use temperature is evident in moving from ethylene copolymers
to homopolymers, reflecting the higher softening point. The greater elongation and
flexibility of the copolymer is also shown. Highest strength is found with high density
polyethylene foams, making these materials very tough and suitable for applications in
areas of high impact stresses.

Some data on the effect of foam structure has been given in [12]. Foams made using
chemical blowing agents are shown to have a more poorly defined cell structure which is
considered to relate to the lower physical properties measured, e.g., tensile strength 45%
lower, elongation at break 30% lower, and compression set up to 3 times greater compared
with autoclave foams.

Some data has been published on autoclave foams produced using metallocene polyolefins
[11, 12]. Compared with LDPE foams of the same density and similar flexural quantities,
metallocene foams have approximately 60% higher tensile strength, 55% higher

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Zotefoams plc

Polyolefin Foams

Table 8.5 Effect of polymer type on properties (autoclave process)


Polymer type
EVA LDPE HDPE
Foam density (kg/m3) 35 33 30
Maximum use temp. (ºC) 80 105 125
Compression strength 25% (kPa) 35 40 60
Compression set (%) 1 33 27 22
Tear strength (N/m) 730 690 1320
Tensile strength (kPa) 620 455 825
Elongation at break (%) 200 135 55
Note 1: 72 h at 50% compression, 0.5 h recovery
Source: Zotefoams plc, data sheets

elongation at break and more than double the tear strength, making these materials
particularly suitable for applications involving hard wear.

8.4 Applications

Polyolefin foams have an extremely diverse range of applications and there are few, if
any, industries where these foams are not used. Some of these areas, and specific
applications, are listed:

• Appliances

Gaskets and vibration pads: foam densities from 15 to 60 kg/m3, using LDPE or EVA,
depending on the particular performance requirements. EVA foam has greater flexibility
and compression recovery whilst LDPE has better load bearing capability.

• Automotive

Gaskets and seals; water barriers; carpet underlay; sound insulation; vibration pads;
headliners; impact protection. LDPE foams in densities from 15 to 45 kg/m3 are generally
used, with EVA and EMA foams having application where greater flexibility is needed,

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e.g., gaskets, carpet underlay. HDPE foams have a use where high impact protection is
needed. Polypropylene copolymer foam sheet, with higher temperature resistance up to
130 ºC, also has a wide application, and recent low density (15 kg/m3) metallocene
foams are also being promoted as they offer good properties with weight saving.
Polypropylene bead foam is widely used in impact absorbing bumpers.

• Building and Construction

Sealing backers; expansion joints; glazing seals; eaves fillers; impact sound absorption;
pipe insulation. LDPE and EVA foams in a range of densities from 15 to 50 kg/m3 are
used, with the higher densities required particularly where load support is needed, e.g.,
under floor blocks providing impact sound absorption. Flame retardant grades are used
where appropriate in conformity with building regulations.

• Aerospace

Sealing; flotation cushions; sound insulation; ducting lining. An important criteria for
almost all aerospace applications is flame retardance to Civil Aviation Authority (CAA)
8 (UK) [13] or Federal Aviation Authority (FAA), Federal Aviation Regulations (FAR)
(USA) standards which involves a vertical burn test for flammability. Airbus have
additional requirements involving smoke and toxicity. LDPE foams with densities up to
50 kg/m3 are in use but lower density foams are preferred (for weight saving reasons)
where these are capable of meeting physical property requirements. Zotefoams’s very
low density (15 kg/m3) flame resistant foam based on metallocene polyethylene is
specifically targeted at aerospace applications.

• Marine

Life jackets; life buoys; fenders; oil booms; floating hoses. Foams used for these
applications are normally LDPE based with densities up to 60 kg/m3. Lower density
foams have slightly greater buoyancy but lower physical properties and are only used
where cost is an important consideration. In some applications, e.g., fenders and floating
hose, the foam is coated with one or more layers of protective skin, for instance
polyurethane, in order to give a surface resistant to impact which could damage
unprotected foam. In the case of floating hose, the ability to withstand and recover from
the compression resulting from occasional deep immersion is important.

• Medical and Health Care

Splinting; cervical collars; orthopaedic shoe insoles; exercise mats; implement handles;
orthotic supports. Foams used cover the whole range of densities and polymers, choice

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Polyolefin Foams

being dependent on degree of support needed (high foam stiffness) or comfort requirement
(soft flexible foams). Thermoforming is frequently used, including direct forming on the
body, to produce the desired shape.

• Sports and Leisure

Buoyancy aids; swim vests; kickboards; pool games; camping mats; waterslide mats;
backpack inserts; sports shoe insoles; body protection; canoe seats; toys and games;
sports mats; helmet liners; surf boards. As with medical applications, a wide variety of
polymers and foam densities are used depending on specific application requirements.

• Electronics

Static dissipative packaging; pin insertion packs; conductive cushion packaging; Faraday
cage shielding; work station mats; tote box liners; conductive shoe insoles. All these
applications aim to prevent damage to sensitive electronic components by safeguarding
against the effects of static discharge. Foam may be LDPE or EVA based and are made
static dissipative or conductive by the addition of high structure (conducting) carbon
black. Relatively high amounts (10-20% phr) are needed to give the required level of
conductivity owing to the low density of the foam. Conductive foams have volume
resistivity typically 5 x 103 Ω cm whilst static dissipative foams have surface resistivities
typically 1 x 107 Ω/sq. ‘Antistatic’ foams are also available, typically with surface
resistivities of 1 x 1011 Ω/sq. These foams, often coloured pink for identification purposes,
are made by incorporation of a partially soluble antistatic agent which diffuses to surfaces
and picks up moisture to form a dissipative surface layer. The product is widely used but
has the disadvantage of performing poorly in dry environments.

• Military

Sleeping mats; missile packaging; weapons packaging; helmet liners; trauma padding;
riot shields. High quality, tear resistant, puncture proof sleeping mats are produced using
EVA foams. Packaging applications normally use LDPE foams, as do trauma padding
and helmet liners. An interesting application is HDPE foam at high density (115 kg/m3)
as an helmet liner in a military helmet designed to protect the wearer from a rifle shot.

• Packaging

Corner pads; case inserts; display packaging; cushion packaging. Some of these
applications are relatively undemanding and cost/appearance are the major criteria.
Cushion packaging however calls upon the foam to provide a consistent level of protection
in packages designed for a particular load and fragility.

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The mechanism of shock protection is impact absorption by plastic deformation of cell


walls when the foam is compressed rapidly. The more rigid foams, or foams with poor
cell structure allowing viscous movement of air between the cells, can give good shock
absorption on first impact but high compression set results in poor performance on
multiple impacts. Flexible foams absorb energy mainly by elastic compression of air in
the cells and deformation of cell walls and do not give a good packaging performance
even on first impact. Best results are obtained with semi rigid foams based on LDPE or
(better) LDPE/HDPE blends. These give good first impact shock absorption and recover
sufficiently after compression to retain a good performance over multiple impacts.

The principles of cushion packaging have been described [14]. Essentially, cushion curves
are generated which show the behaviour of foams of different thicknesses when subjected
to impact over a range of drop heights and impact weights. Peak deceleration (G) is
plotted against static stress to generate a series of parabolic curves. Packaging is designed
so that the expected impact occurs near the trough of the curve, i.e., the lowest peak
deceleration. Foam manufacturers supply data for their products both in graphical form
and as software packages which facilitate the selection of appropriate foam density and
thickness.

Both crosslinked and non-crosslinked foams are used for cushion packaging with better
multi-impact performance from crosslinked foams.

8.5 Foam Specifications

Some applications require foam to meet widely recognised specifications as a prerequisite


of use. A number of those frequently encountered are:

8.5.1 Packaging

• AA-59135 and AA-59136 [15, 16], Gives cushioning, i.e., impact, requirements of
foams for a range of weights, drop heights, etc.

• DEFSTAN 81-116.2 [17]and 93-101.2 [18], Impact requirements for military


packaging, covering two types, i.e., GP - general purpose, and QX - explosive
compatible. The latter requires certified analysis for impurity level.

• UK/SC37767B, military specification for sleeping mats.

• UK/SC4797B, military specification for trauma lining (of combat helmet).

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Polyolefin Foams

• CONEG, Packaging and Packaging Waste Directive 94/62/EC [19], UK Packaging


(Essential Requirements) Regulations 1998. All this legislation specifies maximum
levels of lead, cadmium, mercury and hexavalent chromium in packaging. Levels
started at 600 ppm reducing to 100 ppm after 30th June 2001.

• Quality Standard BS EN ISO 9001 [20]. Whilst this is a site manufacturing standard
rather than a foam specification, it is often a customer requirement and most foam
manufacturers comply. Equivalent environmental and safety standards are likely to
be future customer requirements.

8.5.2 Automotive

FMVSS.302 [21], flammability requirement.

VW/Audi fogging test; requirement for low fogging, i.e., release of organic vapours which
deposit on and obscure windscreens.

8.5.3 Furnishings

S1 1324 (1988) [22] as amended by S1 2358 (1989) [23].

Flammability requirement for furnishing which in the case of polyolefin foam is stated as
BS 5852 [24] ignition source 2 with an FR cover fabric. Some foams meet this test without
FR additives.

8.5.4 Buoyancy

SOLAS [25] specifies foam requirements after temperature cycling, water absorption
and diesel fuel immersion.

BS EN 393 [26], 395 [27], 396 [28] and 399 [29], specify foam requirements for life
jackets. Includes buoyancy test after compression underwater, and a thermal stability test.

8.5.5 Aerospace

CAA 8 [13], FAA FAR 25.853 [30], JAA JAR 25.853 [31].These are the UK, USA, and
joint versions, respectively, of the vertical burn test for flammability assessment.

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ABD 0031 [32] an Airbus specification which adds smoke and toxicity testing to the
CAA 8 [13] assessment.

8.5.6 Construction

UL94 [33], USA Underwriters Laboratory horizontal burning test for plastic materials
which includes foam in Section 12. Materials are ignited in a horizontal orientation, and
assessment includes burn rate and presence of any burning drips.

DIN 4102 (B1/B2) [34], German test for building construction materials. The B2 test is
a vertical burn carried out on a single sample, whilst the more demanding B1 test involves
a vertical chimney with test material on all four sides. An assessment is made of residual
material after ignition and burning, and also temperature of the effluent gases.

8.5.7 Toys

EN 71 [35], this is a wide ranging standard for toys in which part 3, covering toxicity,
applies to foam as manufactured. Other parts refer to the formed final product. Maximum
levels of eight soluble metals are specified.

8.5.8 Food contact

FDA 21 CFR 177.1520 [36] refers to allowable substances for formulations including
foams.

Article 2, 90/128/EEC [37] specifies global migration limits after 10 days at 40 ºC in


contact with a food simulant. These include olive oil and three aqueous types.

8.6 Markets

The market for thermoplastic foams (polystyrene, polyolefin and PVC) is dominated by
polystyrene which has applications mainly in building and construction and packaging.
Polyolefin foams have applications in both these areas, together with many others as
indicated, but tend to be used in niches where requirements are more technically or
physically demanding. Total market is about 10% that for polystyrene.

Some figures for annual demand of polyolefin foams published by Chemical Market
Resources [38] are shown in Table 8.6.

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annual demand Polyolefin foams

Polyolefin Foams

Table 8.6 Annual demand for polyolefin foams, 1997


Country Demand, ktonnes
North America 124
Japan 73
Western Europe 55

Growth was estimated as 4.8% annually. Since, compared with polystyrene, polyolefin
foam is a relatively young product with new products and new applications continuing
to arise, market growth may be expected to continue for some time.

Some further information is included in reference [39].

References

1. Film, Profiles, Beads, Tubes: XE Schaumex and Schaumtandex Lines, Berstorff,


Hannover, Germany, 1998

2. M. Van Calster, Proceedings of Foamplas ‘97 Conference, Mainz, Germany,


p.149.

3. M.H. Mack and J. Meyke, Proceedings of Polyolefins X Conference, Houston,


TX, USA, 1997, p.359.

4. J.R. Cousins and F. Domas, Proceedings of Cellular Polymers Conference,


London, UK, 1991, Paper No.34.

5. J.R. Cousins, Proceedings of Cellular Polymers II Conference, Edinburgh, UK,


1993, Paper No.29.

6. R.R. Puri and K.T. Collington, Cellular Polymers, 1988, 7, 1, 56.

7. R.D. Maier, Kunststoffe Plast Europe, 1999, 89, 3, 45.

8. K.L. Walton and S.V. Karande, Proceedings of SPE Antec ‘97 Conference,
Toronto, Canada, Volume 3, p.3250.

9. R.R. Puri and K.T. Collington, Cellular Polymers, 1988, 7, 3, 219.

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Handbook of Polymer Foams

10. D.E. Eaves, Cellular Polymers, 1988, 7, 4, 297.

11. D.E. Eaves, Proceedings of New Plastics ‘98 Conference, London, UK, 1998,
Paper No.20.

12. D.E. Eaves and N. Witten, Proceedings of SPE Antec ‘98 Conference, Atlanta,
GA, 1998, Volume 2, p1842.

13. The Vertical Burn Test, Civil Aviation Authority Specification No.8, 1974.

14. Cushion Packaging Guide, published by Zotefoams plc

15. AA-59135, Packaging Material, Sheet, 1997.

16. AA-59136, Cushioning Material, Packaging, Closed Cell Foam Plank, 1997.

17. DEFSTAN 81-116/2, Expanded Polyethylene Sheet – Types GP and QX – Grades


A, B, C and D, 1999.

18. DEFSTAN 93-101.2, Expanded Polyethylene Sheet – Hight Density for General
Purpose, 1999.

19. 94/62/EC, European Parliament and Council Directive, 1994/62/EC of 20th


December 1994 on Packaging and Packaging Waste, 1994.

20. BS EN ISO 9001, Quality Management Systems – Requirements, 2000.

21. FMVSS 302, Flammability of Interior Materials – Passenger Cars, Multipurpose


Passenger Vehicles, Trucks, and Buses, 1972.

22. SI 1324, The Furniture and Furnishings (Fire) (Safety) Regulations, 1988.

23. SI 2358, The Furniture and Furnishings (Fire) (Safety) (Amendment) Regulations,
1989.

24. BS 5852, Methods of Test for Assessment of the Ignitability of Upholstered


Seating by Smouldering and Flaming Ignition Sources, 1990.

25. SOLAS, International Convention for Safety of Life at Sea.

26. BS EN 393, Lifejackets and Personal Buoyancy Aids – Buoyancy Aids – 50N,
1994.

27. BS EN 395, Lifejackets and Personal Buoyancy Aids – Lifejackets – 100N, 1995.

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Polyolefin Foams

28. BS EN 396, Lifejackets and Personal Buoyancy Aids – Lifejackets – 150N, 1994.

29. BS EN 399, Lifejackets and Personal Buoyancy Aids – Lifejackets – 275N, 1994.

30. FAR 25.853, Requirements for Compartment Interiors: Crew and Passengers.

31. JAR-25.853, Joint Aviation Requirements for Large Aeroplanes: Compartment


Interiors, Joint Aviation Authorities, Hoofddorp, The Netherlands.

32. ABD 0031, Smoke and Toxicity Test.

33. UL94, Tests for Flammability of Plastic Materials for Parts in Devices and
Appliances, 2001.

34. DIN 4102, Fire Behaviour of Building Materials and Building Components,
1977.

35. EN 71, Safety of Toys, 1998.

36. FDA Title 21: Food and Drugs, CFR 177.1520, Indirect Food Additives:
Polymers – Olefin Polymers, 2002.

37. 90/128/EC, European Commission Directive, 1990/128/EEC of 23rd February


1990 Relating to Plastic Materials and Articles Intended to come into Contact
with Foodstuffs, 1990.

38. W. Dihau, Rubber World, 1998, 218, 6, 17.

39. D.E. Eaves, Polymer Foams, Trends in Use and Technology, RAPRA Technology,
Shawbury, Shrewsbury, UK, 2001.

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Latex Foam

9
Latex Foam

Rani Joseph

9.1 Introduction

Cushionable materials for upholstery, mattresses, etc., have become an indispensable


component of everyday life. Such materials are known as cellular materials because they
are made by providing tiny air cells in a soft matrix such as rubber or plastic. Rubber-
based cellular materials can be made from both dry rubber and rubber latex. Latex-
based cellular material known as latex foam is the topic of this chapter. The number of
air cells, their average size and whether the cells are intercommunicating, partially
intercommunicating or non-intercommunicating determine the properties of latex foam
rubber such as density, cushionability, water absorption, etc. In the case of latex foam
the cells are mostly intercommunicating.

In 1930 a patent was granted for a process which involved mechanical agitation or
whipping of latex into a foam in the presence of additives like soap, gelatin and so on [1]
which assist the foaming process. This led to the production of latex foam by the Dunlop
process in the early 1930s [2]. The essential feature of the process was that after foaming
the latex it could be set using sodium silicofluoride, a delayed action gelling agent. The
product after gelling could be vulcanised in a steam chamber [3, 4]. By 1936, several
alternative methods had been proposed for the production of latex foam but none of
them except the Talalay process [5] was successful. This process originally involved adding
hydrogen peroxide or a low boiling organic solvent to the compounded latex and then
subjecting the compound to reduced pressure for foaming. This was the forerunner of
the current Talalay process, which became the only commercially important alternative
to the Dunlop process.

Initially foam rubber was made using natural rubber field latex but the product had
disadvantages such as high shrinkage, bad odour and poor ageing resistance. There was
a scarcity of natural rubber (NR) latex in the United Kingdom and North America for
the commercial production of foam during the period immediately following the Second
World War, so during this period the use of synthetic latices like styrene-butadiene rubber

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(SBR) latex and polybutadiene rubber (BR) latex were introduced initially as an extender
for NR latex; later foam based entirely on such synthetic latices was developed.

The most important commercial processes used for the manufacture of foam rubber
even today are the Dunlop process and the Talalay process, even though the latter process
accounts for less than 10% of the total foam rubber production.

9.2 Dunlop Process

The Dunlop process can be run as a batch process or a continuous process. As in the case
of every rubber product, a suitable formulation has to be selected in order to obtain a
useful product. A typical formulation based on natural rubber latex is given in Table 9.1.

Table 9.1 Formulation 1: Natural rubber latex foam


PART A (First stage compound)
Compounding ingredients Dry weight (g) Wet weight (g)
Centrifuged natural rubber latex 100 167
Potassium oleate solution (20%) 0.5 2.5
Sulfur dispersion (50%) 2.0 4.0
ZDC dispersion (50%) 1.0 2.0
ZMBT dispersion (50%) 1.0 2.0
SP emulsion (50%) 1.0 2.0
Part B (Ingredients which are added to the compound during processing)
Potassium oleate solution (20%) 0.5 2.5
Potassium castor oil soap solution (30%) 0.25 0.83
Kaolinite clay (dry powder) 20 20
DPG dispersion (50%) 0.75 1.5
Zinc oxide dispersion (50%) 5.0 10.0
Ammonium acetate solution (20%) 1.0 5.0
Sodium silicofluoride dispersion (20%) 1.0 5.0
Colour concentrate dispersion (20%) 1.0 5.0

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Latex Foam

Basically the formulation consists of four parts, namely, latex base, foaming agent, gelling
agent and curing agent. Centrifuged natural rubber latex containing about 60% dry
rubber content and ammonia as the preservative is the usual latex base used. Potassium
oleate/caster oil soap is used as foaming agent. This also acts as a latex stabiliser when
the ammonia content of the latex is reduced for foaming. Sodium silicofluoride is the
primary gelling agent, while a zinc oxide/ammonium acetate combination acts as the
secondary gelling agent. Diphenyl guanidine (DPG) acts as the foam stabiliser. A filler
like kaolinite clay also may be used. Sulfur is the crosslinking agent while zinc diethyl
dithiocarbonate (ZDC), zinc salt of mercaptobenzthiazole (ZMBT) are vulcanisation
accelerators. Styrenated phenol (SP) is the antioxidant to protect the product against
oxidative degradation. Colour may be added as required. The ammonia content of the
latex has to be reduced before the foaming process. Usually compounding is done in two
stages to obtain the optimal properties for the foam [6]. This is because it is advisable to
mature the first stage compound for 24 hours to get uniform distribution of ingredients
and partial precuring. The physical properties of the foam are also improved by the
maturation of the initial compound.

9.2.1 Batch Process

9.2.1.1 Steps in the Batch Process

The batch process involves the following operations:

a) Preparation of dispersions, emulsions and aqueous solutions


b) Deammoniation of latex
c) Compounding
d) Maturation
e) Foaming (whipping)
f) Refining (slow speed whipping)
g) Addition of gelling agent
h) Pouring the sensitised compound into the mould
i) Gelling
j) Curing
k) Removal of the product from the mould
l) Washing, drying and finishing

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The various compounding ingredients are added as dispersions (in the case of water
insoluble solids), emulsions (in the case of water insoluble liquids) and solutions (in the
case of water soluble solids) [7].

The details of the steps are given in the next sections:

a) Preparation of solutions, dispersions and emulsions

• 20% potassium oleate soap solution

Potassium oleate (20%) can be prepared by reacting potassium hydroxide and oleic acid
in equimolar proportions with the required amount of water (part with oleic acid and
part with potassium hydroxide) see Table 9.2.

Table 9.2 Formulation for potassium oleate soap solution


Compound Weight (g)
Oleic acid 100 A
Water 402
Potassium hydroxide 23.3 B
Water 43.0

A is warmed to 75 °C and then B is added to A using a high-speed stirrer.

• 50% sulfur and accelerator dispersions

The two dispersions are prepared as shown in Table 9.3.

Table 9.3 Formulations for sulfur and accelerator dispersions


Sulfur mix Accelerator mix
Compound Weight(g) Compound Weight (g)
Sulfur 50 Accelerator 50
Dispersol F 1 Dispersol F 1
Soft Water 49 Soft water 49

formulation Potassium oleate soap solution


210 formulations Sulfer
formulations Accelerator dispersions
formulation for Antioxidant emulsion
formulation for Filler slurry
Latex Foam

Both the mixes are ball milled for reducing the particle size and to form a stable dispersion.
A dispersing agent, for example, Dispersol F (sodium methylene bis naphthalene sulfonic
acid) is added to improve the stability by preventing chances of reagglomeration. Since
sulfur is hard to disperse, the sulfur mix has to be ball milled for at least 48 hours while
the accelerator mix needs only about 24 hours ball milling.

• 50% antioxidant emulsion

Water insoluble liquid antioxidant can be prepared as 50% emulsion in presence of


ammonium oleate soap as stabiliser as shown in Table 9.4.

Table 9.4 Formulation for an antioxidant emulsion


Compound Weight (g)
Liquid antioxidant 100 A
Oleic acid 5
Ammonia (in water - 25%) 5 B
Distilled water 90

A is warmed to 75 °C and B is added to A with high-speed stirring. The emulsion is more


stable due to the in situ formation of ammonium oleate soap.

• 70% filler slurries

Fillers like whiting, talc, lithopone, etc., can be added to latex to reduce the cost of the
product. Excessive addition will affect the processing as well as the physical properties
of the finished product. Filler addition improves hardness, which may be attractive for
some applications. Normally they are added at a level of 25 to 30 parts per hundred
parts of rubber (phr). Fillers can be added as aqueous slurries of about 70% solids content
and can be prepared by the formulation given in Table 9.5.

Table 9.5 Formulation for filler slurry


Compound Weight (g)
Filler 10 0
Dispersing agent 2.0
Soft water 35-45

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Normally ball milling is not required since the fillers are usually of low particle size. If
the latex compound has good stability, fillers may also be added to latex directly as fine
powder.

b) Deammoniation of latex

Normally, latex is preserved as either high ammonia (HA) latex concentrate (about 60%
dry rubber content) or low ammonia (LA) latex concentrate.

For HA latex concentrate (0.7% ammonia content), the ammonia content has to be reduced
to 0.12 – 0.22%. This is usually done by blowing in a current of moist air over the surface
of latex while it is being stirred by a drum shaped stirrer at about 50 rpm. Potassium soap
may be added at a level of 0.25 to 0.5% to minimise any risk of destabilisation of the latex
during deammoniation [8]. This amount of soap can however be deducted from the total
amount of soap to be added to the mix. The deammoniation step can be avoided in the
case of LA latex concentrate since its ammonia content is only 0.2%.

c) Preparation of the compound

Latex is mixed with the stabiliser and other ingredients as per the first stage compound
formulation (Part A – Table 9.1). All water insoluble solid ingredients are added as
dispersions and all water insoluble liquid ingredients are added as emulsions. The
compounding ingredients are mixed with latex by gentle stirring. The ingredients added
in the first stage (Part A) are soap (for the subsequent generation of froth), curing agent
(sulfur and accelerator required for vulcanisation), an antioxidant (to inhibit ageing of
the final product), and optionally mineral fillers. Mineral fillers of low particle size can
be directly added to the latex as dry powders provided additional stabilisers are added to
the latex or it can be added as slurry. Controlled addition of filler with proper stirring is
essential to prevent destabilisation of the latex and locally concentrated layers.

d) Maturation of the compound

After the first stage compounding, the compound has to be matured for 24 hours. This is
not done in the commercial process, but is known to improve the uniformity and quality
of the product [9, 10].

e) Foaming (whipping)

After maturation the compound is fed into a specially designed mixer known as a Hobart
mixer. The Hobart mixer used for this purpose consists of a bowl in which a wire whip
rotates in epicyclic (sun and planet) motion. The whip can have varying speeds. As
whipping proceeds, the volume of foamed latex increases and passes through a maximum.

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During whipping, the material in the vicinity of the whip gets processed whereas the
larger part of the mix either lies dormant or is tumbled around the mixer in an otherwise
inert fashion. Only a small amount of the compound is effectively processed at any time.
The wire whip should move so fast that it can create a void behind it. The void gets filled
with air and thus a large air bubble gets trapped in the latex compound. Subsequent
rotation of the whip breaks the large bubble into little ones. This process is continued
until the desired expansion is attained. The linear motion of the wire whip ensures the
addition of more materials from the dormant zone to the processing zone. The last turn
of the whip incorporates a few large air bubbles, which usually work to the surface of
the compound and get discharged. So, at this stage the compound contains bubbles of
varying range of sizes.

f) Refining

When the compound has attained the desired degree of expansion, the whipping speed is
reduced and this process is called refining. During refining all the large air bubbles either
get eliminated or comminuted, so that all the bubbles are of more or less uniform size. At
this point the foam stabiliser is added.

g) Addition of gelling agent

Zinc oxide, ammonium acetate and a delayed action gelling agent – sodium silico fluoride
(used for setting the foam before vulcanisation) are added separately in that order. As
mentioned earlier the gelling agent is usually added as an aqueous dispersion (20% w/w)
and its pH is adjusted to 6-7 just before addition to the latex compound [11].

h) Pouring the sensitised compound into mould

The compound is immediately transferred into a two-piece mould (pre-warmed to 30-


40 °C) designed to produce the desired shape and size of the finished product. Mould
shrinkage has to be taken into consideration when designing the mould. Slight excess
material will overflow through the sides and the fine holes provided on the mould lid.
This overflow is useful for checking the onset of gelling.

i) Gelling

Gelling is the destabilisation of the colloidal phase whereby the rubber particles join
together to become a single entity. The gelling can be monitored by checking the
consistency of the overflow material, which won’t come off easily once gelling has taken
place. The gelling time depends on the amount of gelling agent used, and the temperature
of the mould. Normally the time required for gelling is about 3-5 minutes.

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j) Curing

After proper gelling the mould is kept in a steam chamber for vulcanisation. The time of
vulcanisation varies from 20-50 minutes depending upon the thickness of the final product.

The majority of the commercial products like mattresses, cushions and pillows with
thickness greater than 2.5 cm have a cored structure This structure is obtained by using
moulds with regularly spaced pins/bushes which project (usually from the top plate of
the mould) into the cavity of the mould, thereby giving a honeycomb structure to one
side of the finished product.

Earlier big bush moulds were used. They had bushes with a core size of 35-40 mm
diameter and later the bush size was reduced to 18-22 mm for more uniformity. Nowadays
pencil bush and pin core type moulds are used. For pin core moulds, the pins are made of
aluminium rods having a diameter of 8-12 mm, whereas steel rods having a 6 mm diameter
are used for pin core moulds. As the number of cores increases and their size decreases
the rubber content of the mattress usually increases. However, in such cases the product
may have a tendency to tear while being stripped from the mould, if it doesn’t have
sufficient hot tear strength due to the decrease in wall thickness between cores. So,
normally, only superior quality foam is made using pin core moulds. In pin core moulds,
pins on both sides (lid and bottom of the mould) are preferred in order to make stripping
easier. In such cases there is a middle layer of about 6-10 mm in between the cores. The
mattresses made using pin core moulds need more time for drying, about 4-5 days whereas
a small bush mattress needs only about 12-14 hours at 60-70 °C. Usually the drying of a
pin core mattress is done in steps: drying for one day, then cooling, drying again for
another day, and cooling, etc., for about 5 days. This process is more efficient in removing
water from the inside of the foam rubber.

k) Removal of the product from the mould

After curing, the mould is taken out from the steam chamber and the wet cured product
is stripped carefully from the mould.

l) Washing and drying

The product is washed in running water. This is done by passing it through a series of
water sprays and squeeze rolls and finally through dry squeeze rolls to remove water.
Washing removes residual water-soluble substances like soap, which can lead to poor
ageing, poor resilience and bad odour.

Finally, the foam is dried in an air-circulating oven kept at 60-70 °C for 12-14 hours in
the case of a small bush mattress. The mattress made using pin core moulds needs more

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time for drying, about 4-5 days and is usually done in steps: drying for one day, then
cooling, drying again for another day and cooling, etc. During drying the product is laid
flat without distortion to avoid permanent deformation. The products are usually laid
on an open mesh grid. Products, if dried in contact with each other, have a tendency to
stick together. Slight post curing takes place during drying.

After drying, the products are trimmed to remove the flash and examined for defects.
Defects such as tears and small surface problems can be repaired by using latex adhesive.

9.2.2 Selecting a Formulation for Latex Compounds

• Latex Selection

Natural rubber latex or synthetic latices like SBR latex, Neoprene latex or nitrile rubber
latex can be used for making foam. Natural rubber latex is mainly used for commercial
production.

• Natural rubber latex

Both high ammonia and low ammonia latex can be used for making latex foam. The two
types should have the following specifications, for use in the manufacture of foam.
Characteristics of high ammonia and low ammonia latex are given in Table 9.6.

Table 9.6 Characteristics of high ammonia and low ammonia latex


High ammonia Low ammonia
Total solid (%) 61.5 61.5
Dry rubber content (%) 60.0 60.0
Alkalinity (ammonia content of latex) (%) 0.7 0.2
Secondary preservative (%) 0.1 0.25
KOH number 0.45-0.65 0.45-0.95
Mechanical stability time (seconds) 600-1250 600-1200
Volatile fatty acid number 0.05-0.1 0.01-0.03
Coagulam content (%) 0.005-0.01 0.005-0.01

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Variation of total solid content and dry rubber content can lead to variable shrinkage
resulting in variation in the size of foam products. The ammonia content of the latex is
very important, as the gelling is pH dependent. The KOH number is the amount of
potassium hydroxide needed to neutralise the total acid present in latex containing 100 g
of dry rubber. This includes both volatile and non-volatile fatty acids, produced during
the breakdown of the non-rubber constituents. The volatile fatty acid number represents
the amount of KOH required to neutralise the volatile fatty acids in the latex sample
containing 100 g total solids. The volatile fatty acids are mainly acetic acid, formic acid
and propionic acid, which are formed from the breakdown of some of the non-rubber
constituents present in the latex, when acted upon by bacteria. Mechanical stability time
(MST) is an indication of the time period the latex can remain stable under high mechanical
agitation, i.e., how effectively the rubber particles are protected in the latex [12, 13].

Two other important tests, which are recommended to be carried out, are the zinc oxide
thickening test (ZOT), also called the zinc oxide viscosity test (ZOV), and the zinc stability
time (ZST). ZOT and ZST represent the zinc sensitivity of the latex compound [14].
ZST is the change in MST of the latex mix with the addition of dry zinc oxide powder
(5%), whereas ZOT is the change in viscosity of the latex mix with the addition of zinc
oxide powder (5%) as a slurry. So ZST is directly proportional to the stability the latex
mix while ZOT is inversely proportional to the stability. ZST and ZOT give a good
indication of the foam rubber processability by the silicofluoride gelation in foam
production. For good processability ZOV should be between 500-700.

• Synthetic rubber latices

The primary requirement for synthetic rubber latices is also that it should have good
mechanical stability. The requirements are shown in Table 9.7.

Table 9.7 Requirements of synthetic rubber latices


used for latex foam manufacture
Property Limit
MST (s) 1000
Dry Rubber Content (%) 50
pH 10-11

The latices based on SBR and NBR usually contain carboxylated polymers. Carboxylated
latices give foam rubber of higher wet gel strength. These latices are usually stabilised
exclusively by fatty acid soaps. The styrene:butadiene ratio is in the range of 25:75.

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Latex Foam

Neoprene (polychloroprene) latex also can be used for the manufacture of foam rubber.
The gel content should be low to facilitate particle integration and good wet gel strength.
Sulfur modified polymer is used for foam rubber manufacture because of its higher wet
gel strength and hot tear strength, which is necessary for foam as it is a cored product
and has to be taken out from the mould at elevated temperature. Typical formulations
based on nitrile rubber latex and Neoprene latex are given in Tables 9.8 and 9.9.

Variation in dry rubber content may result in variation in shrinkage of the product and
consequently products of low strength. Variation of ammonia content will result in
variation in the gelling time. It is better to use latex aged for not less than 10 days and
not more than 2 months.

9.2.3 Selection of Other Compounding Ingredients

Foam promoters used in the Dunlop process are usually carboxylate soap, of which the
most widely used are oleates, ricinoleates and castor oil soaps either alone or in combination.
In general, mixtures of carboxylate soaps promote foaming more effectively than do the
separate components. Castor oil soaps are less efficient as foam promoters compared to
oleates, which are highly frothing and give fine froth. For natural rubber latex foam the
amount of foam promoter required varies over a range of 0.5-2 phr. Synthetic latices normally

Table 9.8 Formulation for nitrile rubber latex foam


Compound Dry weight (g) Wet weight (g)
Part A
Medium NBR latex (50%) 100 200
Sulfur dispersion (50%) 2.0 4.0
ZDC dispersion (50%) 1.0 2.0
ZMBT dispersion (50%) 1.0 2.0
Nonox SP emulsion (50%) 1.0 2.0
Part B
Zinc oxide dispersion (50%) 5.0 10.0
Ammonium acetate (20%) 1.0 5.0
Sodium silicofluoride (20%) 3.0 15.0

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Table 9.9 Formulation for polychloroprene rubber latex foam


Compound Dry weight (g) Wet weight (g)
Part A
Sulfur modified polychloroprene latex (50%) 100 20 0
Zinc oxide dispersion (50%) 7.0 14. 0
Sulfur dispersion (50%) 1.0 2. 0
Thiocarbanilide dispersion (50%) 2.0 4. 0
2,2´methylene bis (4-methyl-6-tert butylphenol) 2.0 4. 0
dispersion (50%)
ZDC dispersion (50%) 1. 0 2. 0
Part B
Sodium dibutyldithiocarbamate solution (25%) 1 4
O-dihydroxy benzene dispersion (50%) 1 2
Foam stabiliser dispersion (20%) 0.1 0. 5
Sodium silico fluoride dispersion (20%) 2 10

require less foam promoter to get the same expansion, as they contain larger amounts of
soap compared to NR latex. The foaming tendency is also dependent on pH. The pH
range required for optimum foaming is 6-9. The ability to promote and stabilise foam
depends on the hydrophobic moiety of the soap. Generally a longer hydrocarbon chain
length improves efficiency but reduces its solubility in water [15, 16].

The vulcanising system used in the manufacture of latex foam rubber is sulfur in
combination with accelerator and activator. The usual dosage used is sulfur (2 phr) and
primary accelerator (1 phr) in combination with a secondary accelerator at a dosage of
about 0.5 phr, and activator at about 1 phr. A commonly used primary accelerator is
ZDC and as secondary accelerator ZMBT and zinc oxide as activator. The function of
the secondary accelerator is to improve the elastic modulus of foam rubber and thus the
load bearing capacity. Zinc oxide has the dual function of activator and gelling promoter.

There are four classes of foam stabilisers used with the Dunlop process.

1. Quaternary ammonium surface-active compounds

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Latex Foam

2. Amino compounds

3. Organic hydroxyl compounds in particular phenols

4. Water-soluble hydrocolloids

These are usually added in the second stage of compounding. They actually function as gel
sensitisers rather than foam stabilisers. Commonly used quarternary ammonium compounds
are n-hexadecyl trimethyl ammonium bromide, cetyl trimethyl ammonium bromide, etc.
Amino compounds like DPG, triethylene tetramine, etc., are also used. The third class of
compounds include nitrophenols, cresols, naphthols, etc. Principal examples of the fourth
category of foam stabilisers, water-soluble hydrocolloids, are substances such as glue, casein,
polyvinyl alcohol, etc. The amounts used are variable usually ranging from 0.1 to 0.2 phr.
These materials enhance the stability of the aqueous phase/air interface by getting adsorbed
at that interface and thereby the aqueous phase/rubber interface gets destabilised earlier
compared to the aqueous phase/air interface, so that the latex gels before the foam has collapsed
appreciably. So these materials can be described as gel sensitisers rather than foam stabilisers.

Fillers are incorporated into latex foam rubber mainly to improve the stiffness of the
product and to reduce cost. Filler addition also reduces shrinkage. As fillers are
incorporated, the physical properties of the foam tend to deteriorate. Elongation at break
and resistance to cyclic compression are reduced. At higher dosages of filler the product
breaks down under cyclic deformation. Commonly used low cost fillers are talc, calcium
carbonate, kaolinite clay, etc., up to 20-30 phr. Fillers can be added either as slurry or as
fine powder, provided the latex is properly stabilised.

Softeners such as mineral oil can be used at low dosages (up to 4 phr) to promote
interparticle coalescence during gelation. Antioxidants like styrenated phenol or N,N´´di
2-naphthyl-p-phenylene diamine, etc., are used in latex foam rubber for improving the
ageing resistance. Normally such antioxidants are used at a dosage of 1.0 to 1.5 phr.

Addition of chlorinated paraffins, antimony trioxide, zinc borate and hydrated aluminium
hydroxide, etc., can improve the flame resistance of latex foam rubber. Polychloroprene
latex based foam rubber is found be flame resistant [17].

A commonly used gelling agent is sodium silicofluoride in combination with zinc oxide.
The sodium salt is preferred in natural rubber latex whereas a combination of sodium
and potassium salt is used in synthetic latices. In NR latex about 1.5 phr of sodium
silicofluoride is used together with about 3-5 phr of zinc oxide. The gelling is found to be
highly influenced by the pH, the optimum value being approximately 8.6. Gelling can be
retarded by addition of a solution of dilute aqueous alkali to the silicofluoride dispersion
[18]. Commonly used alkalis are ammonium hydroxide, sodium hydroxide and trisodium

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orthophosphate. Normal practice is to adjust the pH of sodium silicofluoride to at least


7 and then add to the foamed latex.

Gelling in the Dunlop process involves the following steps. The latex compound contains
ammonia and soap in addition to the curing ingredients. After frothing, zinc oxide and
sodium silicofluoride are added separately. The pH of the mix is in the range of 10.0-
10.5. At this pH sodium silicofluoride hydrolyses slowly as shown [19]:

Na2SiF6 → 2Na+ + SiF6 2-

SiF6 2- + 4H2O → Si (OH) 4 +4H+ + 6F-

The hydrolysis brings about gelation of the latex foam in three ways:

1. The fall in pH due to the presence of hydrofluoric acid.

2. The absorptive effect of silicic acid

3. The destabilisation effect of zinc amine complex formed by the reaction of zinc oxide with
ammonium fluoride, which is formed by the reaction between hydrofluoric acid (HF) and
ammonium hydroxide (NH4OH). These zinc amines when destabilised attack soaps in
latex to form insoluble zinc soap. By adjusting the levels of zinc oxide and sodium
silicoflouride and by the use of secondary gelling agents such as diphenyl guanidine, cetyl
trimethyl ammonium bromide, etc., the reactions leading to the destabilisation of the air
liquid system and the rubber liquid system can be balanced to get an open cell foam.

The foamed latex is essentially a three-phase colloidal system. It comprises of two dispersed
phases, rubber particles and the air bubbles and a single continuous water phase. Of
course there are other dispersed phases such as fillers, curing agents antioxidants, etc.
These dispersed phases are of comparatively minor importance for the fundamental
processing technology of foamed latex and for the behaviour of the foamed latex colloidal
system. There exist two interfaces, one between the latex aqueous phase and rubber
particles and the second between aqueous phase and air bubbles. The successful
manufacture of foam rubber depends on the proper manipulation of these interfaces.

As the same stabilisers give stability to both interfaces the destabilisation of one interface
always results in the destabilisation of the other interface. However, for the production
of foam, the destabilisation of the water/rubber interface should occur first and then
only the destabilisation of water/air interface should occur. If the destabilisation of the
water/air interface occurs first, the foam will collapse. To avoid this, the foam stabiliser
should preferentially stabilise the water/air interface. Pure latex foam is off white in
colour. Depending upon the requirement, colour may be added.

Photographs of the process are shown in Figure 9.1.

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Latex Foam

Figures 9.1a-p Foam compounding process

Figure 9.1a Deammoniation process

Figure 9.1b Measuring the latex for compounding

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Figure 9.1c Compounded latex in the mixer for foaming (whipping)

Figure 9.1d Open mould

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Latex Foam

Figure 9.1e Pouring foamed latex into the mould from the mixer

Figure 9.1f Spreading the foamed latex compound in the mould

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Handbook of Polymer Foams

Figure 9.1g Closed mould in the steam chamber

Figure 9.1h Mould opening after curing

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Latex Foam

Figure 9.1i Product stripping

Figure 9.1j Washing the product in water

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Handbook of Polymer Foams

Figure 9.1k Passing through rollers

Figure 9.1l Final pass through squeeze rollers

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Latex Foam

Figure 9.1m Laying the product on wire net for oven drying

Figure 9.1n Samples in the drier

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Figure 9.1o Trimming of the product

Figure 9.1p Foam mattress

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Latex Foam

9.2.4 Continuous Process for Latex Foam Production

Modern high capacity latex foam plants use continuous foaming process. The motivation
for the continuous process is two fold: to reduce labour cost and to reduce compound
variation thereby improving product uniformity.

A typical example is the production of latex foam rubber using an Oaks mixer. The Oaks
mixer used in this process is similar to the Hobart mixer in the batch process but which
is designed to mix continuously.

The first continuous latex foaming process was patented by Murphy and co-workers
[20]. Compounded latex and air are metered into the base of a long vertical chamber and
beaten to foam. The foamed latex compound is fed into another chamber, which is also
provided with a beater, where dispersions of zinc oxide and gelling agent are added and
then it is fed into the mould. After gelling it is cured.

The advantages for the products made by the continuous process are:

a) they are more uniform and have a superior texture


b) variation of foam density is possible
c) reduction in whipping time compared to batch process for getting the same density foam
d) material wastage in the bowl can be reduced
e) rejection rate can be reduced
f) labour cost is reduced

The mixer head is constructed with stainless steel and can be easily dismantled and cleaned.
The head consists of a rotor, which is completely enclosed with two stators. The rotor has
a large number of square section teeth arranged in concentric circles. The stators also have
teeth arranged similarly, spaced in between the teeth on the rotor as shown in Figure 9.2.
The latex compound is fed into the mixer along with required amount of air by way of the
inlet shown. The compound enters the mixing chamber, which is formed, between the
rotor and the stator. As the rotor rotates it intimately mixes the material in between the
teeth of the rotor and the stator. The mixing achieved may be described as being two-
dimensional: the material moves in a tangential direction; as the rotor revolves it also
moves radially from one circular path to another under the influence of the incoming
material. So all the material gets processed to the same extent. As the latex compound and
air get mixed, it results in fine-celled foam of uniform structure. It is claimed that natural
rubber latex foam of specific gravity as low as 0.06 can be made by this method. Such a
low density needs the latex compound to have about 17 times expansion. The ratio of air
to latex can be varied to make latex foam rubber of varying density. The rotor speed is

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always kept as low as possible, usually in between 100 and 400 rpm. Zinc oxide and
sodium silicofluoride are injected into the mix using a hypodermic syringe.

A typical layout of the continuous process is shown in Figure 9.3.

Figure 9.2

Figure 9.3 Lay out for the continuous Dunlop process

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Latex Foam

Steps in the process are:

a) Cleaning of the mould


b) Application of a mould release spray
c) Drying of the mould
d) Inspection of the mould
e) Warming of the mould
f) Opening of the mould
g) Filling of the mould with latex foam
h) Closing of the mould
i) Gelation of foam
j) Vulcanisation of the foam
k) Cooling of the mould
l) Opening of mould
m) Stripping of the product

9.3 Talalay Process

The Talalay process is different from the Dunlop process in that the chemical gelling
agent in the latter process for setting the foam is replaced by carbon dioxide in the
former and hence is more environmentally friendly. However, as in the Dunlop process
this also requires accurate control in which rubber/water and water/air interfaces collapse
and are manipulated by the matrix temperature [21].

Dr. Anselm Talalay of BFGoodrich Sponge Products is the pioneer of the Talalay process.
There have been minor changes in the process over the years and the modern Talalay
process can be divided into the following operations:

a) Preparation of dispersions, emulsions and solutions


b) Deammonisation in the case of natural rubber latex
c) Compounding
d) Maturation

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e) Foaming
f) Pouring the foamed compound into the mould and vacuum expansion
g) Freezing
h) Gelling
i) Curing
j) Removal of the product from the mould
k) Washing, drying and finishing

The compound preparation is similar to that for the Dunlop process. Usually the Talalay
process uses SBR latex or a blend of SBR and NR latex, probably because the process is
more popular outside the NR producing countries in the world. It may be observed that
the basic process used is more or less the same as that of the Dunlop process except the
gelling stage. Silicafluoride gelling agent is avoided in this process. Since the latex base is
likely to be ammonia free, a small amount of ammonia is added to improve the gelling.
KOH and Vulcastab VL (polyethylene oxide condensate) are added as the stabilisers. A
small amount of process oil is added to improve the flexibility of the product. Sulfur
along with accelerator and zinc oxide function as the curing system while Nonox SP is
used as the antioxidant.

The Talalay process is generally not used for the manufacture of speciality foams based
on nitrile or Neoprene latex. A typical formulation using SBR latex is given in Table 9.10.

In one process the expansion is brought about by the chemical decomposition of hydrogen
peroxide by an enzyme. The latex compound after maturation is mixed with the required
amount of hydrogen peroxide and a slurry of bakers yeast preferably at a low temperature
(about 10 °C) to delay the decomposition of the peroxide. The mixture is then quickly
placed in a specially designed mould (Figure 9.4).

The enzyme catalase (EC 1.11.1.6) present in the yeast decomposes hydrogen peroxide
to liberate oxygen, which expands the compound into a froth. Due to the difficulty in
controlling chemical frothing, in the modern process this is replaced by a combination of
mechanical frothing and vacuum expansion. Gelling agents are not used. The partially
expanded froth is placed in the mould and as the mould is closed vacuum is applied so
that the froth expands and fills the mould. Products of varying density can be made by
this method by adjusting the froth density in the mixer. Due to the complicated design of
the mould it is difficult to apply a mould-releasing agent in the Talalay mould. This is
overcome by the use of an internal lubricant added to the froth prior to it entering the
mould. The usual lubricant is a small amount of dilute hydrogen peroxide solution,
which is blended with froth just prior to feeding it in to the mould.

232
formulation SBR latex

Latex Foam

Table 9.10 A typical formulation using SBR latex


Dry weight (g) Wet weight (g)
SBR latex (50%) 100 20 0
Polystyrene co-agglomerated with SBR latex 17.5 35
(50%)
Potassium oleate solution (20%) 0.5 2. 5
Process oil emulsion (40%) 2. 0 5. 0
Nonox SP emulsion (50%) 1.0 2. 0
Sulfur dispersion (50%) 1.5 3. 0
Vulcastab VL solution (20%) 0.25 1.2 5
Zinc oxide dispersion (50%) 5.0 10. 0
ZDC dispersion (50%) 1.25 2. 5
ZMB dispersion (50%) 0.6 1. 2
Ammonia solution (35%) 2.0 6. 0
Potassium hydroxide solution (10%) 0.1 1. 0

Figure 9.4 Cross sectional view of typical Talalay mould

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The gelling and curing are controlled by heating, cooling process and so the mould should
have provisions for effective heating and cooling rapidly and reliably. The mould is fitted
with channels through which glycol/water mixture at precisely controlled temperature are
circulated, and the heat is conducted into and out of the foam by a series of closely spaced
pins penetrating the foam from both surfaces of the mould. Four glycol/water streams are
used to get the following temperatures:

Cold 30 °C
Low intermediate –4 °C
High intermediate –38 °C
Hot 110 °C

The mould periphery is fitted with a double groove with a vacuum moat between the
two grooves. The outer groove is provided with a permanent temperature resistant rubber
gasket, which seals the mould cavity with an air tight fit when the mould is closed. The
inner groove is fitted with a replaceable semi permeable paper gasket through which air
or gas can pass but froth cannot pass. When the required amount of the partially foamed
compound is metered into the mould, the mould closes and vacuum is applied to the
moat which withdraws the air from the mould, through the paper gasket. This causes
the foam to expand and fill the mould cavity. An automatic valve then operates to circulate
glycol/water mixture at –30 °C through the passage in the mould causing the expanded
foam to freeze rapidly. The rapid rise in surface tension destabilises the air/water system
and this together with the growth of ice crystals, causes the air bubbles to connect together
resulting in the formation of open cell foam. There is a chance for the collapse of the
foam during destabilisation of the air/water interphase but this is prevented as the froth
is in the frozen state. With cold glycol/water mixture still circulating vacuum is removed
and carbon dioxide is pumped into the moat. Here it passes through the paper and the
frozen foam. The pH falls from about 12 to 9.5 and the rubber-water phase breaks down
due to precipitation of zinc soaps from the destabilisation of zinc amines, and the formation
of zinc carbonate. When the rubber is coagulated in a stable foam structure, the mould
and its contents are rewarmed with the so-called intermediate glycol/water mixture. The
high intermediate and finally hot glycol/water mixture is passed through the mould. The
final stream raises the temperature to 110 °C and the foam is kept at this temperature for
curing. The time schedule of the various processes is given in Table 9.11.

At the cure temperature, as ammonium carbonate breaks down into ammonia and carbon
dioxide, the pH rises and it causes the reformation of potassium oleate soap, which aids
the removal of the foam from the mould. Further, as the lid of the mould is hotter than
the base, the product gets withdrawn from the pins in the base and is held on to the pins
in the lid, where it is easier to strip. In order to get high contact area and to have efficient
heat transfer a number of closely spaced pins are provided in the mould. The compound

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Latex Foam

should be designed to have high hot wet tear strength to avoid damage during stripping
of the product from the mould. Finally the product is washed and dried. Typical Talalay
foams are shown in Figure 9.4.

Table 9.11 Time schedule for various operations


Time (min)
Vacuum expansion 2
Freezing (cold) 8
Carbon dioxide gassing 5
Low intermediate 2
High intermediate 2
Hot (cure) 10
Drying (post cure) 7.5

Figure 9.4 Examples of Talalay foams

9.4 Troubleshooting in Latex Foam Manufacture

Since foam manufacture involves the interplay of the stability of different interfaces, the
quality of the product will be affected if the process isn’t properly controlled. The
commonly observed defects in latex foam are given in Table 9.12.

9.5 Testing

The testing of latex foam is generally done as per ASTM D1055-97 [22]. Latex grades
have their grade numbers designated by two letters which identify the kind of latex foam
rubber as follows:

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Table 9.12 Common defects observed and their remedies


Nature of defect Possible Reason Remedy
1 Coarse structure and Gelation at too low a pH Increase the dosage of
rat holes secondary gelling agent
2 Loose skin Slow gelling due to either Increase dosage of gelling
insufficient gelling agent or agent and/or use a warmer
mould too cold mould
3 Thick skin Mould too hot Use cooler mould
4 Flow marks on the Mould too hot or gelation Use cooler mould and/or
surface too fast reduce gelling agent
5 Surface lakes Excess mould release agent Reduce the amount of mould
release agent
6 Splitting in the Gelation too fast Reduce the dosage of gelling
centre agent and/or use cooler mould

RC – Latex foam rubber, cored and


RU – Latex foam rubber, uncored

9.5.1 Compression Set

Compression set under constant deflection is measured using a cylindrical test specimen
having 29 mm height and diameter not less than 19 mm. The apparatus and procedure
are described in method B of ASTM D395 [23]. Here the sample is compressed to 50%
of its original thickness in between two aluminium plates and the sample is kept at 70 °C
for a specified time. The force is released at the end of the test and then the thickness of
the sample after 30 minutes at room temperature is measured. The constant deflection
compression set can be expressed either as a percentage of the original height or as a
percentage of the original deflection as shown in the following equations:

t 0 − t1
Compression set in original height Ch = x100
t0
t 0 − t1
Compression set in original deflection Cd = x100
t0 − t s
where:

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Latex Foam

to = original height of test specimen


t1 = height after removal from the apparatus
ts = height of the spacer bar

The compression set of the sample should not exceed 15%

9.5.2 Indentation Hardness

A flat circular indenter foot 0.03 m2 in area is connected to a force measuring device by
means of a ball and socket joint, and mounted in such a manner that the specimen can be
deflected at a rate of 0.2 to 10 mm/s. A maximum radius of 2 mm is allowable on the
edge of the indentor foot. The sample is supported on a perforated horizontal plate to
allow rapid escape of air during the test. The test specimen should have at least 300 mm
x 300 mm surface for indentation and a thickness of not less than 19 mm.

The test specimen is placed on the perforated plate in such a way that the cored or
honeycombed surface faces the perforated plate. The specimen position should be such
that the indentation is made at the centre. The indenter foot should be brought into
contact with the specimen and the original height determined after applying an initial
force 4.5 N, then compressing the specimen to 25% of the original height and observing
the load in Newtons including the 4.5 N preload. This is usually measured at 23 ± 1 ºC
and 5.0 ± 2% relative humidity after conditioning the sample for 12 hours.

The indentation hardness index is the load in kilograms required to give an indentation
in the sample equal to 40% of the original thickness under specified conditions. It is a
measure of the load bearing capacity of the foam. Foam products are graded as A B C D
E F G and H according to their indentation hardness index as shown in Table 9.13.

The hardness change of the sample after ageing at 70 ± 1 oC for 168 hours should be
within ± 20%.

9.5.3 Flexing Resistance

The flexing test consists of subjecting the sample to repeated compression and noting the
effect on cellular structure. The amplitude of compression and decompression should
vary between 25% and 50% of the thickness of the sample depending upon the indentation
value. Failure of the specimen is evidenced by the break down of the cellular structure as
observed by visual examination.

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indentation hardness Latex foam

Handbook of Polymer Foams

Table 9.13 Indentation hardness grading of latex foam


Grade Indentation hardness index
A 7–14
B 15–21
C 22–28
D 29–34
E 35–45
F 46–55
G 56–65
H 66–75

9.5.4 Density

The density of foam rubber is a measure of the expansion which is calculated by taking
the weight in air and loss of weight in water. A sinker has to be used to sink the foam
sample in water. The surface of the test piece must be coated with wax to prevent water
absorption when immersed in water. The measurement is done at a temperature of 20 °C.

9.5.5 Metallic Impurities

Maximum amount of copper and manganese in the foam should be copper (0.001%, by
weight) and manganese (0.005%, by weight).

The product should not have any objectionable odour. The colour should be as per the
specifications.

9.6 Important Uses of Latex Foam

9.6.1 Transportation

Transportation is the single largest outlet for latex foam. Depending upon the specific
need, products of different properties are needed. Automobile seating has a variety of

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Latex Foam

shapes and designs. This may vary from a foam pad resting on a spring or full depth
cushioning in the case of a light motor vehicle. The back support in automobile seating has
to resist only a minor load and consequently can be made of a much lighter density foam.

In the case of bus seating a high density shallow seat may be good enough due to the frequent
interchange of passengers. For a coach, the seat design must obviously be more luxurious.

An aircraft seat does not need to absorb much vibrations. It should have sufficient padding
to accept body contours and remove high pressure contact areas for comfort.

For train seats also, there is not much need for vibration absorption. Mainly it is the
static seating comfort which is of significance.

Motor cycle seats generally require a foam of very high density, partly because of the intensity
of the shock that has to be absorbed and partly because of the high loading per unit area.

9.6.2 Furniture

The static requirements of foam rubber cushioning, for example mattresses, are different
from the dynamic ones in transport. The main objectives in this case are the optimum
support of the body and comfort. The cavity pattern of the mattress and the movement
of air through the surface due to the highly porous nature of the product and the pumping
action on deflection, etc., add to comfort. In hospital and institutions the foam rubber
mattress is of particular advantage due to the simplicity of bed making, and its nondusting
and bactericidal attributes. The pillow uses one of the lowest density products.

9.6.3 Special Uses

In addition to the conventional uses mentioned above, there are other special uses such
as therapeutic cushions, packing material for electronic equipment and household goods,
gap fillers, shock absorption, shoe insoles, lining for many products, etc.

References

1. F.H. Untiedt, inventor; no assignee; US1777,945, 1930.

2. E.A Murphy, W.H. Chapman and D.W. Pounder, inventors; Dunlop Rubber
Company Ltd., assignee; GB332, 525, 1930.

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Handbook of Polymer Foams

3. E.A. Murphy, Transactions of the Institution of the Rubber Industry, 1955, 31, 90.

4. E.W. Madge, Latex Foam Rubber, Maclaren and Sons, London, UK, 1962.

5. J.A. Talalay, inventor; no assignee: GB 455,138, 1938.

6. D.C. Blackley, Polymer Latices - Science and Technology, Volume 1: Fundamental


Principles, 2nd Edition, Chapman and Hall, London, UK, 1997.

7. R.L. Kelly, Proceedings of the 123rd ACS Rubber Division Meeting, Toronto,
Canada, Spring 1983, Paper No.12.

8. C.W. Jurado and K.G. Mayhan, Rubber Chemistry and Technology, 1986, 59, 1, 84.

9. M.E. Myers Jr., A.M. Wims and W.R. Lee, Rubber Chemistry and Technology,
1973, 46, 2, 464.

10. E.B. Bradford and J.W. Vanderhoff, Rubber Chemistry and Technology, 1968,
41, 2, 514.

11 B.J. Newey and R.G. James, inventors; International Latex Process Ltd., assignee;
GB 574, 131, 1945.

12. A.D.T. Gorton, Rubber Chemistry and Technology, 1972, 45, 5, 1202.

13. H.C. Chin, M.M. Singh and S.C. Loke, Plastics and Rubber: Materials and
Applications, 1979, 4, 164.

14. D.C. Blackley, Polymer Latices - Science and Technology, Volume 3: Applications
of Latices, 2nd Edition, Kluwer Academic Publishers, Dordrech, The
Netherlands, 1997.

15. G.D Miles and Ross, Journal of Physical Chemistry 1944, 48, 280.

16. A.D.T. Gorton, Rubber Chemistry and Technology, 1970, 43, 5, 1255.

17. C. Anolick, G.S. Cook and C.W. Stewart, Rubber Chemistry and Technology,
1979, 52, 4, 871.

18. H.E. Schweller, Proceedings of the 123rd ACS Rubber Division Meeting, New
Orleans, LA, USA, Fall 1975, Paper No.5.

19. J.C. Fallois in Polymer Latices and their Applications, Ed., K.O. Calvert, Applied
Science Publishers, London, UK, 1982, 207-228.

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Latex Foam

20. E.A. Murphy, Transactions of the Institution of Rubber Industry, 1955, 31, 90.

21. E.V. Thomas in Rubber Products Manufacturing Technology, Eds., A.K.


Bhowmick, M.M. Hall and H.A. Benarey, Marcel Dekker, New York, NY, USA,
1994, 845-853.

22. ASTM D1055-97, Standard Specifications for Flexible Cellular Materials-Latex


Foam, 1997.

23. ASTM D395-02, Standard Test Methods for Rubber Property—Compression Set,
2002.

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Microcellular Foams

10
Microcellular Foams

Vipin Kumar and Krishna V. Nadella

10.1 Introduction

Microcellular foams refer to thermoplastic foams with cells of the order of 10 μm in size.
Typically these foams are rigid, closed-cell structures, although recently there is much
interest in creating open-cell, porous structures that have cells in this size range. The
microcellular process that sparked the growth in this field over the past two decades was
invented at Massachusetts Institute of Technology, USA, in the early eighties [1], in
response to a challenge by food and film packaging companies to reduce the amount of
polymer used in their industries. As most of these applications used solid, thin-walled
plastics, reducing their densities by traditional foaming processes that produced bubbles
larger than 0.25 mm was not feasible due to excessive loss of strength. Thus was born
the idea to create microcellular foam, where we could have, for example, 100 bubbles
across 1 mm thickness, and expect to have a reasonable strength for the intended
applications.

It would be reasonable to say that the potential of microcellular foams has yet to be
realised. These materials have not yet appeared in mass produced plastic items, and the
promised savings in materials and associated costs have yet to materialise. This is largely
due to manufacturing difficulties encountered in scaling up for large scale production.
However, enthusiasm for these materials remains high, and today researchers and
commercial enterprises on every continent are in a global race to harness the potential
benefits.

Much has been learned about the processing and properties of microcellular foams since
the first patent was granted in 1984 [2]. An early review of the subject appeared in 1993
[3]. In this chapter the state-of-the art of processing will be reviewed in the next section,
followed by a discussion of structure and properties. This chapter will conclude with a
look at some of the current research directions involving microcellular technology.

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10.2 Processing of Microcellular Foams

10.2.1 The Solid-State Batch Process

The basic solid-state microcellular process is a two-stage batch process shown


schematically in Figure 10.1. In the first stage, the polymer is placed in a pressure vessel
with a high-pressure and a non-reacting gas. This step is usually conducted at room
temperature. Over time, the gas diffuses into the polymer, and attains a uniform
concentration throughout the polymer specimen. When this specimen is removed from
the pressure vessel and brought to atmospheric pressure, a ‘supersaturated’ specimen

Sample

Foamed sample

CO2 gas Pressure Heated


cylinder vessel bath
Stage I Stage II
Saturation Foaming of
of specimen specimen

Figure 10.1 Schematic of the batch process to make solid-state microcellular foams

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Microcellular Foams

that is thermodynamically unstable due to the excessive gas dissolved into the polymer is
produced. In the second stage, the supersaturated specimen is heated to a temperature
above the glass transition temperature (Tg) of the polymer-gas mixture, termed the foaming
temperature. This step is typically carried out in a heated bath with temperature control.
The dissolved gas lowers the Tg of the polymer [4] and the foaming temperature needs
only to be above the Tg of the gas-polymer system in order for the bubbles to nucleate
and grow.

Since the polymer is still in a solid state, the foams produced are called ‘solid-state foams’
to distinguish them from conventional foams that are typically produced in an extruder
from a polymer melt. The term ‘solid-state’ is meant to convey an essential difference
from the extrusion processes, namely that in the former process the bubbles are formed
in the rubbery state, near the Tg and the polymer is never melted. Thus, while surface
tension effects play an important role in the bubble growth dynamics of extrusion foams,
these effects are not important in the solid-state process. Instead, the viscoelastic properties
of the gas-polymer system become important.

The solid-state batch process has been used to create microcellular foams from a number
of amorphous and semi-crystalline polymers, such as polystyrene (PS) [1, 5-7],
polycarbonate (PC) [8, 9], acrylonitrile-butadiene-styrene (ABS) [10], polyethylene
terephthalate (PET) [11], glycol-modified PET (PETG) [12], crystallisable polyethylene
terephthalate (CPET) [13], and polyvinyl chloride (PVC) [14], etc. Examples of solid-
state microcellular structures in several polymers are shown in Figure 10.2. The
microcellular structure is remarkably uniform compared to the structure in extruded
foams or structural foams.

A unique aspect of the batch process is the ability to create an integral unfoamed skin on
a foam specimen [15]. This can be understood with reference to Figure 10.3, which
shows gas concentration profiles in a saturated specimen, just after it is removed from
the pressure vessel (time zero) and at a later time t. During this time, called desorption
time, the gas is allowed to escape from the surface layers. Then if C* is the minimum gas
concentration needed for bubble nucleation, one can see that there is a surface layer in
which bubbles will not nucleate due to a lack of sufficient amount of dissolved gas. Thus
a skin of solid polymer with a desired thickness can be created when the specimen is
heated after a suitable desorption time. This provides a means to create skin-core structures
that can be optimised to achieve the desired properties.

The basic solid-state microcellular process discussed above is called a temperature soak
process to signify that after initial saturation of the polymer by gas, bubble nucleation is
induced by heating the polymer. The reduction in gas solubility upon heating provides
the driving force for bubble nucleation. The bubble nucleation can also be achieved by a

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Handbook of Polymer Foams

Figure 10.2 Examples of microcellular foams in a number of thermoplastics: (a) PVC;


(b) PC; (c) ABS; (d) PET. All specimens show a remarkable homogeneity in
microstructure. The cell sizes range between 1-10 μm except for PET where the cells
are in the 100 μm range

sudden reduction of pressure, provided that the gas-saturated specimen is already above
the glass transition of the polymer-gas system. This is called the pressure-quench method,
and has been used for creating microcellular foams using supercritical carbon dioxide
[16-18]. This method has also been used to create open-cell microcellular foams discussed
later in Section 10.4.2.

Bubble nucleation in the solid state process was first studied by Colton [5] who applied
classical nucleation theories to this process. Later experiments by Kumar [6] and Kweeder
and co-workers [7] showed that classical theories did not adequately explain nucleation
in the solid state. This is the subject of on going inquiry.

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Microcellular Foams

Figure 10.3 Schematic showing the creation of an integral, unfoamed skin in the batch
microcellular process

10.2.2 The Semi-Continuous Process

A process to scale-up the batch process in order to produce a roll of microcellular sheet
was proposed by Kumar and Schirmer [19, 20] and is shown schematically in Figure 10.4.
Normally, if a roll of polymer film of say 10 cm radius was put in the pressure vessel for
saturation with gas, it would take hundreds of years at the typical rates of diffusion for
the gas to achieve a uniform concentration throughout the polymer roll. The breakthrough
idea in the semi-continuous process is that the polymer roll is first interleaved with some
sort of gas channelling device, such as a roll of paper towel. When this roll is now put in
the pressure vessel, the entire roll gets saturated in the same amount of time that it takes
for one polymer layer, which is of the order of hours to days depending on the gas and
polymer under consideration and the thickness of the polymer sheet. As shown in

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Handbook of Polymer Foams

Figure 10.4 Schematic of the semi-continuous process for industrial scale production
of solid-state microcellular foam sheets. Paper towel was used in the laboratory to
establish feasibility of the process

Figure 10.4, the gas-saturated roll is passed through a hot bath to create the foam, and a
chilled bath to quench the microstructure, and the foamed polymer roll is collected as
shown. The gas-channelling device (paper towel in the laboratory version of the process)
can be collected and re-used.

A laboratory-scale machine was built by Branch [21] to investigate the key processing
parameters of the semi-continuous process. In this design a breaking mechanism was
incorporated in order to systematically vary the tension in the line. The effect of tension
on the structure and properties of the microcellular foam was investigated. It was found
that the tension in the line does not affect the density of the foams. However, the tension
elongates the cells in the processing direction. One consequence of this alignment in the
tension direction is that the tensile strength in the semi-continuous specimens is about
10% higher at a given relative density, compared to the foams produced by the batch
process.

10.2.3 Extrusion and other Processing Methods

Since the first patent on a process to make microcellular foams was issued [2], a number
of efforts have been made to enable large-scale production of these novel materials. The

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Microcellular Foams

strongest emphasis has been on development of extrusion processes (see, for example,
Park and co-workers [22, 23], Shimbo and co-workers [24], and Seibig and co-workers
[25]). Other developments include a thermoforming process (Kumar and Suh [26]), and
a sintering process where gas-saturated powder is first compacted and then heated to
create a net-shaped part (Seeler and co-workers [27, 28]). A semi-continuous process to
convert a roll of film to a roll of solid-state microcellular foam as described previously
presents an alternative to extrusion for production of foam sheets. Technology for
producing microcellular parts in injection moulding has been developed at Trexel [29].

As the interest in this technology grows and we get closer to commercial realisation, an
understanding of the development of microstructure in these processes becomes important
both from the viewpoint of process control as well as for optimisation of the properties
of the final product. For the extrusion-based processes, where the bubbles are formed in
a polymer melt, a number of studies have been made that address the issues related to the
growth of bubbles (see for example, Gent [30], Saunders [31], Arefmanesh [32, 33], and
Ramesh [34]). This subject has been reviewed by Ramesh [35] where one can find the
related bibliography.

Carbon dioxide is by far the most widely used gas for solid-state microcellular processing
[8-14, 18, 36]. Microcellular foams have also been produced by a polymer solvent phase
separation process [37, 38]. Recently Handa and Zhang [39] have presented a novel
stress induced nucleation process to obtain a variety of microcellular structures.

10.3 Properties of Microcellular Foams

Although innovations in processing have developed at a rapid pace, the property data on
microcellular foams have been slow in coming. The early publications on microcellular
foams conjectured that the microcellular structure, believed to be on a scale that was
smaller than the ‘critical flaw size’ for polymers, would enable these foams to retain their
mechanical properties even as the density was reduced. No quantitative information on
the critical flaw size was ever presented, nor was any property data presented in support
of the hypothesis. This is likely to be due to the emphasis placed on process development,
as opposed to property characterisation, in the early years of evolution of this field. Over
time, however, this conjecture has become a myth that microcellular materials are as
strong as the solid polymers but have a lower density, thus providing an opportunity to
lower costs with no penalty in performance.

The tensile property data [40] show that the tensile strength of microcellular foams decreases
in proportion to the foam density, and can be approximated quite well by the rule of
mixtures. Thus a 50% relative density foam can be expected to have 50% of the strength

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of the solid polymer. Figure 10.5 shows relative tensile strength as a function of relative
foam density for a number of microcellular polymers. In this figure the relative tensile
strength, is obtained by dividing the tensile strength of the foam by the tensile strength of
the solid polymer. Similarly, the relative density is foam density divided by the solid polymer
density. In Figure 10.6 we have plotted the strength data on a specific basis. Thus the
specific relative tensile strength for the foam of a given relative density is obtained by
dividing the relative tensile strength by the relative density. Figure 10.6 shows that on a
specific basis, the tensile strength of microcellular foams is essentially constant over the
entire range of foam densities. Unfortunately, similar data on conventional foams is not
readily available for a direct comparison with microcellular foams.

A unique aspect of data in Figure 10.5 is that in the relative density range of 0.1 to 0.5,
the microcellular foams represent novel materials for the engineer with properties not
previously available. Most conventional foams fall either in the low-density region (relative
density less than 0.1) or belong in the structural foams category (relative density greater
than 0.5). The modulus of microcellular foams can be reasonably estimated by the Gibson-
Ashby cubic cell model [41], which predicts that the relative tensile modulus equals the
square of the relative density. The gas composition in the cell may affect the long term
thermal conductivity of the foams [42]. Microstructures, tensile strength, and thermal

Figure 10.5 Tensile strength data on microcellular foams produced by the batch
process. The tensile strength is closely approximated by the rule of mixtures over the
entire range of foam densities

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Microcellular Foams

Figure 10.6 Plot of specific relative tensile strength as a function of relative density of
microcellular foams. Note that specific strength is essentially constant over a wide
range of foam densities

expansion properties for a number of low density foams have been reviewed by Williams
and Wrobleski [43].

Fatigue and creep behaviours of microcellular polycarbonate foams have been investigated
[44-46]. An interesting result from fatigue studies is that introduction of very small bubbles
in PC, with less than 1% reduction of density, led to a thirty-fold increase in fatigue life
compared to the solid PC. This might suggest a process similar to heat treatment of
metals, where a PC part may be saturated with carbon dioxide at 5 MPa and then heated
to say 60 ºC to introduce the microcellular structure without an appreciable density
change, to increase the fatigue life of a part. Due to the low processing temperatures,
very little dimensional change was observed in the experiments.

The tensile data for all gas-polymer systems investigated falls on one reduced plot where
relative tensile strength can be plotted against the relative density, as is shown in
Figure 10.5. However, energy absorption measures, such as an impact test, are more
sensitive to variations from polymer to polymer, and the results cannot be generalised.
Figure 10.7 shows Gardner impact strength for PVC foams [47] with relative densities of

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Handbook of Polymer Foams

Figure 10.7 Gardner impact strength of microcellular PVC foams as a function of


foam relative density. The impact strength is seen to be independent of the saturation
pressure used to prepare the foam specimens [47]

0.5 and higher. It is seen that the impact strength decreases linearly with foam density.
This result is contrary to the popular belief, long held without proof, that the microcellular
structure will always improve the energy absorption behaviour due to the increased
resistance to crack propagation offered by the micro voids [48].

Another point to note from Figure 10.7 is that the gas saturation pressure used to prepare
the foam specimens appears to have no significant effect on the impact resistance. Such
is not the case for the impact resistance of CPET foams [13], shown in Figure 10.8. We
find that foams prepared at 5 MPa carbon dioxide pressure have significantly higher
impact strength than the foams prepared at 3 or 4 MPa pressure. In this system, there is
crystallisation of CPET at 5 MPa, that changes the composition of foam matrix, and
results in entirely different properties compared with virgin CPET. Thus, impact results
can vary even qualitatively from polymer to polymer.

Figure 10.9 shows a comparison of the impact strength of PVC and CPET microcellular
foams. It can be seen that at a given relative density the CPET foams possess a higher
impact resistance. The Gardner impact data presented should only be used for relative
comparison of materials. The engineer and designer is warned against using these data in

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Microcellular Foams

Figure 10.8 Gardner impact strength of CPET microcellular foams as a function of


foam relative density. Note that specimens prepared at 5 MPa saturation pressure has
significantly higher impact strength compared to those prepared at 3 or 4 MPa. There
was carbon dioxide induced crystallisation of CPET at 5 MPa [13]

Figure 10.9 A comparison of Gardner impact data on PVC and CPET. The CPET
microcellular foams retain a larger fraction of the impact strength of the virgin
polymer compared to PVC microcellular foams [48]

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design, for the impact conditions in actual use are likely to be significantly different from
the idealised conditions for the Gardner test.

10.4 Current Research Directions

New insights and innovations continue to drive the field of microcellular foams forward.
Holl [49, 50] discovered that the cell growth mechanism in solid-state process is self-
limiting. Further, he identified a new triaxial tensile failure mechanism that contributes
to cell nucleation in solid state [51]. Handa’s recent discoveries of retrograde vitrification
[52] and stress-induced nucleation in solid-state [39] have added new dimensions to this
evolving field.

10.4.1 Microcellular Materials for Construction

Microcellular technology has evolved around thin-walled applications. Can the


microcellular process be scaled up to make thick parts for load-bearing applications? In
an effort aimed at producing lightweight and energy efficient panels for advanced panel
systems for future housing construction, Nadella and co-workers [53] have produced
10 mm thick ABS sheets with 50% or higher, reduction in density. Their process is
illustrated in Figure 10.10. The key difference from the batch process of Figure 10.1 is

Figure 10.10 Schematic of batch process modified to produce flat and thick
microcellular foams. Specimens 10 mm thick with 50% density reduction have been
produced from ABS using this process [53]

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Microcellular Foams

that the foaming is done inside a heated press in order to keep the foamed specimen flat.
The other key difference is that the time required for saturating the thick specimens is
much higher compared to thin sheets (the saturation time increases as square of the
thickness). A key focus of the research is to look for processing strategies to reduce the
saturation time to make the process more cost-effective.

11.4.2 Open-Cell (Porous) Microcellular Foams

Many applications are envisioned in the biomedical field for porous microcellular foams
made from biocompatible or biodegradable polymers. For example, it is hypothesised
that a polymer implant with surface layers that are porous with pores in the 20 to 30 μm
range might elicit a better healing response compared to an implant with a solid surface
[54]. Tissue engineering is another large area of application, where porous scaffolds are
needed to support natural tissue regeneration and growth. Figure 10.11 shows a porous
85/15 poly (DL-lactide-co-glycolide) foam made by the pressure quench method using
supercritical carbon dioxide [55].

Various research groups around the globe are involved in the investigation of microcellular
open cell foams. These foams have significant use in tissue engineering and other
biomedical applications. The primary techniques used to produce these materials are
phase separation and supercritical CO2 microcellular foaming.

Figure 10.11 Scanning Electron Micrograph of 85/15 poly(DL-lactide-co-glycolide)


foam produced using the pressure quench method. The samples was saturated at
35 °C at 15, MPa, respectively. The foam had a porosity (open-cell content) of 76%
as measured by an air picnometer [55]

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Handbook of Polymer Foams

Tang and co-workers [56] used pressure-induced phase separation in a supercritical fluid
to produce micro and ultra microcellular porous polymer membranes. Image, chemical
and calorimetric analysis from their study reveals that membranes prepared by a
combination of pressure-induced phase separation and plasma polymerisation with
ethylene, are easier to control and have better characteristics. Huang and co-workers
[57] produced open cell microcellular polycarbonate hollow fibers in a custom co-rotating
twin-screw extrusion system. Carbon dioxide was used at the blowing agent. An average
cell density of 109-1010 cell/cm3 and cell size in the range of 5-10 μm were achieved.
Roweton and Shalaby [58] used a continuous crystallisation induced microphase
separation process to make open cell thermoplastic microcellular foams. They suggest
relationships between morphology and modes of microphase separation based on thermal
property studies of representative foams. Porous biodegradable structures for cell
transplantation are one of the applications for open cell microcellular foams. Open cell
microcellular polylactic acid and polyphosphoester foams have been studied by Lo and
co-workers [59], for cell culturing applications. They used the phase separation technique
to produce a porous structure that allows dispersion of drugs and nutrients to the cells
attached to the foam interior. Studies on thermally induced phase separation and gelation
of rod shaped macromolecules to generate microcellular materials were conducted by
Jackson and Shaw [60]. Low density materials were achieved by cooling the dilute isotropic
solutions till phase separation and solvent freezing occurred. Cell sizes in the range of 1–
10 μm with cell walls 0.2 to 2.0 μm thick were reported. They also presented observations
and theories explaining the underlying mechanism.

Rodeheaver and Colton [61] experimented with the supercritical CO2 method to produce
open cell microcellular polystyrene foam. Using saturation pressures above 17 MPa,
foaming temperatures around 200 ºC and a scaled foaming time between 1 and 2 seconds
they produced PS foam samples with 1 μm open cell pores. The resulting foam had both
internal and surface porosity.

10.4.3 Sub-Micron Foams and Nanofoams

When a crystallised PET specimen is foamed by the solid-state batch process using carbon
dioxide, it is found that it has many orders of magnitude higher bubble density, and
much smaller bubbles compared to amorphous PET [62]. Figure 10.12 shows an example
of what some have termed ultramicrocellular foams - foams with cells in the range 0.1-
1 μm. In this case we have a significant reduction in density of 26%, due to a very high
cell nucleation density. Although this system is known to crystallise during the gas
saturation step, the link between crystallites and the high nucleation density has not yet
been established.

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Microcellular Foams

Figure 10.12 Scanning electron micrograph of an ultramicrocellular CPET foam of


0.74 relative density. The average cell size is approximately 0.4 micrometers, and the
cell density is estimated to be 1013 cells per cm3

Nanofoams - foams with pore sizes in the range of nanometers - are in concept an extension
of microcellular foams. The idea of creating nano-scaled cells in polymeric materials is
exciting and largely unexplored. Due to the unique structures, nanofoams are expected
to have many properties that are superior to those of existing materials, such as much
higher strength-to-weight ratios. It is expected that nanofoams would provide novel
functional materials that could be tailored for the properties needed, for example, thermal
conductivity, dielectric constant, acoustic and damping coefficients. Nanofoams have
the potential to be used for any applications where foamed polymers are currently used,
with possibly improved performance. These novel materials are expected to find a wide
range of applications in construction, packaging, motor vehicle, microelectronics, and
household products.

In microelectronic devices, one of the potential application areas for nanofoams, the
speed of pulse propagation is inversely proportional to the square root of the dielectric
constant of the medium. Decreases in the dielectric constant of the insulator materials
translate directly into improvements in microchips’ cycle time. In today’s microelectronics
industry, the standard dielectric material used is SiO2, which becomes conductive when
the clock speed of the chips becomes very high. It is therefore not a good enough insulator
to prevent ‘cross talk’ between the closely spaced copper wires of the latest generation of
semiconductors [63-65]. As chip-making technology advances from the current 0.18 mm

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lines to 0.13 mm and to 0.10 mm, there is an urgent need for new materials with much
lower dielectric constants. Foamed materials possess air bubbles that have a very low
dielectric constant of one. In order for foamed material to be used in microelectronics,
the size of the air bubbles inside the polymeric materials must be smaller than the film
thickness or any microelectronics features. The higher the volume fraction of the air
bubble, the lower the dielectric constant. High volume fraction nanofoams have the
potential to become the dielectric material in the next generation of microelectronic
devices with much higher clock speed.

The processing technique of polymeric nanofoams is currently very limited. Nanofoams


have only been produced using a block copolymer method for microelectronics
applications [64, 66]. In this method, the copolymer consists of thermally stable and
thermally labile blocks. Upon heating, the thermally labile block undergoes thermolysis,
leaving pores the size and shape of which are commensurate with the initial copolymer
morphology. High thermally stable nanofoams have been produced with a low dielectric
constant. However, the nanofoams produced have only 15-25% volume void fraction.
The block copolymer method is also expensive and often requires chemicals that are
environmentally hazardous.

Polyimide nanofoams and their mechanical behaviour have been studied by Hilborn and
co-workers [67] and Carter and co-workers [68]. More recently, Krause and co-workers
[69] have reported open nanoporous morphologies based on carbon dioxide foaming.
The research microcellular and nanocellular materials and their characterisation will
benefit from advances in measurement of glass transition at the nano scale [70] and
development of x-ray microtomography techniques for three-dimensional imaging of
foam structure [71, 72].

To create nanofoams we have to achieve many orders of magnitude higher cell nucleation
rates than realised to date. Experience with the microcellular process has shown that
bubble nucleation density is exponentially related to gas concentration in polymers [6,
9]. Figure 10.13 shows the cell nucleation density in PS as a function of nitrogen saturation
pressure. Over the range of nitrogen pressures explored, the number of cells nucleating
increases exponentially with gas saturation pressure. The higher the gas saturation
pressure, the more the gas will be dissolved in the polymer. Thus, the cell nucleation
density is directly related to the amount of gas dissolved in the polymer. Recently, in a
departure from convention, Handa and co-workers [52] have proposed a novel approach
to achieving higher gas concentrations in polymers that is based on the phenomenon of
retrograde vitrification described in Section 10.4.3.1.

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Microcellular Foams

Figure 10.13 Cell nucleation density, cells per cm3, as a function of the gas saturation
pressure in nitrogen-polystyrene system [6]. The number of cells nucleated is seen to
increase exponentially with the gas saturation pressure

10.4.3.1 Phenomenon of Retrograde Vitrification

To produce nanofoams, it is desirable to have high gas solubility and diffusivity. However,
these are two conflicting objectives based on conventional wisdom. It is well known that
the solubility of gases in polymers decreases with temperature and increases with pressure.
It is also known that the diffusivity increases with temperature. In some gas-polymer
systems, the diffusivity can be a strong function of gas pressure. Figure 10.14 shows the
diffusion coefficients of CO2 in poly (methyl methacrylate) (PMMA) at temperatures
below the Tg of PMMA. At low pressures (below about 2.7 MPa), the diffusion coefficient
is higher at a higher temperature. At higher pressures, however, it is interesting to see
that the gas diffusivity grows exponentially [52].

The observed phenomenon in Figure 10.14 is quite unusual. In the figure, the pressure at
which the sharp change in diffusion coefficient occurs can be defined as the glass transition
pressure, above which the polymer will transit from the glassy state to the rubbery state.
When the glass transition pressures are plotted against the corresponding temperatures,
as shown in Figure 10.15, it can be seen that for a given pressure, there are two glass
transitions, which is contrary to the conventional knowledge of polymers. The high Tg is
what has been usually observed. The low Tg is where the polymer transit from rubbery
state to glassy state with heating. This phenomenon was first found by Condo and Johnson,

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Figure 10.14 Diffusion coefficients of CO2 in PMMA as a function of the gas


saturation pressure at temperatures below the Tg of neat PMMA [ 52]

Figure 10.15 The glass transition temperature of the CO2 - PMMA system as a
function of the gas saturation pressure showing the retrograde vitrification
phenomenon [52]

260
Microcellular Foams

in 1992 in a theoretical study on the glass transition behaviour of polymers with


compressed fluid diluents [73]. It was later verified experimentally [52, 74]. Due to the
fact that the glass transition can result from increasing the temperature, rather than
decreasing the temperature, this phenomenon is termed ‘retrograde vitrification’.

Retrograde vitrification is a consequence of the complex effects of temperature and


pressure on the gas sorption process. At a constant pressure in this retrograde region,
sorption increases with a reduction in temperature, thus causing a glass-to-rubber
transition. This phenomenon has opened a new avenue for polymer processing under
milder conditions, because it allows polymers to be plasticised with compressed gas
under much lower pressures and temperatures.

A low-temperature foaming process has recently been developed by Handa and Zhang
[75] for the CO2-PMMA gas-polymer system. The polymer PMMA is first saturated in
CO2 at 0 °C and 3.4 MPa. After the PMMA is fully saturated, the pressure is slowly
released. Then the polymer-gas solution is quickly heated to 80 °C. The importance of
the low temperature process is that a high gas solubility can be achieved at low
temperatures and low pressures, which is essential in generating very small cells and high
cell densities. Furthermore, the diffusion coefficient at low temperature can be the same
as at higher temperatures such that the gas saturation process at temperatures below the
retrograde vitrification temperature is as fast as that at higher temperatures. Using this
process, ultra-microcellular foams with closed cells as small as 0.35 μm and cell density
as high as 4.4 x 1013 cells/g have been produced [52].

10.5 Commercial Opportunities

Over the past 20 years since microcellular foams were first invented many groups around
the world have spent considerable research effort to design and develop viable industrial
manufacturing processes for these materials. Initial efforts on developing an extrusion
process did not yield the expected results due to numerous technical difficulties. To begin
with, the gas had to be injected at supercritical pressures due to the low solubility of gas
at melt temperatures. Another challenge was that gas injection into the polymer melt
yielded a two-phase mixture in the barrel. For microcellular foaming to occur it is
important for the gas and polymer to be in a one-phase solution. This problem of going
from a two phase mixture to a one phase solution is not trivial. Die design to obtain an
acceptable surface finish was another challenge as surface bubbles affected the surface
finish. Moreover, these design changes were found to be polymer specific. A further
difficulty in extrusion process development was arresting bubble growth beyond the
desired micro-scale at the die exit. To the best of our knowledge, PS is the only polymer
for which microcellular extrusion has been successfully commercialised.

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The semi-continuous process described earlier has been slow to get attention due to the
perception that gas saturation into the polymer roll takes too long for the process to be
commercially viable. Major strides in commercialising microcellular foams have been
made with the development of the microcellular injection moulding process. Trexel, Inc.,
of Woburn, MA, USA has successfully developed and licensed microcellular injection
moulding technology to processors around the world [29]. Teaming up with equipment
manufacturers like Milacron, Trexel is designing and marketing microcellular attachments
for standard injection moulding machines.

Numerous applications are envisioned for microcellular foams. Current efforts towards
commercialisation are focused on automotive, construction, food packaging, and
industrial foams markets. Microcellular parts made using injection moulding have diverse
applications in markets such as business equipment, automotive, electrical, precision
trays, encapsulated products, etc. Examples of these applications are internal printer
components in business equipment market, under dash components, housings and power
train components in automotive market. Microcellular automotive liners, house siding
panels (exterior panel finished with a plastic sheet) and vinyl window profiles are some
of the products that can be made in an extrusion process. Thermoformed disposable
food packaging, building interior cushion (carpet underlay) and industrial foam
applications are areas where microcellular foams made by the semi-continuous process
can be used. Examples of such products are clamshells (disposable food container with a
hinge), carpet cushion and marine pads (a floating product used as a marker). Although
commercialisation of microcellular foams has been slow so far, we believe that with
continuing worldwide efforts to address the manufacturing challenges, the next decade
will see the potential of these novel materials realised in many areas.

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268
Abbreviations

Abbreviations

ABA Alternate blowing agent(s)


ABS Acrylonitrile-butadiene-styrene
ACGIH American Conference of Governmental Industrial Hygienists
ADC Azodicarbonamide
AFPF Alliance for Flexible Polyurethane Foams
API Alliance for the Polyurethane Industry
APP Aromatic polyester polyol(s)
ASTM American Society for Testing and Materials
BHT Butylated hydroxy toluene
BP Boiling point
BR Butadiene rubber
BS British Standard
CAA Civil Aviation Authority
Cal TB California Technical Bulletin
CBA Chemical blowing agent(s)
CEFIC European Chemical Industry Council
CFC Chlorofluorocarbon(s)
CFC-11 Chlorofluorocarbon-11
CFC-114 1,1-Dichloro,1,2,2,2-tetrafluoroethane
CFC-12 Chlorofluorocarbon-12
CFD Compression force deflection
CFR Code of Federal Regualtions
CO2 Carbon dioxide
CONEG Coalition of Northeastern Governors
C-PAT Quasi-continuous form pressure and temperature system

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Handbook of Polymer Foams

CPET Crystallisable PET


DCP Di-cumyl peroxide
DEG Diethylene glycol
DIDP Di-isodecyl phthalate
DIN Deutsches Institut für Normung (German Institute for Standardisation)
DMEA Dimethyl ethanolamine
DMT Di-methyl terephthalate
DOE US Department of Energy
DPB Dimethylether/propane/butane
DPG Diphenyl guanidine
EMA Ethylene methyl acrylate
EO Ethylene oxide
EPA US Environmental Protection Agency
EPDM Ethylene-propylene diene terpolymer
EPP Expanded polypropylene
EPS Expanded polystyrene
EU European Union
EVA Ethylene vinyl acetate
FAA Federal Aviation Authority
FAR Federal Aviation Regulations
FDA Food and Drug Administration, USA
FKS Vereniging van Fabrikanten van Kunststofleidingsystemen (The Dutch
Federation of Plastic Pipe System Manufacturers)
FMVSS Federal Motor Vehicle Safety Standard
FPF Flexible polyurethane foam
GCD Gaseous carbon dioxide
GRAS Generally regarded as a safe
GWP Global warming potential
HA High ammonia
HBCD Hexabrominated cyclodecane
HBFC Hydrobromofluorocarbons
HC Hydrocarbon(s)
HCFC Hydrochlorofluorcarbon(s)

270
Abbreviations

HCFC-124 Tetrafluroethane
HCFC-141b Dichlorofluoroethane
HCFC-142b 1-Chloro-1,1, diflurorethane
HCFC-22 Chlorodifluoromethane
HDPE High density polyethylene
HFC Hydrofluorocarbon(s)
HFC-134a 1,1,1,2-Tetrafluoroethane
HFC-152a 1,1-Difluoroethane
HFC-227ea 1,1,1,2,2,3-Heptafluoropropane
HFC-245fa 1,1,1,3,3-Pentafluoropropane
HFC-365mfc 1,1,1,3,3-Pentafluorobutane
HFE-245 Pentafluoro methyl ether
HFE-254mf 2,2,2, Trifluoroethyl difluoro methyl ether
HFE-356 Hexafluoroethane
HR High resilience
ICF Insulated concrete form
IFD Indentation force deflection
III International Isocyanate Institute
IR Infra red
ISOPA European Isocyanate Producers Association
JAA Joint Aviation Authorities
JAR Joint Aviation Regulations
JIS Japanese Industrial Standard
JUFA Japan Urethane Foam Association
L/D Length:diameter ratio
LA Low ammonia
LCD Liquid carbon dioxide
LDPE Lowdensity polyethylenen
LLDPE Linear low density polyethylene
MDI Methylene diphenyl diisocyanate
MDPE Medium density polyethylene
MMDI Di-cyclic monomeric MDI
mPE Metallocene catalysed polyethylene(s)

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MSDS Material safety data sheet


MST Mechanical stability time
MVSS Motor Vehicle Safety Standard
N/A Not available
N2 Nitrogen
NIH National Institute of Health
NR Natural rubber
OBSH Oxybisbenzenesulfonyl hydrazide
ODP Ozone depletion potential
ODS Ozone depleting substance(s)
OEL Occupational Exposure Limit as measured by manufacturer
OSHA Occupational Safety & Health Association
PA Phthalic acid
PAT Pressure and Temperature System
PBA Physical blowing agent(s)
pbw Parts by weight
PC Polycarbonate
PET Polyethylene terephthalate
PETG Glycol-modified PET
PFA Polyurethane Foam Association
PHD Polyharnstoff (polyurea) dispersion
phr Parts per hundred rubber
PIR Polyisocyanurate
PMDI Polycyclic polyisocyanates
PMMA Polymethyl methacrylate
POE Polyolefin elastomer(s)
POP Polyolefin plastomer(s)
PP Polypropylene
pph Parts per hundred
PPSO Polyphenylene sulfoxide
PS Polystyrene
PS Polystyrene
PU Polyurethane(s)

272
Abbreviations

PURRC Polyurethane Recycle and Recovery Council


PVC Polyvinyl chloride
PVC-U Unplasticised PVC
RC Latex foam rubbers, cored
RH Relative humidity
rpm Revolutions per minute
RU Latex foam rubbers, uncored
SAN Styrene acrylonitrile
SBC Sodium bicarbonate
SBR Styrene-butadiene rubber
SELCHP South-East London Combined Heat and Power Consortium
SI Statutory Instrument
SOLAS International Convention for the Safety of Life at Sea
SP Styrenated phenol
SPI Society of the Plastics Industry
S-PVC Suspension polyvinylchloride
STP Standard, temperature and pressure
TCFM Trichlorofluoromethane
TCPP Tris monochloro isopropyl phosphate
TDCP Tris dichloro isopropyl phosphate
TDI Toluene diisocyanate
Tg Glass transition temperature
TLV Threshold Limit Value
TMP Trimethylol propane
TPE Thermoplastic elastomer(s)
TPU Thermoplastic polyurethanes(s)
TSH p-Toluenesulfonylhydrazide
TSS p-Toluenesulfonylsemicarbazide
UNEP United Nations Environmental Programme
UV Ultraviolet
VLDPE Very low density polyethylene
VOC Volatile organic compounds
VPF Variable pressure foaming

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WEEE Waste electrical and electronic equipment


XPS Extruded polystyrene
ZDC Zinc diethyl dithiocarbonate
ZMBT Zinc salt of mercapto benzthiazole
ZOT Zinc oxide thickening test
ZST Zinc oxide viscosity test

274
Contributors

Andrew Barnetson
British Plastics Federation, 6 Bath Place, Rivington Street, London, EC2A 3JE

David Eaves
The Barns, Station Road, Harbury, Warwickshire, CV33 9HQ

Christopher Howick
European Vinyls Corporation (UK) Ltd, The Heath, Runcorn, Cheshire, WA7 4QF

Tyler Housel
Inolex Chemical Company, Jackson and Swanson Streets, Philadelphia, PA 19148, USA

Rani Joseph
Department of Polymer Science and Rubber Technology, Cochin University of Science
and Technology, Kochi - 682022, Kerala, India

Vipin Kumar
Department of Mechanical Engineering, University of Washington, Seattle, Washington
98195, USA

Krishna Nadella
Department of Mechanical Engineering, University of Washington, Seattle, Washington
98195, USA

Sachchida Singh
Huntsman Polyurethanes, 286 Mantua Grove Road, West Deptford, NJ 08066-1732, USA

Noreen Thomas
Institute of Polymer Technology and Materials Engineering, University of Loughborough,
Loughborough, Leicestershire, LE11 3TU

275
Handbook of Polymer Foams

276
Author Index

A E
Arefmanesh, A. 249 Eaves, D. 1, 55, 173
Ashby, M.F. 6, 250
Ashford, P. 79 G
Gale, M. 125, 137
B Gent, A.N. 249
Ball, G.W. 77, 78 Gibson, L.J. 250
Barnetson, A. 37 Gibson, W. 6
Beckmann, G. 126, 127, 128, 129 Glicksman, L.R. 6
Bertucelli, L. 69
Birch, S.J. 165 H
Branch, G. 248
Brenis, K.L. 132 Han, C.O. 125
Handa, Y.P. 249, 254, 258, 261
Hansen, R.H. 125
C Hilborn, J.G. 258
Carter, K.R. 258 Holl, M.R. 254
Collington, K.T. 189 Hooke, R. 3
Colton, J.S. 246, 256 Housel, T. 85
Condo, P.D. 259 Howick, C.J. 155
Cousins, J.R. 178, 179 Huang, Q. 256
Cunningham, A. 6 Hughes, R. 124

D I
Decker, R.W. 141 Ide, F. 138
Dey, S.K. 137
Dobrowsky, J. 124 J
Domas, F. 178
Jackson, C.L. 256
Johnson, K.P. 259
Joseph, R. 207

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Handbook of Polymer Foams

K Rodeheaver, B.A. 256


Ross, M. 138
Kaufung, R. 79
Roweton, S. 256
Kim, B.C. 131, 132
Rowland, F. 15
Krause, B. 258
Kumar, K. 243
Kumar, V. 246, 247, 249 S
Kweeder, J.A. 246 Sarvetnick, H.A. 157
Saunders, J.H. 249
L Schirmer, H.C. 247
Seeler, K.A. 249
Landrock A.H. 58
Seibig, B. 249
Lo, H. 256
Shalaby, S.W. 256
Shaw, M.T. 256
M Shimbo, M. 249
Mack, M.H. 177 Singh S.N. 9
Maier, R.D. 184 Suh, N.P. 249
Meyke, J. 177 Szamborski, G. 138, 140
Molina, M. 15
Murphy, E.H. 229 T
Talalay, A. 231
N Tang, C. 256
Nadella, K.V. 243, 254 Thomas, N.L. 123, 132
Niven, W.G. 157 Throne, J.L. 143
Tideswell R.B. 60

O
Okano, K. 138 W
Weigand, E. 79
P Williams, M.J. 251
Park, C.B. 249 Wrobleski, A.D. 251
Patterson, J. 124, 140
Pfennig, J-L. 138 Z
Puri, R.R. 189
Zhang, Z. 249, 261
Zipfel, L. 69
R
Rabinovitch, E.B. 131, 132
Ramesh, N.S. 249

278
Company Index

A F
ARC 82 Furukawa Electric Co. 181, 182, 183,
186
B
G
BASF AG 37, 45, 46, 54, 76, 177, 178,
179 Goldschmidt 73
Bayer AG 75, 79, 82
Beamech 100, 101, 102 H
Berstorff GmbH 176, 177, 179
BFGoodrich Sponge Products 231 Hennecke GmbH 75
Borealis 177, 184 Hitachi 182, 183, 186
BP 54 Hitachi Chemical Co. 181

C I
Celotex Corporation 73 IBM 38
Congoleum Corporation 167, 168
K
D Kodak 38
Dex Plastomers 184
Dow 184 M
Dunlop 207, 208, 232
Matheson 137
Dupont Dow 184
Meccano Toy Company 38
Dynisco 137
Montell 177, 179

E
N
Elenac 184
Nitroil 72
Exxon 184
Nova Chemicals Corporation 54

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Handbook of Polymer Foams

P
Phillips 184
Puren Schaumstoffe 76

R
Reifenhauser GmbH 176

S
Sekisui Electrical Co. 180, 186, 190
Solvay 69

T
Trexel Inc. 249, 262

Z
Zotefoams plc 189, 192, 195, 196, 197,
198

280
Subject Index

A CFC 174
characteristics of 66
ABS
chemical 25, 28, 29
microcellular foams 246
chemical inhibition 167
Accelerator dispersions
dichlorodifluoromethane 62
formulations 210
dihydrooxadiazinone 33
Additives
encapsulated physical 25
anti-static 94
endo/exo blends 33
biocides 94
endothermic 32
clickability 94
environmental acceptability 11
plasticisers 94
fluorinated ethers 24
Anisotropy 2
fluoroiodocarbons 24
Antioxidant emulsion
foam type 25, 26, 27
formulation for 211
global warming 11
Appliance insulation 67
HCFC 174
Aromatic polyester polyols 59, 60
health impacts of 11
Azodicarbonamide
hydrazine derivates 31
blowing agent 165
hydrocarbons 174
inert gases 22
inert 175
B liquefied CO2 97
Blend compatiblisers 73 methyl chloride 14
Blowing agents 9, 175 methyl chloroform 24
acetone 24 methylene chloride 14
alcohol 24 n-nitroso compounds 32
alternative 66, 97 n-pentane 68, 69
application 25, 26, 27 nitrogen 22, 23, 24, 174
azo compounds 30 oxybisbenzenesulfonyl hydrazide 133
azodicarbonamide 31, 133, 134, 135, oxygen 22
136, 156, 159, 174, 185 ozone depletion 11
bicarbonates/carbonates 32 physical 10, 24, 25, 26, 27
blends of physical 24 polycarboxylic acid derivatives 33
carbon dioxide 10, 22, 23, 24, 97, 174 polyphenylene sulfoxide 32

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Handbook of Polymer Foams

properties of 14 Chlorofluorocarbons 7, 13
selection criteria for physical 10 chemical stability 15
sodium bicarbonate 133, 134, 135, properties of 14
136 solubility 15
solubility of the physical 12 trichlorofluoromethane 13
sulfonyl semicarbazides 31 Closed cell foam 12, 13
supercritical fluid 23 Compression force deflection 105
tetrazoles 33 Compression modulus 105
trichlorofluoromethane 62 Core pipe
vapour pressure 12 PVC foam 142
water 24 Cushion packaging 5
Blown foams Cushion vinyl floorings 167, 168
carbon dioxide water 68
Bubble nucleation 245, 246
D
Dunlop process 207, 208, 217, 231, 232
C
fillers 219
Carpets flame resistance 219
foamed PVC backings 168 foam stabilisers 218, 219
Catalysts gelling 220
blow 91 softeners 219
delayed 91 stabilisers 220
gel 91 Durometer 105
metallocene 174
potassium hydroxide 57
E
potassium salts 71
quaternary ammonium salts 71 Expanded polystyrene 37
reactive 92 applications 43
tertiary amines 71 automotive industry 44
tin 72 bead 38, 39
tin compounds 71 chemical properties 46
Cell openers 72 construction 42, 43
Cell shape 3 construction industry 37
Cell size 2, 107 conversion of bead to product 39
Cell uniformity 107 cycle helmets 44
Celuka process 126, 136, 143 development of 37
Chemical blowing agents energy recovery 53
exothermic 30 European market 47
polyvinyl chloride 29 European production 48
thermoplastics processing 29 final moulding 40

282
Subject Index

fire retardants 50 chalk 162


floating pontoons 43 mineral fillers 162
fruit and vegetable packing 46, 47 Flame retardant
garden containers 42 hexabrominated cyclododecane 50
global structure of markets 47 Flexible PVC foams
incineration 53 suspension PVC 155
insulated concrete form 44 Flexible polyurethane foams 5, 85
insulation 41 additives 94
landfill 53 adhesion promoters 94
major manufacturers 54 antioxidants 92
maturing 40 blow reaction 86
mechanical performance 45 blowing gas 97
mechanical recycling 53 carpet cushion 110
mouldings 38 catalyst 91
packaging 41 cell growth 96
physical properties 45, 46 cell nucleation 96
pre-expansion 39 cell opening 97, 98
pre-foamers 39 cell structure 107
production in Asia 48, 49 chamber pressure 96
production in USA 49 characterisation 104
properties 46 chemistry 85
properties of 44 colorants 92
recycling 51, 52 comfort 110
Regional Trade Associations 54 compression set 108
smoke 50 cure 98, 99, 101
surf boards 44 density 104
underfloor insulation 45 environmental issues 111
wall insulation 45 environmental stability 107
Expanded polystyrene packaging fatigue 108
applications 41 flame retardants 93
Expanding fillers 25 flammability 108, 109
Extruded sheet foam rise 101
chemically crosslinked 181, 182, 183 foaming process 94
irradiation crosslinked 180, 181 gel reaction 86
hardness 104, 105
isocyanate 88
F
light stabilisers 93
Filler slurry manufacturing equipment 99
formulation for 211 markets 109
Fillers methylene diphenyl diisocyanate 88

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Handbook of Polymer Foams

mixing 95, 96, 101 SBC concentration 135


moulded 85 screw speed 132
packaging 111 Foam expansion
polyol 88, 89 kicker 159, 160
porosity 106 Foam extrusion 124
production in 2001 109 basic principles 125
raw material conditioning 95 Celuka method 126, 128, 129
recycling 113 free-foam sheet 127
resilience 105 free-foaming method 126
slabstock 85 processes 126
specialty applications 111 Foam morphology 125
starting materials 87 Foam polyol 89
surfactant 90 Foam profile
storage and delivery 100 co-extruded 131
strength properties 106, 107 rigid PVC 141
toluene diisocyanate 88 Foam properties 3
transportation 110 compression 3
water 90 energy absorption 5
Flexible PVC foams 155 stress-strain curve 3, 4
blowing agent 165 Foam sheet
blowing agents 159 rigid PVC 142
cell types 160 Foam specification
closed cell 160, 161 aerospace 201
dispersion 156 automotive 201
emulsion resins 162 buoyancy 201
foam formation 159 furnishings 201
gelation 159 packaging 200
liquid plasticiser 163 Foam structure 1
open cell 160, 161 gas bubbles 1
paste resin 156 surface tension 1
pigments 163 viscous 1
plasticiser 164, 165 Foamed plastisols
plastisol 155 carpet backings 166
Foam cladding cushion vinyl flooring 166
co-extruded 130 floorings 166
Foam density 2, 139, 196 PVC leathercloth 169
azodicarbonamide 136 synthetic leather 169
concentration 134 wallcoverings 168
blowing agent 139 Foamed PVC
processing aid 138, 139 properties of 144

284
Subject Index

Foams index 87
chemically blown 156
FPF L
environmental issues 112, 113
slabstock 100 Latex 217
ammonia content 216
high ammonia 215
G
low ammonia latex 215
Gases thickening test 216
inert 22 zinc oxide 216
Glass fibre 73 zinc oxide viscosity test 216
Global warming potential 11, 20 zinc stability time 216
Latex compounds
H formulation 215
Latex foam 207
HC blowing agents
accelerator 210
cyclo-pentane 21
antioxidant 211
iso-pentane 21
batch process 209
isobutane 21
bush moulds 214
n-butane 21
compression set 236
n-pentane 21
curing 214
propane 21
deammoniation 212
properties of 21
density 238
HCFC 15
Dunlop process 208, 230
ozone depleting potential 16
filler 211
phase out schedule 18
flexing resistance 237
HCFC blowing agents
foaming 212
properties of 17
formulation 209
HFC blowing agents
furniture 239
characteristics of 70
gelling 213
properties of 19
indentation hardness 237, 238
Hydrocarbons 20
manufacture 216
halogenated 13
maturation 212
Hydrofluorocarbons 18
metallic impurities 238
natural rubber 208
I nitrile rubber 217
Indentation force method 105 polychloroprene rubber 218
Insulation material preparation 212
Western European market 79 refining 213
Isocyanate 60, 62, 85, 87 Talalay mould 231, 233

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Handbook of Polymer Foams

testing 235 Montreal Protocol 15, 16, 18, 57, 62,


transportation 238 66, 81, 175
uses 238, 239 Moulded foam 101
washing and drying 214 Moulding machines 99
Latex foam manufacture mPE
troubleshooting 235 commercial availability 184
Latex foam production MuCell process 146, 147
continuous process for 229
N
M Nanofoams 257, 258
Maxfoam 102, 103 carbon dioxide foaming 258
MDI polyimide 258
composition of 61 Natural rubber latex 215
Microcellular foam 23, 243 Neopolen P
batch process 254 bulk density 179
commercial opportunities 261 moulded density 179
creep behaviours 251 Neoprene 217
extrusion processes 248, 249 Nitrogen autoclave process
fatigue 251 blowing agent 192
for construction 254 cell size 192
Gardner impact strength 251, 252, crosslinking 192
253 expansion 192
nanofoams 256 foam cell structure 192
open-cell 255
pressure-induced phase separation
256
O
pressure-quench method 246
processing of 244 Open cell foam 1
properties of 249 Open cell/closed cell ratio 2
relative density 250, 251 Ozone depleting substances 65
relative tensile strength 251 consumption phase-out of 63, 64
retrograde vitrification 259
semi-continuous process 247, 248
solid-state batch process 244, 245 P
sub-micron foams 256
supercritical CO2 256 Pentane blown PIR foam
temperature soak process 245 properties of 77
tensile property data 249 Physical blowing agents
tensile strength 250 carbon dioxide 137
unfoamed skin 245, 247 nitrogen 137

286
Subject Index

Plasticisers blowing agents 185


benzoates 163 body forming 195
butylbenzyl phthalate 163, 164 building and construction 198
dialkyl phthalate esters 163 butt welding 194
DIDP 163, 164 closed cell 173
Plastisol construction 202
gelation temperatures 165 crosslinking agent 185
lamination 170 electronics 199
Plastisol foam expanded (non-crosslinked) beads
coating 157 177
expansion 158 extruded crosslinked 179
formation 157 extruded non-crosslinked foam 174
fusion 158 foam density 196
gelation 158 foam structure 196
microsuspension resin 161 food contact 202
PVC resins 161 heat impression moulding 195
semi-gelation 157, 158 heat moulding 194
Polycarbonate injection moulded process 189
microcellular foams 246 manufacturing processes 174
Polyester foams 94 marine 198
Polyester polyols 58 materials 174, 176
Polyesters medical and health care 198
melting points of 60 military 199
Polyether foams 94 MuCell technology 176
Polyether polyols 57 nitrogen autoclave process 189
Polyethylene foam non-CFC blown 176
closed cell 5 open cell 173
Polyethylene terephthalate packaging 199
microcellular foams 246 polymers 183
Polyisocyanurate foams 57 post manufacturing operations 194
fire resistance 60 press moulding 189
Polymer foams press moulded crosslinked 186
extrusion of 125 Pressure and temperature system 179
Polyolefin foams 173 properties of 195
additives 185 recycling processes 193
aerospace 198 sheet lamination 194
annual demand 203 single stage extruder 174
appliances 197 single stage process 187
applications 197 specifications 200
automotive 197 sports and leisure 199

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Handbook of Polymer Foams

tandem extrusion system 174 applications 78


temperature 196 blowing agents for 65
thermoforming 194 comparative costs 69
toys 202 construction 78
two-stage process 188 glycolysis 75
vacuum forming 195 insulating board 59
Polyols 57 laminated panels 74
copolymer 89, 90 manufacturing processes 73
functionality of 58 properties of 76
polyester 89 recycling 76
polyether 89, 91 recycling processes for 75
Polystyrene foam 5 refrigerators and freezers 80
Polyurethane foams 94 sandwich panels 79
polyols for 58 Rigid PU foam boards
Potassium oleate soap solution thermal conductivity of 78
formulation 210 Rigid PVC foam 123
PVC 246 blowing agents 133
plastisols 156 Celuka process 128, 130
chemical blowing agents 133
R co-extrusion 130
flexural properties 145
Recycled expanded polystyrene foam density 131
slate replacement 53 foam formulation 132
wood substitute 52 foamed composites 147
Recycling formulations 141
compaction machines 52 impact behaviour 145
consolidated granules 193 lubricants 141
energy recovery 193 markets 124
extrusion 193 mechanical properties 143, 145
granulation 193 microcellular foam 146
heat moulded 193 physical blowing agents 137
reuse 193 processing aids 138
solvent-based system 52 processing temperature 132
thermal system 52 properties 143
Reticulated foams 111 recycled 146
Retrograde vitrification 261 recycling 145
Rigid foams stabilisers 140
isocyanate-based 55 volumetric flow rate 132
Rigid polyurethane foams 7, 55
appliance industry 80

288
Subject Index

S W
Sandwich boards Wallcoverings
metal faced 67 inhibited foamed 168
Styrene-butadiene rubber latex
formulation 233 Y
Silane crosslinking 185
Slabstock 101 Young’s modulus 3
mix head 100
Slabstock machines 99
Solid PVC
properties of 144
Stabilisers
carboxylates 140, 141
lead and zinc stearates 140
mercaptides 140
organotin 140
Sulfer
formulations 210
Surfactants 72
Synthetic rubber latices 216

T
Talalay process 207, 231, 232
curing 234
gelling 234
Technical foams 111
Thermal expansion coefficient 8
Thermal insulation foam 16
Thermal properties 6, 7
melting point 7
softening point 7
thermal conductivity 6, 7
Toluene diamine 61
isomers 88

V
Variable pressure foaming 90, 103
VarioCast process 75

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Handbook of Polymer Foams

290