Update On Mouldable Particle Foam Technology

Update on Mouldable
Particle Foam Technology
Robin Britton
Smithers Rapra Update

Update on Mouldable
Particle Foam
Technology
Robin Britton
iSmithers – A Smithers Group Company
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom

Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net
First Published in 2009 by
iSmithers
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©2009, Smithers Rapra
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.
ISBN: 978-1-84735-406-8
Typeset by Argil Services

Printed and bound by Lightning Source Inc.
C
ontents
1. Introduction ......................................................................... 1
2. Expandable Polystyrene (EPS) – A Mature Technology? ....... 7

2.1 Brief Description of the Product and
Processes .....................................................7
2.2 Developments in (Non-Halogen) Fire Retardation
of EPS ....................................................................... 12
2.3 Developments in Insulation Performance of EPS ....... 16
2.4 Modification of Other Properties of EPS ................... 21
2.4.1 Enhanced Temperature Resistance .............21
2.4.2 Enhanced Cushioning Performance ...........23
2.5 Reduced Levels of EPS Blowing Agents and
Alternatives .............................................................. 27
2.5.1 The Need to Reduce Volatile Organic
Compound (VOC) Emissions ....................27
2.5.2 ‘Low-pentane’ EPS Developments .............28
2.5.3 Alternative Blowing Agents .......................31
2.6 Developments in Making or Processing EPS Beads ... 36
2.6.1 Extrusion Processes for Bead Making ........36
2.6.2 Foam Nucleation .......................................38
2.6.3 Moulding of EPS .......................................38
2.6.4 Recycling of EPS........................................39
3. Expanded Polyolefin Moulded Foams (EPE and EPP) –

Materials with Growing Application .................................. 51
iii
Update on Mouldable Particle Foams
3.1 Key Features of Polyolefin Moulded Foams,

Compared with EPS .................................................. 51
3.2 Developments in Materials for EPP and EPE
Manufacture ............................................................. 55
3.3 Developments in Processing of EPP and EPE ............ 59
3.4 Development of Applications for Expanded
Polyolefin Bead Products .......................................... 62
4. ‘Sustainable’ Polymers – The Future? ................................. 69

4.1 Why Sustainable Polymers? ...................................... 69
4.2 Polylactic Acid (PLA) ................................................ 75
4.2.1 Production and Properties of
PLA Polymers ............................................75
4.2.2 Processing of PLA-based Beads – A Trend
Towards Carbon Dioxide ..........................78
4.2.3 Processing of PLA-based Beads – Interactions
Between PLA and Carbon Dioxide ............80
4.2.4 Processing of PLA-based Beads – Review of
Recent Patents and Patent Applications .....83
4.2.5 End-of-life Aspects of PLA Foam
Products ....................................................89
4.3 Starch and Starch-based Foams ................................ 91
4.3.1 Production and Properties of Starch-based
Polymers....................................................91
4.3.2 Processing of Starch-based Foamable
Beads .........................................................92
4.3.3 End-of-life Aspects of Starch-based Foam
Products ....................................................95
4.4 Polyhydroxyalkanoates (Including
Polyhydroxybutyrate (PHB) and Copolymers) .......... 96
4.4.1 Production and Properties of
PHA Polymers ...........................................96
iv
Contents
4.4.2 Blowing Agents and Processing of PHA

Foamable Beads.........................................98
4.4.3 End-of-life Aspects of PHA Foam
Products ....................................................99
4.5 Cellulosic and Other Sustainable Polymers ............... 99
5. Concluding Remarks – What Forces Will Drive

Development in this Field? ............................................... 107
Abbreviations ........................................................................... 111
Author Index............................................................................ 113
Subject Index............................................................................ 125
v
vi
P
reface
This Update has been written for technologists active in the mouldable
particle foam industry, who require an up-to-date account of the
status of the field, including areas with which they may not be so
familiar. It is also written for those who may have only recently come
into the industry, and though acquainted with polymer technology,
are not yet fully immersed in the specifics of particle foams.
This Update attempts to place the technology in context, beginning

with an account of expandable polystyrene and how its evolution
has responded to the demands of the market. This is followed by
a description of the expanded polyolefins and their development
trajectory, examining the way the differences between polystyrene
and the polyolefins have influenced their technology and applications.
Thirdly, there is a review of the emerging field of particle foams based
on renewable or sustainable polymers. Because these polymers are
not as familiar to many technologists, each has a short account of
how they are made and of their key properties, before going on to
examine their development status and the way their individual natures
may affect their market potential. Finally come a few thoughts on the
future and the influence of the critical factors we can envisage being
important in the way the field continues to develop.
I must first acknowledge the help and advice I have received from
my colleagues in the Synbra Group, especially Jan Noordegraaf and
Jürgen de Jong at Synbra Technology bv, who have been very helpful
in reviewing the text and suggesting improvements. I have to thank
all those within this industry who have helped me to explore what,
less than ten years ago, was to me an esoteric branch of polymer
vii
knowledge and one I had never expected to understand. I must

also acknowledge the assistance and encouragement I have received
from the editorial team at Smithers Rapra Technology, particularly
Dr. Stuart Fairgrieve. Finally, and most importantly, I am grateful
for the continuing support and patience of my wife, Rosemary, who
has tolerated my unavailability for more important or interesting
activities through much of the winter months, while this book has
taken shape.
Robin Britton,
Spring 2009
viii
1
Introduction
Particle foams form a significant part of the plastics foam industry,

and have their own technologies and markets. While there exist good
general reviews of polymer foam markets and technologies [1, 2],
these are now a few years out of date and do not go into the detail
of particle foams to the depth that a technologist working in that
industry would desire. This update is intended to fill that gap and
provide an overview of the most important technical developments
in this field.
The term ‘mouldable particle foams’ describes an industry which

manufactures small beads of thermoplastic polymers such as
polystyrene and polyolefins, expands those beads, usually by heating
a physical blowing agent (a volatile fluid) dissolved in the beads, and
subsequently moulds the expanded beads into shaped products. These
products can be as small as drinking cups or as large as blocks for
wall insulation or ground stabilisation. The purpose of foaming is
to reduce the weight of those products to obtain properties which
cannot be achieved in the solid form, such as thermal insulation or
impact protection. The particle foam industry is therefore defined
by its use of discrete foamed particles to mould into useful shapes.
Because such foams have found many and varied applications, their
technology has developed to meet the specific requirements of those
applications, as this update will show.
The foaming of thermoplastics, particularly polystyrene, has been

practised for many years – the first commercial process was patented
by Dow Chemical in 1935, and the buoyancy and water resistance of
their foamed ‘logs’ much exploited during World War II. Processes
1
were later developed for making sheets of foamed polystyrene, and,

by the 1950s, for mouldable expandable beads, the subject of this
update. ‘EPS’ (the abbreviation serves equally for expanded as well
as expandable polystyrene) has become a familiar product met with
at every turn of modern life – and when it has been discarded, or
crumbled into small white lightweight beads, a very obvious sign of
environmental degradation out of proportion to its quantity.
Surveys of the market for EPS suggest that 2007 saw worldwide
consumption of some 5 million tonnes [3, 4], compared with only
35,000 tonnes in 1960 [5]. Growth continues to be strong, especially
in Asia, which now produces around half the world total, the majority
for protective packaging. The second largest market is in Europe,
where construction (principally insulation) takes more than 70%,
while NAFTA countries are the major users of EPS for drinking cups.
The strength of manufacturing of consumer goods in Asia is clearly
the reason for the high proportion used for packaging there (and the
low proportion in Europe).
Although the technology of EPS manufacture and moulding can

reasonably be described as mature, there remains a steady flow
of innovation, and there are increasingly new challenges to its
position. Some of those challenges arise as a result of the perceived
environmental disfigurement alluded to above, the use of volatile
organic compounds in the production of the foam, the presence
of brominated compounds in fire-retarded EPS, and inevitably the
prospect of rising costs as the primary source of styrene monomer,
crude oil, becomes more scarce. The industry is addressing these as
well as the inevitable pressures of competitive products in its major
markets, and continues to develop new solutions.
Other polymers have also been produced as mouldable beads,

principally polyethylene and polypropylene, for applications where
EPS is inadequate, and there have also been successful efforts to modify
EPS in various ways to improve particular aspects of its performance.
There is now increasing interest in more ‘environmentally friendly’
foamed materials, made from ‘sustainable’ or ‘bio’ polymers, and
2
Introduction
in foam products which degrade quickly in the environment, should

they be discarded or composted. This interest applies just as much
to mouldable bead foams as to sheet products.
The main applications of moulded expandable foams are in protective

packaging and in insulation (mainly thermal). As beads can be
moulded into relatively convoluted shapes, they can be used to hold
and cushion irregularly shaped products within cartons or boxes, with
a minimal effect on the package weight. Moulded foams are also used
in impact-absorbing situations such as liners for cycle helmets, while
expanded, but not moulded, beads are used as loose fill in cushions
such as bean bags. There are also markets in food packaging and in
horticulture, where the lightness and rigidity of EPS allows delicate
products or plants to be handled without risk of damage.
The construction industry uses a great deal of EPS insulation within

roof structures, as interlayers within walls and also in floor structures,
as well as in very lightweight concrete shuttering systems which can
double up as moisture barriers. There has also been increasing use of
large EPS blocks to stabilise poor ground for construction of roads,
railways, etc. [4]. Loose expanded beads can also be blown into wall
cavities to improve their insulation. The long life and water resistance
of EPS are important in such applications, where legislation also
demands flame retardation.
Other applications exploit the water resistance and low density of

foamed polymers, such as in flotation aids for people, boats and
even buildings. The sound-deadening ability of polyolefin foams
leads to applications in vehicles (such as door liners). A low-volume
application is in a ‘lost wax’ process for metal casting, where the
desired product shape is first moulded in foam, then embedded in
sand. In the casting process, molten metal is poured onto the foam
which decomposes and leaves a precise cavity for the metal to fill.
The applications of mouldable bead foams are therefore many and

varied. This update reviews the most recent innovations in the field,
divided between polystyrene, polyolefins and ‘bio’ polymers. In the
3
course of addressing the issues that are currently driving development,

the discussion will highlight the key features that have made EPS so
successful, and show how the differences between polystyrene and
the other expandable polymers have affected their development
(and will certainly shape the development of new expandable bead
systems). Chapter 2, therefore, describes how the technology of EPS
is continuing to develop in the face of the challenges to its position
as the low-cost, large-volume market leader. Chapter 3 considers
polyolefin particle foams, competitive in particular niches, but
always held back by their relatively higher cost and complexities of
processing. Chapter 4 looks to the future for particle foams made
from ‘sustainable’ polymers (where the feedstock for the polymers is
plant materials rather than crude oil). There are a number of candidate
polymers, and their specific features, strong points and weaknesses
are reviewed; then the literature on the way the technology for each
is developing is summarised. Chapter 5 draws the update together
with a few thoughts on how particle foam technology is likely to
develop in the near future.
I have mostly drawn on ‘hard copy’ publications such as journal

articles and patents, although there are increasingly useful sources
of information on company web pages, etc. The difficulty with these
is that they are always likely to change, rendering the reference
outdated, though the reader is recommended to make use of these
sources in addition to the printed archive. Patents present another
challenge to the reader – the applicant is under no obligation to
make it easy for the researcher either to find the patent in the first
place or to work out the optimum embodiment of the invention. As
a result, it is quite possible that relevant patents have not come to
light, or that important points have been missed, and for any such
failings I apologise in advance. I have often referred to US patents
because they are in English and the other family members are in other
languages, but US patents are often less informative because they tend
to have a slighter discussion of the background and prior art than, for
example, European filings. The reader is encouraged to review those
other patent family members where more detailed insight is needed.
To add further words of caution, the existence of a patent does not
4
Introduction
guarantee that the product or process has been commercialised, or

is even commercially viable – there are undoubtedly examples in the
references of this update.
The references are up to date at the time of writing (early 2009), but,
as always, some may already have been superseded – new publications
may be on the way, or further patent grants or refusals. It is worth
the effort to follow up any point that is of interest and check for new
information – the field does not stand still, and this is particularly
true of the materials of Chapter 4, where significant progress can be
expected in the coming years.
References
1. Handbook of Polymer Foams, Ed., D. Eaves, Rapra
Technology, Shawbury, Shrewsbury, UK, 2004.
2. D. Eaves, Polymer Foams, Trends in Use and Technology,

Rapra Technology, Shawbury, Shrewsbury, UK, 2001.
3. W. Glenz, Kunststoffe, 2007, 10, 82.
4. M. Riethues and E. Klement, Kunststoffe, 2005, 10, 74.
5. E. Klement, Kunststoffe, 2004, 10, 80.
5
6
2
Expandable Polystyrene (EPS) –
A Mature Technology?
2.1 Brief Description of the Product and Processes

As described in Chapter 1, processes for making EPS beads were
first developed in the 1950s, and there are good descriptions of the
conventional suspension polymerisation process in a number of
texts [1–3] as well as the subsequent processes of pre-expansion and
moulding which are used to deliver EPS products. A brief summary
will therefore suffice in order to identify the most important aspects
which give EPS its main advantages and disadvantages.
Unexpanded EPS beads are typically 0.1–2 mm in size, and the

predominant production route is via a suspension polymerisation
which yields a range of sizes of spherical beads. These are charged with
a volatile organic blowing agent (often a mix of isomers of pentane) in
the final stage before dewatering and drying. They are then given an
organic coating (this works as an antistatic to prevent agglomeration
and also assists in the later processes) and sieved to different size
fractions to suit particular applications – smaller beads are used for
thinner-walled products – before they are stored in silos, or filled into
gas-proof bags or octabins. Each manufacturing site will have its
own set of recipes and process settings for the polymerisation, which
depend at least partly on the design and size of the reactors and also
on the product desired. There is a great deal of (‘secret’) proprietary
information about such aspects as suspending agents, bead size control
and cell nucleation additives, initiator and chain extender recipes,
process times and temperatures, blowing agent blends, bead coatings,
etc., although one suspects there has also been some convergent
evolution over the years that EPS has been produced.
7
More recently, extrusion processes have been developed which yield

‘microbeads’ of uniform size directly from a melt of polystyrene
(which may already contain blowing agent) by the use of an
underwater micropelletiser. The polystyrene melt may be supplied
from a one- or two-stage extrusion line, or even directly from a
polymerisation reaction carried out in a series of static mixers
and melt pumps. These extrusion processes offer the potential
for efficient incorporation of additives which create difficulties
in suspension polymerisation, and the uniform size of the beads
reduces the potential for waste when only a specific product size
fraction is required. For more discussion of the extrusion process,
see Section 2.6.1. The subsequent processing of extruded beads is
precisely the same as for polymerised beads.
The pre-expansion process involves using steam to heat and agitate

the beads and can be either a batch or continuous process, and may
be a single stage or be completed over a series of expansions. As
the beads are warmed by the steam to above the glass transition
temperature of the material, they soften and the blowing agent
boils at a large number of nucleation points, forming cells which
grow so that the whole bead is foamed throughout. Typically there
will be hundreds of cells formed within each bead, sometimes even
more. The key variables in prefoaming are the steam pressure
(temperature), the amount of dilution air and time – some pre-
expanders have a level sensor which stops the expansion when a
desired volume has been reached. Following expansion, the beads
(now a ‘prepuff’) are dried and discharged and allowed to mature
for a period of several hours (often overnight or even longer). This
allows them to cool and the cell walls to become rigid, able to
support the negative pressure once the residual blowing agent has
condensed. As maturing progresses, air diffuses into the beads,
and they become stable enough to be processed further. It is well
known that for a given bead type a lower final density can be
reached in two or more expansion stages than can be achieved in
a single steaming. In the case of multi-stage expansion, maturing
is required between expansions – usually these expansions are
individually less severe than a single-stage process (lower steam
8
Expandable Polystyrene (EPS) – A Mature Technology?
pressure, or shorter steaming time), but ultimately result in a

lower foam density.
Moulding is also effected with steam – the prepuff beads are blown
into an aluminium mould and steam applied through a number of
small vents. This softens the beads and expands them further, using the
residual blowing agent which remains in them after the prefoaming
and ageing steps, in order to fuse adjacent beads together. Vacuum
may be applied to the mould in the later stages, to help create a well-
fused surface on the moulding. The distribution of steam between
the mould halves can be adjusted to optimise the moulding process,
prevent distortion, etc. Cooling follows before the moulding can be
ejected and allowed to dry. Moulding cycles are much longer than,
for example, those of injection moulding, as the insulating properties
of the foam dictate long heating and cooling times, although section
thicknesses are also generally much larger than can be achieved in
injection mouldings. Tolerances on product dimensions are usually
quite wide – p1.5 mm is not unusual – as these are rarely critical in
the end application.
The machinery used for processing of EPS has developed to match

the properties of the material, and is quite different from that used
for more conventional plastics processing. Most moulded products
are (relatively) simple in shape and have wall thicknesses of several
to tens of millimetres – when a bead of 0.3 mm unexpanded diameter
is reduced to a density of 30 kg/m3, it has a diameter around 1 mm,
and it is good practice to design for sections which include several
beads in order to optimise bead fusion and product strength. Blocks
made for insulation purposes can be more than a metre wide and
high, and several metres long – smaller blocks and sheets are then
cut from them using hot wires or band saws. These differences have
tended to separate EPS and other foam moulding processes from
the plastics mainstream, but there remains a great deal of polymer
science which is applicable across the divide.
Key features of the standard EPS process give the material some key
strengths and weaknesses, summarised (not exhaustively) next:
9
Strengths
• Polymerisation can be carried out economically in relatively

small plants, so that the entry cost into the market is not high
– this tends to lead to a diversity of suppliers and strong local
competition. A few tens of thousands of tonnes per year is a
typical plant capacity (although larger producers have capacities
much greater than this) – this becomes a very large volume of
product when expanded and moulded. The cost of EPS products
tends to be kept low as a result.
• The blowing agent is well retained inside the beads at ambient

temperatures (provided the packaging has a gas barrier) so that it
is economic to transport beads in unexpanded form to dispersed
factories where they can be expanded and moulded to the final
shape.
• Steam at relatively low pressures is an ideal medium for expanding

and moulding EPS, as its glass transition temperature (Tg) lies
close to 100 °C. As the blowing agent plasticises the polystyrene,
lowering Tg, this helps to stabilise the expansion process – as the
beads grow and the blowing agent is driven off, so the material
becomes stiffer and more resistant to temperature. Because steam
has a high heat capacity, is easily applied and its temperature
controlled (via regulation of its pressure), the process is easy to
adjust and to optimise.
• Polystyrene is a stiff glassy polymer at ambient temperatures,

so that for applications which do not exceed 70 °C or so, it has
predictable strength and dimensional stability. It is also unaffected
by water and many environments.
• EPS is easily and widely recycled. Foam products may be

granulated back to the primary beads which can then be
incorporated into new mouldings with very limited effect on
properties, while crushed foam can be remelted (in more energy-
intensive processes) and recycled into solid applications.
10
Weaknesses
• The blowing agents used are mostly flammable organic solvents,

with consequent risks of explosion and fire during manufacture,
transport, processing and storage. Emissions of volatile organic
compounds are closely associated with EPS production and
are increasingly limited by environmental legislation, and the
costs of reducing the emissions continue to grow as those limits
are tightened. There is, however, no ozone-depletion issue as
has been the case with the chlorofluorocarbons (CFC) and
hydrochlorofluorocarbons (HCFC) used as blowing agents in
other polymeric foam systems.
• Both polystyrene and the blowing agent are flammable, and fire
retardation is required in many applications. This is particularly
important for construction insulation products. Almost all EPS
products for construction include brominated hydrocarbon
fire retardants often with peroxide synergists. Brominated fire
retardants are coming under increasing scrutiny as potential
persistent organic pollutants, and although the compound most
commonly used in EPS, hexabromocyclododecane (HBCD), has
not as yet been so designated, it is now proposed that it should be
considered under the European REACH legislation as a Substance
of Very High Concern. This issue is potentially very serious for
the EPS construction market, and much work has been done to
try to find solutions, without dramatic success to date.
• Because polystyrene is a glassy polymer, EPS has quite poor ductility

and toughness. Although a well-designed protective package can
offer its contents considerable protection against impact, this is
achieved at the expense of damage to the foam structure and
subsequent impacts are much less well cushioned.
These strengths and weaknesses will be explored further as we

consider recent developments in EPS and in other mouldable polymer
foam systems – they affect material choice for particular applications
and also the approaches which can be deployed to improve foam
performance.
11
2.2 Developments in (Non-Halogen) Fire Retardation

of EPS
As described in Section 2.1, fire retardation in EPS is almost always
achieved using brominated fire retardants and peroxides as a means
to pass the standard fire tests – the brominated additive releases
hydrogen bromide (a free radical scavenger) to quench the flames,
and the peroxide accelerates its release. The polystyrene matrix is also
attacked and breaks down, allowing the foam to shrink away from
the flame. There has long been interest in alternative fire retardants
for EPS, as for polystyrene in general, but the effectiveness and
economy of the bromine agents has meant that their position has
been hard to challenge. It is likely that only legislation (against the
bromine compounds) will ultimately drive the use of alternative fire
retardant systems, as the alternatives have their own disadvantages
– most significantly cost and the amount of fire retardant required to
meet test requirements, which can have effects on the quality of the
EPS. A recent review article [4] gives a good picture of the current
position and development directions.
There is a wide variety of tests used to assess the fire performance

of foams, depending on the application and the country in which
they are to be used. For automotive applications, for example, the
FMVSS302 horizontal burning test [5] can be used to measure a
burning rate, and the user can then specify a maximum value. The ISO
3795 [6] and UL94 [7] horizontal burn tests are frequently used in, for
example, specifications for domestic appliance insulation. Where the
foam is to be used in railway trains, CEN TS 45545 [8] is required.
For construction insulation the position is currently complicated by
the slow progress of harmonisation of standards within Europe – each
country has its own historically preferred test methods and standards.
Classification to EN 13501-1 [9], which employs the ‘single burning
item’ test (EN 13823 [10]), or a small-scale ignitability test to EN ISO
11925-2 [11], will soon be required throughout Europe, although
at present the DIN 4102-1 [12] test (similar to EN ISO 11925-2
[11]) is widely accepted, and EPS foam products with a B2 rating
are generally used in construction applications. Each of these many
12
tests is different from the others to some extent, and correlation of

performance between them is usually very difficult. A comprehensive
review of tests and requirements can be found elsewhere [13]. For
the formulator, therefore, it is essential to know the application and
to which fire test the EPS must conform – a good product for one
application can be overprotected (and therefore costly) for another.
HBCD/peroxide recipes work by a combination of flame quenching
and foam shrinkage – other fire retardants work in different ways
and often respond differently to the precise conditions of the tests
they must meet.
As with solid polystyrene compounds, the fire retardants most

examined in the literature are the phosphorus compounds, and a
number of patents have been filed in the past decade. One of the first
was for a combination of HBCD and a phosphorus compound such as
triphenyl phosphate (TPP), filed by Dow Chemical in 1999 [14, 15] –
the use of up to 4% of TPP allowed a significant reduction in the level
of HBCD, although not its elimination. The most active company
in the field has been BASF, with patents covering several different
combinations of additives filed over the period 1999–2005 [16-
22]. There are also patents from GE Plastics (now Sabic Innovative
Plastics) covering compositions which include polyphenylene oxide/
ether and phosphorus compounds [23, 24]. Dow Global has recently
been awarded a patent for a combination of a phosphorus compound
and an epoxy [25] and Kanegafuchi has a Japanese patent for a
recipe using sulfur and boron compounds [26]. These will now be
considered in more detail, as they illustrate the difficulties in finding
a good fire retardant system for EPS.
The four BASF patents all cover the use of phosphorus compounds
(always claiming for a list of such compounds, although some are
obviously more effective than others) but in combination with other
additives to improve the material performance. The first patent [16]
describes a combination of expandable graphite with a phosphorus
compound. The examples mention 5% of either red phosphorus
or dimethylphenylphosphonate (DMPP), with 15% of expandable
graphite – red phosphorus is preferred for an extrusion process. The
13
second patent [17], which was filed in 1997 but only granted in 2004,
takes a different approach, mixing the phosphorus compound with
a water-releasing metal hydroxide (such as magnesium hydroxide
or alumina trihydrate) at a combined addition rate of greater
than 12%. The best-performing examples have 10% TPP and 5
or 10% magnesium hydroxide. The third patent [18-21], which
is actually a family of four patents filed in different jurisdictions,
brings another phosphorus compound into play, 9,10-dihydro-9-
oxa-10-phosphaphenanthrene 10-oxide (DOPP), in combination
with a peroxide such as dicumyl peroxide or di-tert-butyl peroxide.
The ignitability test used to assess the samples is, in contrast to the
other patents that use the DIN 4102-1 B1 or B2 rating [12], a very
ad hoc horizontal burning test with a very short application of the
flame, and it is not clear how well any of these formulations would
perform in national or international standard test methods. BASF’s
most recent patent [22] for non-halogen compositions combines
the first two approaches mentioned above [16-21], claiming for
recipes which include a filler (chalk in the examples, but metal
hydroxides are also claimed), expandable graphite and a phosphorus
compound (red phosphorus, TPP and DOPP are all mentioned in
the examples), plus optionally carbon black or laminar graphite to
improve the insulation performance (see Section 2.3). Clearly the use
of phosphorus compounds is not an easy route to fire retardation –
the mechanism by which these agents operate, char formation, is less
effective in EPS than the flame quenching and shrinking mechanism
of the HBCD/peroxide system, and the amounts of additive used are
far higher – in a typical current recipe HBCD is present at less than
1% and the peroxide even less, where all of these patents describe
recipes with more than 10% of additive, sometimes much more. Such
a volume of ‘dead’ (non-expandable) filler can only be detrimental
to expandability, mechanical properties, etc.
One aspect that is not much discussed in the BASF patents, but is
relevant to the GE Plastics documents, is the strong tendency of
phosphate compounds to lower Tg of the polystyrene, reducing the
heat resistance of the foam. To overcome this, two patents [23, 24]
describe compositions which combine a phosphate such as resorcinol
14
diphosphate (RDP), TPP, DMPP, etc., with polyphenylene oxide

(PPO; GE Plastics’ name for polyphenylene ether). The PPO raises Tg
(back towards the 100 °C region of EPS) and also provides oxygen
to promote char formation.
Dow Global has pursued a slightly different track with their recently
granted patent [25], which employs a modified multifunctional epoxy
compound together with a phosphate such as DOPP. This patent
is not aimed specifically at EPS as the other are, but at polystyrene
applications in general, and mentions extruded foamed sheet (XPS)
products but not expandable beads. There is, however, no obvious
reason why this system could not be used in bead products.
Kanegafuchi Chemical Industries (also known as Kaneka Corporation)

filed an application for a Japanese patent [26] in 2003 describing a
combination of sulfur with boron compounds (plus, ‘advantageously’,
phosphorus compounds also). The fact that this remains only a
Japanese patent filing suggests that the approach did not have the
necessary performance/cost-effectiveness to justify wider patenting.
There have recently been patents for a quite different approach to the
challenge of improving the fire performance of EPS for construction
applications. Rather than incorporate a fire retardant package in the
beads, both BASF [27] and Ertecee, part of the Dutch Synbra Group
[28], have taken the route of applying a fire-resistant coating to pre-
expanded beads of EPS, then moulding the coated beads into slabs
or other shapes. The common feature to both is the use of sodium
silicate (waterglass), but the coatings are otherwise quite different.
BASF’s method bonds the waterglass to the beads with an aqueous
dispersion of an acrylate adhesive, which can then be used to fuse
the beads together in the moulding step, while Ertecee’s process for
Xire reacts the waterglass to form a coating on the beads which
becomes insoluble after moulding. In both cases the weight of the
coating is much greater than that of the EPS – the moulded products
have densities of 80–100 kg/m3 or more, with the beads contributing
less than 20 kg/m3 – but the fire performance is in a different league
from that of a more conventionally retarded EPS. The panels are more
15
fire-resistant and retain their integrity in a fire situation, rather than

shrinking away from the flames with a limited degree of burning.
2.3 Developments in Insulation Performance of EPS

The good insulation performance, low weight, moisture resistance
and long-term stability of EPS led quickly to its widespread use as
a thermal barrier layer within the walls and floors of buildings, and
within roof structures. At present, some 70% of EPS produced in
Europe is for such applications. The construction industry has in
recent years sought improved performance, either for thinner and/or
lighter but equally insulating structures, or for higher insulation levels,
and as energy efficiency is becoming an ever more central concern,
this demand is only likely to grow. The manufacturers of EPS have
responded with a series of innovations. ‘System solutions’ such as
composite panels for rapid construction of walls or roofs have become
popular, but this account will focus on the developments in the foam
materials themselves which have brought about improvements in
insulation performance.
The transfer of heat through a panel of foamed EPS is usually

measured (to ISO 8301 [29], using apparatus to EN ISO 8990
[30]) at an average of 10 °C, and the coefficient of heat transfer
(L is expressed in units of W/m/k. Heat transfer is controlled by
four mechanisms – conduction through the material of the cell
walls, conduction through the gas in the cells, radiation through
the structure and convection within the cells [31]. The convection
contribution is very small if the cells are smaller than around 3
mm in diameter, so unless the foam structure is very coarse it
can be ignored for practical purposes. The combined conduction
contribution reduces with foam density, as the polymer has a higher
conductivity than the air in the cells. There could therefore appear
to be an advantage (apart from the economic argument for lower
densities) in reducing foam density, but, unfortunately, the radiative
transfer (at ambient temperatures it is predominantly due to infrared
radiation) rises more rapidly. As a result, the curve of L against foam
16
density shows a minimum around 25–30 kg/m3. As it is economically

desirable to work at rather lower densities, much effort has been
devoted to reduce the minimum value of L, and to reduce the rate
of rise at densities below that minimum.
A number of additives have been found to improve L, by increasing

the extinction coefficient of the matrix material of the cell walls,
and a large number of patents have been filed for the use of such
additives, although only a small number have proved to be cost-
effective. The most popular are carbon in various forms – graphite,
carbon black and activated carbon – all of which absorb infrared
radiation. Other effective additives include metal powders and oxides.
As these products are aimed at the building insulation market, all
have a fire-retardant additive package, usually HBCD with a peroxide
synergist (see Section 2.2). There exists a great deal of intellectual
property relating to additives to improve L, going back a number of
years. Some of it overlaps, and it can be difficult to reliably ascertain
whose claims have primacy. It is clear, however, that BASF, with its
Neopor product based on graphite, has generally set the pace in this
field. Other established products are Silver from Nova Chemicals,
which incorporates carbon black [32], and Lambdapor from Sunpor
Kunststoff GmbH.
The BASF patent portfolio introduces the term ‘athermanous’, i.e.,

not permeable to radiant heat, to describe particulate additives for
the reduction of heat transfer through EPS, and the first in what is
now a large family were filed in the late 1990s. The effectiveness of
carbon black and graphite, for example, in reducing the heat transfer
through foam blocks (e.g., XPS) was known rather earlier, and there
are patents dating from the early 1990s, but there are two [33-35]
that are the earliest for an expandable bead product with improved
L. These patents describe beads made by extrusion, subsequently
suspended in water and impregnated with blowing agent. The
composition of the first patent [33, 34] claims the use of 2–8% of a
carbon (furnace) black with a primary particle size of 80–120 Mm,
while the second [34] uses 0.5–8.0% of graphite particles, with a
size between 2.5 and 12 Mm. A fire retardant is also incorporated
17
and the beads are finally coated with a hydrophobicising coating

including a paraffin wax. Other athermanous particulate additives
claimed include carbon black, metal powders such as aluminium
and metal oxides such as iron or aluminium oxides. A slightly later
patent [36, 37] claims extrusion of graphite-containing beads with
the blowing agent injected before underwater pelletisation. In the text
is a reference to the strong nucleating effect of graphite, requiring
the beads to be cooled under pressure. Suspension polymerisation is
stated to be possible, but is not mentioned in the claims.
A polymerisation process is claimed [38-40], where the use of

0.5–30% polystyrene dissolved in the styrene monomer is stated
to help to increase the viscosity of the reaction mixture (and
presumably help the dispersion of the graphite). Another patent
[41] covers the use of up to 10% of aluminium powder in a
suspension polymerisation process, pointing out the need either to
vent hydrogen or to prevent its formation by passivating the metal
powder, which should be platy with a maximum dimension of 30 Mm
and is suspended in styrene monomer before adding it to the reactor.
Carbon black or graphite may also be added. Aluminium blocks
the transmission of infrared radiation by reflecting it (whereas
carbon absorbs it) so that it may be advantageous to have both a
reflector and an absorber present – more recent patent applications
highlight this approach.
Sunpor Kunststoff GmbH of Austria obtained a patent in 2000 [42]

which combines additives in this way. The process claimed is either
extrusion or polymerisation, and the recipes include (a) up to 4%
of platy aluminium particles (greatest dimension 15 Mm) and (b)
0.3–1.0% of aluminium powder and antimony trisufhide powder
(quantity not specified, but size between 10 and 60 Mm). Additionally,
up to 2% of carbon black or graphite may be used. This patent
appears to overlap to some extent with BASF’s patent [41], although
it was granted earlier.
BASF has continued to file patents covering refinements to the

graphite technology, including one [43, 44] that describes the use of
18
an ‘expansion assistant’, an olefinic oligomer with unsaturated groups

at the chain ends, which is claimed to improve the expandability of
the beads (see Section 2.5.3 for more discussion of expansion aids),
a second [45, 46] that claims advantage for an extrusion process
which results in a fine dispersion of water droplets (up to 1.5%)
within the beads as an auxiliary blowing agent and a third [47, 48]
that describes the use of surfactants to improve the dispersion of the
graphite, in either a suspension polymerisation process (exemplified)
or an extrusion process (claimed but not in the examples). There
is also a 2007 application [49] for use of a mixture of absorbing
and reflecting particles – this document does not appear to have
any examples of the invention, and it may be revised before it can
be granted.
Synbra Technology BV of The Netherlands obtained two patents

in 2007 which cover different additives to reduce L [50, 51] – the
first claims the use of metal powders, specifically copper powder at
an addition level of 2.5–3.0%, while the second claims the use of
activated carbon powder (smaller than 5 Mm) at 3–8%. The possible
incorporation of further additives such as graphite, metal powders
or metal hydroxides is also mentioned in this patent, although
not exemplified.
Polimeri Europa SpA of Italy has recently been active in patenting

methods to reduce the heat transmission of EPS, including one [52]
for the use in extruded bead manufacture of high-refractive-index
infrared reflectors such as titanium dioxide or barium sulfate – this
would yield white insulating products, and would therefore be
at an advantage in the market on the grounds of distinctiveness.
The fact that there does not yet appear to have been a successful
commercialisation suggests that either the cost is high or the
improvement in L is insufficient. More conventional approaches
are covered in three further filings [53–55]. The first of these offers
an explanation as to why suspension polymerisation with carbon
particles present can be problematic – the carbon interferes with
the activity of the peroxide initiators, and the patent claims that
the way round that interference is to use peroxides without benzene
19
rings. The second is at present ungranted and appears to be on the

same track as a previous patent [42] in terms of the mix of additives
(which also includes talc, hydrotalcites, montmorillonites, etc.), but
also claims for a method of heat-treating the beads, after coating
them with a lubricant, for about an hour at 50 °C – what change this
brings about in the beads is not stated, but it is claimed to improve
L by up to 10% – perhaps this treatment affects the nucleation
and subsequent cell structure of the foam. The third is also as yet
ungranted, and takes a different route to bead manufacture. In
this application, the composition incorporates a range of possible
additives, including carbon black, graphite, oxides, sulfates or
dichalcogenides of various metals and lamellar inorganic silicon
derivatives as well as a nucleating agent which is a polyolefin or
polyamide wax. This is melt-compounded, blowing agent is injected
and the beads extruded in the form of strands which are cut to
produce non-spherical particles. The benefit of the nucleator, which
is essential to the invention, is to eliminate the need for annealing of
the beads after extrusion. Finally, Polimeri has filed a voluminous
patent application [56] which claims the use of graphite dispersed
(in a masterbatch, therefore) within a polymeric matrix which
is not fully miscible with the polystyrene, and therefore forms a
heterophase structure within the foam. The foam still has more
than 60% closed cells.
Although there has been a great deal of effort devoted to improving

insulation performance, it has tended to be along similar lines –
that of including within the foam structure additives that block
infrared transmission. A more speculative idea, which certainly has
not yet been realised, is to reduce the size of the cells within the
foam to such a small size that the Knudsen effect comes into play.
Here, when the cell size approaches the mean free path of a gas
molecule (a few hundred nanometres for air at ambient conditions),
heat transfer is significantly hampered and L will improve. BASF
researchers have been looking into the possibility of producing such
‘nanofoam’ structures, but their realisation appears to be some way
off [31, 57].
20
2.4 Modification of Other Properties of EPS
2.4.1 Enhanced Temperature Resistance
The relatively high Tg of polystyrene, at around 100 °C, makes EPS a

very useful material in many applications, but there are more in which
higher temperature resistance is required. These include insulation for
water heating appliances, and even in space heating – the long-term
temperature limit for EPS (80–90 °C, dependent on how long ‘long
term’ is) falls uncomfortably close to service temperatures for such
applications, and at present thermoset foams such as polyurethanes
capture much of this market. Even higher levels of temperature
resistance open up opportunities in, for example, steam-sterilisable
items for health care. It is no surprise therefore that EPS producers
have sought ways to add value to their products.
One well-established method for enhancing the heat resistance of

polystyrene is to blend it with poly(2,6-dimethyl-1,4-phenylene
ether), known by the abbreviations PPE or PPO. As PPE has a
Tg around 210 °C, and blends with polystyrene are miscible and
have Tg values linearly related to their composition, solid moulded
or extruded products based on such blends have found wide
application – Noryl from Sabic Innovative Plastics (formerly GE
Plastics) is probably the best known brand name, but other polymer
manufacturers also offer such blends. It was therefore logical to
produce foamable grades, and several manufacturers have done so,
including GE Plastics (Noryl EEF) and Nova (Dytherm). It has,
however, proved impossible to achieve narrow bead size distributions
in polymerisation, and as the market for such products has proved
relatively small, it has proved difficult to reduce waste levels by
finding customers with applications across the full size range. As a
result, polymerised beads with high-temperature performance have
been significantly more expensive than standard EPS grades and their
market share has shrunk, to the point where most grades have been
withdrawn. The introduction of extrusion routes to produce beads
with specific sizes has improved the economics to some extent, and
21
grades are currently offered by, among others, Sunpor Kunststoff

GmbH and Synbra Technology BV. Grades with PPE contents up
to 30% (temperature resistance up to 120 °C) have been produced
and marketed – this remains, however, a niche and volumes are
very small. Fire-retarded grades are often demanded, and the only
route to making extruded beads of polystyrene/PPE blends is to use
phosphorus-based fire retardants (see Section 2.2) which are very
effective plasticisers – as a result the blend formulation even for a
110 °C service temperature is very expensive.
The other feature which handicaps these high-temperature EPS grades

is that very heat resistance – pre-expansion and moulding require
higher temperatures (high steam pressures) than are achievable
with conventional EPS equipment. Although suitable equipment
is available, the additional challenges and costs have acted as an
additional brake on the appeal of these grades.
The polystyrene/PPE blends are aimed at uplifting the heat resistance

significantly, but there are markets where even a few degrees extra
performance can be advantageous, for example in drinking cups
for hot beverages. Such relatively undramatic improvements in
heat resistance have been sought via copolymerisation, and a
series of papers from Turkey reports the results of such studies.
Copolymerisation with up to 5% of A-methylstyrene (which when
made into a homopolymer has a Tg value of around 170 °C) raised
Tg by a few degrees [58], but as the co-monomer is less reactive
than styrene, it was not possible to achieve copolymers beyond that
level. The resulting foamed material had acceptable properties. The
second paper in the series [59] reported experiments with silicone
acrylate as the co-monomer, but targeted more at improved surface
properties. Up to 0.5% of a polydimethylsiloxane prepolymer was
copolymerised into styrene and foamed beads produced. The siloxane
side chains give the foam a smooth glossy surface with a significantly
higher contact angle than the control EPS, and Tg was around 2 °C
higher. Interestingly, the mean bead size increased with siloxane level,
but the spread of sizes reduced. Foam density was higher, although
figures are not reported. The third of these papers [60] reports further
22
studies with siloxane co-monomer, this time using a ‘macroinitiator’

prepared from the same polydimethylsiloxane prepolymer. The effect
of using this longer chain co-monomer was to reduce mean bead size
as well as its spread, but increased the foam density to some extent.
The increase in Tg was again a few degrees and contact angle was
again increased, with a glossy smooth surface – it was remarked that
these foam beads flowed better than standard EPS beads and were
less prone to blocking the pre-expander.
A copolymer of styrene that has, in the solid form, a higher heat

resistance is styrene-maleic anhydride (SMA) and although there
does not appear to be any reference in the literature to foamed beads
made from this polymer, there is no obvious reason why it should
not be attempted. It is possible that the cost of the polymer would
effectively exclude it from the market – SMA grades find somewhat
specialised applications and are therefore much more expensive than
polystyrenes, but have Tg values some 25 °C higher.
2.4.2 Enhanced Cushioning Performance
The purpose of any packaging is to protect its contents, and should

ideally be as cheap and as light as possible, with minimum bulk –
it will be discarded (preferably to be reused or recycled) once the
contents are unpacked. EPS is widely used to protect fragile items
such as electrical or electronic goods against impact damage during
transport and handling, because it has good cushioning performance,
low weight and low cost, but it does have some drawbacks. In
particular, EPS packaging absorbs an impact shock by breakage
of the foam cell walls, and is thereby itself damaged – subsequent
impacts are less well absorbed. There are many applications where
protection against multiple impacts is needed, and this is one where
the advantages of moulded polyolefin foams are often exploited.
These do have a cost penalty, and EPS manufacturers have long
sought to modify their foams to offer better resilience in order to
improve their competitiveness.
23
The cushioning performance of any protective packaging can be

assessed by dropping the assembled package onto a hard surface
from a height that is representative of the likely service conditions,
then checking the contents for damage. The drop height will depend
on the package size and weight – for example, a heavy package
(such as a washing machine) is unlikely to be dropped very far,
perhaps a metre at most, while lighter packages may well be treated
much more roughly. A great deal of expertise has been developed in
package design and materials characterisation [61, 62], so only the
key features will be described here.
When protective packaging is designed, the first property to be

quantified is the tolerance of the contents to impact shock (G-value
of acceleration, though usually as a deceleration). This can be an
expensive process, but there are good protocols for minimising the
number of destructive drop tests to be done. Once the designer knows
the maximum G-value the product can tolerate, and can estimate the
likely exposure to dropping in transit (e.g., one trip from the factory
to the end user, with minimal handling, or shipping by air freight
with multiple loading and unloading), a package can be designed to
minimise the probability of seeing damaging G-values. This is where
the cushioning properties of the packaging material are considered,
as the designer seeks to design a protective package with the smallest
bulk (to maximise the number of packages that can be shipped in
a given volume), lowest weight and lowest cost (as the cost of the
packaging is additional to the product cost but adds no value).
Cushioning performance of packaging foams is measured, for

example to EN ISO 4651:1995 [63] or ASTM D1596-2003 [64], by
using a series of drops of different weights from different heights onto
blocks of foam of different thicknesses, and measuring the maximum
instantaneous G-value as the weight is brought to rest. Analysis of
the results is then required in order to be able to use them in package
design. The response of a series of samples of a foam to increasing
drop weights from a chosen height yields a ‘cushion curve’. At low
drop weights the foam is not much compressed and the G-value is
relatively high. As the drop weight is increased, the foam absorbs the
24
shock by internal damage and deformation, and the peak G-value

falls, before rising again as the shock-absorption capacity of the
foam is exhausted and the weight ‘bottoms out’ through the sample.
Repeated drops onto the same sample show a steady increase in the
G-value, as the foam sustains accumulated damage and is unable
to decelerate the weight so efficiently. Traditionally a series of such
cushion curves would be required at different drop heights and sample
thicknesses, and for five successive drops on each sample, involving a
huge number of tests, but it is now possible to characterise a material
using a ‘stress-energy’ approach and a relatively small number of tests
[65]. Such testing requires specialised test equipment and skills, so
can still be expensive to carry out – but the cost of getting a package
design wrong can also be very high.
As mentioned, EPS absorbs shock, after the initial compression of the

air in the foam and flexing of the cell walls, by crushing of the cells
and breaking their walls. After the load is removed, the foam does
not recover completely, as its internal structure has been damaged.
Subsequent shocks are therefore less well absorbed – the cushion
curves show an increase in the minimum G-value for that drop
condition – corresponding to a greater likelihood of the package
contents being damaged. EPS is also relatively brittle, even when the
beads are well fused together, so the protective cushions may become
cracked or broken after one or more impacts, further reducing the
protection they offer.
Efforts to improve the resilience of EPS were originally focused on

the standard polymerisation route to beads, so that any modification
to the recipe was required not to interfere with the polymerisation of
the styrene. In 1997, Asahi Kasei patented a polymerisation route to
an expandable polystyrene bead toughened with dispersed styrene–
butadiene copolymer regions [66], but this product has made little
impression on the market, probably for reasons discussed next.
A route was found by Sekisui to incorporate polyolefin domains

within the beads. The technology was licensed to and taken forward
by Arco, later absorbed into Nova Chemicals [67]. This is actually
25
accomplished by impregnating a very finely divided polyolefin powder

[usually powdered ethylene–vinyl acetate, (EVA)] with styrene
monomer, then polymerising the styrene around the olefinic polymer.
Typically the styrene content is around 70%. The polymerised beads
are then impregnated with pentane before the usual steps of drying,
coating, sieving and packing. The presence of the polyolefin domains
within the beads brings real improvements in resilience, but has some
adverse consequences, which have made Arcel (Nova) and Piocelan
(Sekisui) expensive products and limited their market penetration.
The first consequence is that the pentane is much less well held in
the beads, so a high level (up to 12%) is required to achieve good
expansion (much more pentane escapes during pre-expansion than
in standard EPS). The second is that the pentane diffuses out of the
beads readily during storage and transportation, so that the beads
must be refrigerated to below 4 °C until they are pre-expanded. One
countervailing benefit is that once pre-expanded the beads do not age
as quickly as EPS, so can be stored for long periods before moulding
without loss of mouldability, although shrinkage during moulding is
noticeably greater than for EPS, as there is little pentane present to
help expand the beads against the pressures of moulding.
Other manufacturers have found methods to produce blends of

polystyrene and polyolefins for improved resilience (e.g., Dow [68],
using their interpolymer technology), but at present the market
only supports the two suppliers. The performance of these foams is
markedly better than EPS on repeated drops [32] (see also Nova’s
technical literature) and products made from them are much tougher
so that repeated reuse and multiple impacts are far better tolerated. As
the ‘first drop’ cushioning is almost as good as for standard EPS (not
the case for expanded polypropylene; see Chapter 3), these materials
find application where this performance is important, despite their
high cost (up to four times that of EPS).
A recent US patent application on behalf of Nova Chemicals [69]

contains a good description of the process of making these polyolefin–
polystyrene interpolymer beads. This application is actually aimed at
interpolymers which can be used in other processes such as injection
26
moulding, sheet extrusion and foamed sheet processes, where the

crosslinking of the polyolefin that occurs during polymerisation of
the styrene is a handicap. By eliminating the crosslinking (a side effect
of the dicumyl peroxide initiator for the styrene polymerisation),
materials of lower melt viscosity and better processability can be
made. This is not a particular benefit for expandable beads (and may
actually reduce their resilience) but the application does contain a
deal of useful information about the patent background as well as
the production and use of styrene–olefin interpolymers.
In recent years several manufacturers have sought ways to achieve

improved resilience at lower cost, and products such as Sunpor’s
TM-B, Synbra’s SHOCK and Huntsman’s R-MERII have been
marketed. These appear to be a half-way house between EPS and
Arcel, employing the more conventional technology of high-impact
polystyrene (droplets of styrene–butadiene copolymer dispersed
within a polystyrene matrix) and made by the extrusion route (see
Section 2.6.1). These grades can be processed just like EPS, and do
have improved multi-drop cushioning, but are still relatively brittle,
so have not achieved much market penetration to date.
2.5 Reduced Levels of EPS Blowing Agents and

Alternatives
2.5.1 The Need to Reduce Volatile Organic Compound

(VOC) Emissions
Pentane and other blowing agents commonly used in EPS are very
effective but they are nowadays seen to have an environmental
downside. When EPS beads are produced, stored, pre-expanded,
moulded and post-aged, some blowing agent is vented to the
atmosphere at each stage (particularly during pre-expansion and
moulding). Typically beads are produced with some 5–6% of blowing
agent, so that the 5 million tonnes of EPS produced in 2007 released
250,000–300,000 tonnes of volatile organic compounds (VOC) to the
27
atmosphere (and as each pentane molecule will quickly be oxidised

to five carbon dioxide molecules this adds almost 1.5 million tonnes
of greenhouse gas, additional to that arising from the processing,
transport and final disposal of the EPS). There is also a question mark
over links between pentane emissions and ozone formation [70].
Increasingly, emissions are being regulated by national and regional
governments, and the EPS industry is not immune. Although it is often
possible to capture and destroy (usually by burning, which releases the
carbon dioxide more quickly) the VOC emitted from polymerisation,
pre-expansion and even moulding processes, it is never possible to
capture all of the blowing agent – in thick-section products it may
take weeks for the last of the pentane to escape. There is therefore
a demand for grades which contain and emit smaller quantities of
VOC, and most EPS manufacturers now offer ‘low-pentane’ grades
(typically 3.0–4.5% pentane content, although Nova Chemicals offers
an ‘ultralow-pentane’ grade with 2.5% pentane [71]).
2.5.2 ‘Low-pentane’ EPS Developments
The challenge to be met in developing an EPS with reduced blowing

agent content is to obtain a material which can be expanded
comparably quickly and to a similarly low density as standard grades.
As the lower pentane level means that the starting Tg of the polymer
is higher and there is also a lower internal gas pressure to expand the
beads, some means must be found to weaken or plasticise the polymer.
This enables the cells to expand more quickly and thus expansion
can compete more effectively with evaporation of the blowing agent
from the bead surface.
Various methods exist and have been tried for plasticising the
polystyrene, and development work continues. There are probably
rather more proprietary formulations than are to be found in the
patent literature, as not all manufacturers are willing to publish
their findings in this way – or they use obscure wording so that their
patents are hard for competitors to find. A number of patents have
been found and are discussed next.
28
The first patents in this area were filed by BASF, which has a family of
US patents dating to the early 1990s. One from 1992 [72] is a typical
example, and claims a bead with a pentane level of 2.0–4.4%. The
key to its improved expandability is stated to be the precise control of
molecular weight distribution and limited branching. The molecular
weight should be between 180,000 and 300,000, with polydispersity
below 2.5 and less than 5% branching. Even so, a series of expansion
stages, with the beads allowed to mature between them, is required
in order to reach commercially useful (20 kg/m3 or less) product
densities. More recent patents appear to contradict this prescription,
but that was the state of development at that time.
The plasticisation approach was developed around the same time,

and a variety of additives have been covered in patents from a
number of companies. A Czech patent granted to Kaucuk [73]
claims an ‘internal additive’ comprising a mixture of partial esters of
unsaturated higher fatty acids with pentaerythritol (and optionally in
combination with similar esters with glycerol) added at up to 0.8%
A patent [74] granted to Kanegafuchi of Japan in 1999 describes the
use of a ‘foaming assisting agent’ such as a mixture of hexane and
cyclohexane, added to the beads at 0.3–2.0%. Another [75] granted
to Cheil Industries Inc., of Korea in 2001 has a more complicated
recipe for a fire-retarded EPS, with less than 4% pentane, 0.5–1.0%
glycerol tristearate, 0.05–0.5% of an EVA/ethylene vinyl alcohol
polymer, 0.1–1.0% HBCD and 0.05–0.5% dicumyl peroxide in a
styrene-based polymer. All three of these patents were filed only in
the home countries of the applicant companies (and in their own
languages) and it is not clear how far these products have been
successfully commercialised.
Within a very recent patent (see next [76]) is a summary of the

technology of another Japanese patent [77] granted to Mitsubishi
Kagaku in 2002, quoted as an example of prior and less satisfactory
art. The bead formulation contains up to 5% of a plasticiser such
as a liquid paraffin or an ester with a boiling point above 200 °C,
as well as more than 0.1% residual styrene and less than 0.2% of
total of aromatic solvents such as ethylbenzene, toluene, xylenes, etc.
29
These are said to expand well, but to produce foamed beads that
are hard and tough.
BP Chemicals were awarded a patent in 2005 [76] which claims

improved expandability using a petroleum wax (alkanes from C18
to C80) and a nucleant (a Fischer–Tropsch or polyolefin wax). The
description of the prior art discusses the (known) use of waxes to
improve moulding by migrating to the bead surfaces and improving
their adhesion to one another (although this also leads to clumping
during pre-expansion) and also accelerated cooling. The petroleum
wax of this patent is uniformly distributed within the beads – addition
levels from 0.1 to 1.0%, although for low pentane contents 0.3–0.6%
is best. There is a list with a number of trade names of potentially
useful waxes.
A recent patent using the plasticisation approach to improve

expandability was granted to Dow Global in 2008 [78], and claims
advantage for a combination of three additives which together make
up no more than 3.5% of the bead composition, and a pentane level
of 3–5%. The examples use isobutyl stearate (up to 1.5%), a mixture
of C20–C50 saturated aliphatic hydrocarbons (also up to 1.5%) and
isopropylbenzene (0.1%) – the patent purports to show that all
three additives are needed, otherwise the expansion is inadequate
(densities 20 kg/m3) or the foamed beads are ‘hard and tough’. It is
notable that the base polystyrene has a molecular weight in the region
of 200,000–220,000 and polydispersity around 2.75 – a broader
distribution than in a patent mentioned previously [72].
BASF has taken a slightly different path with another 2008 patent
[79, 80] which demonstrates development since the early 1990s. Now
a broad, even multimodal molecular weight distribution is seen as
essential, and the ‘best’ examples are blends using a low-molecular
weight terpolymer (Joncryl ADF1300) of styrene, acrylic acid and
A-methylstyrene at up to 10% addition to polystyrene with molecular
weight of 280,000 and polydispersity of 2.8. Another example
has a 1:1 blend of two polystyrenes with molecular weight values
of 195,000 and 280,000 and no low-molecular weight polymer –
30
this also has improved expandability, although not as good at low

pentane levels as the terpolymer blend. Such a low-molecular weight
(between 2000 and 10,000) terpolymer is effectively a plasticiser,
with Tg around 56 °C – the patent claims that it is most efficient
when added at 3–8%. These blends can only be produced using
an extrusion and micropelletising process (see Section 2.6.1) rather
than via polymerisation (it is possible to obtain bimodal molecular
weight distributions in suspension polymerisation, but not easy to
incorporate the low-molecular weight terpolymer).
A particular type of low-pentane EPS is described in a family of

BASF patents from the early 2000s [81-83]. These cover ‘expandable
styrene polymers containing carbon particles’ – a Neopor type of
product (see Section 2.3) which incorporates graphite particles to
block infrared radiation in the finished foam insulation block, but
also uses the graphite as a carrier for water as an auxiliary blowing
agent. The description of the prior art mentions the known use to
improve expansion of plasticisers such as the higher hydrocarbons
mentioned in patents described previously, or the use of dimeric
A-methylstyrene as a ‘regulator’, and also the advantage of a
specific molecular weight distribution in avoiding the need for
such remedies. The preferred embodiment contains 3–4% pentane,
3.5–6.0% water and around 5% finely powdered graphite (average
particle size of 30 Mm) and can be expanded to around 15 kg/m3
without difficulty.
2.5.3 Alternative Blowing Agents
As has already become clear, pentane and similar organic solvents

make ideal blowing agents for EPS – they dissolve in polystyrene and
are therefore well retained in storage, they plasticise the polymer,
helping to start and stabilise the foaming process and they volatilise at
temperatures that lie conveniently between typical ambient values, Tg
of the polymer and the temperature of the steam used for expansion.
This does not guarantee that their use will continue to be encouraged
or even permitted, as their flammability alone brings significant risks,
31
and they also present health and environmental concerns. There is

increasing pressure on the industry to reduce or eliminate as many
of such hazards as possible, and it is therefore no surprise that EPS
producers have been exploring ways to reduce levels and possible
substitutes for the pentane they have been using for many years.
The challenge remains formidable, however, and it is likely that
complete replacement will only come about if legislative or customer
pressure demands it, as there will inevitably be consequences for
the production, expansion and moulding processes which are well
developed and efficient. The resulting costs and compromises may
affect the competitive position of EPS against other materials or
systems in each of its applications.
One ‘obvious’ alternative approach is to use water dispersed

within the beads as the sole blowing agent, and Nova Chemicals
has pursued this route, in conjunction with workers at the
Catholic University of Leuven and the University of Eindhoven,
over a number of years [84-86]. The key challenges are firstly to
incorporate water into the beads, secondly to retain it there and
thirdly to be able to foam the beads in a conventional pre-expander
and obtain mouldable expanded beads. Polystyrene and water do
not mix well, and so a carrier is useful to hold the water within the
beads until it is needed for expansion – microcrystalline starch was
the chosen carrier in the Leuven studies. This has its own difficulties,
as starch is incompatible with polystyrene – the first two papers
described work done to improve the interaction, by grafting or
compatibilisation, in order to be able to achieve a fine dispersion
of starch in the polystyrene beads. A 2003 conference paper [87]
describes these and the downstream processing challenges – in the
prefoaming process the steam temperature must be above 100 °C in
order to boil the water, and this is also above Tg of the polystyrene.
As the temperature resistance of the polystyrene does not increase
as expansion progresses (as occurs with pentane) there is a risk of
collapsing the beads. Finally the moulding process requires more
care, as there is no residual plasticisation to assist in fusing the
beads together to form a strong product, and again higher steam
temperatures are needed.
32
A later paper [86], the final one in a series of four from Eindhoven
University of Technology, takes a different approach. The polystyrene
is first prepolymerised in a bulk polymerisation process, and the water
is dispersed in it as a water-in-oil emulsion during this stage. Sodium
chloride in the water is used to control its droplet size and dispersion
and the polymer viscosity is sufficient to preserve the emulsion
through the second stage. The prepolymer with its dispersed water
is then finished in a normal free radical suspension polymerisation.
Beads with up to 4% of finely dispersed water can be achieved in this
way. In order to increase the melt strength and temperature resistance
of the polystyrene so that it is more robust during the expansion and
moulding processes, a proportion of PPE/PPO is added to the reaction
mixture. The optimum recipe yields beads with up to 8% water (the
PPE also increases the amount of water which can be held in the
beads) and Tg around 108 °C. This paper does not report or discuss
the expansion and moulding processes for these beads, simply stating
that molecular weight is important, and that the PPE is expected to
improve the processing window.
Although the foregoing suggests that water-expandable polystyrene

(WEPS) has been developed to a workable level, such a product has
not yet been commercialised. Presumably the economics are still
adverse while conventional pentane-expanded grades are permitted
and available (including low-pentane types).
A recent patent application from Nova Chemicals [88, 89] is very

wide in its scope and may not be granted in its entirety. It describes a
process which eliminates the maturing step for pre-expanded beads.
Instead of using a blowing agent dissolved in the beads to generate
the foaming, they are impregnated with air or carbon dioxide (or a
mixture) at high pressure until they are saturated. This pressure may
be 0.5–8 MPa, and the impregnation time for polystyrene beads may
be 1–8 hours, at up to 90 °C. The beads can then be pre-expanded
using heat and/or steam, before a drying step using a flow of hot
air. These dry beads are stable, with a residual internal gas pressure.
They are then transported directly to the moulding machine (or
may be stored for a short time until the moulder is ready) and have
33
sufficient expansion power to fuse well in the mould. The process may
be applied to solid beads (which can be polystyrene, polyethylene,
polypropylene or even other polymers) and allows the elimination
of the volatile blowing agents normally used, as well as the large
storage bags needed for the maturing step and the emissions that arise
during it. It is, however, advantageous to ‘pre-nucleate’ the beads by
carrying out a mild pre-expansion (e.g., from a bulk density of more
than 600 kg/m3 to 400 kg/m3 or so) which creates the structure of
foam nuclei for the later expansion and for which a (low) pentane
content is very useful. This process may allow the elimination of the
storage bags for maturing, but it does instead require equipment
for the impregnation of the beads under high gas pressures. As this
does not seem to be a great advance on the well-known PAT system
for expanded polypropylene/polyethylene (see Chapter 3), in which
prepressurisation of the prepuff beads gives them enough internal
pressure to expand during moulding, it might not appear to be very
inventive, and it is possible that the application will be revised and
narrowed before it is granted.
Other possibilities have also been considered as a means to eliminate

VOC, though this is easier in extruded polystyrene (XPS) sheet
processes, where the material is allowed to expand immediately at
the die of an extruder, having had the blowing agent injected into
the melt shortly before the die. Two such XPS developments have
been reported recently, and although it is difficult to see how they
could be transferred directly to expandable bead production, as we
will see later (Section 4.3), circumstances may dictate that some kind
of alternative process may become necessary. These later methods
are, therefore, included as signposts to possible future developments
rather than existing technology for mouldable expandable foams.
The first of these papers [90] describes how an XPS process using
carbon dioxide alone is difficult to control because of its poor
solubility in the polymer (maximum around 4 wt%), but the
addition of a similar level of ethanol (boiling point of 78 °C, so
potentially useful in steam expansion) gives better plasticisation and
expandability. The paper concludes that combining the two blowing
34
agents yields advantages which cannot be obtained by using one or

the other alone.
The second paper [91] describes the use of water and n-butane together
to produce ‘bi-cellular’ foam – a sheet with two cell size populations
which reportedly improves the insulation performance of the sheet.
The polystyrene also included a low percentage of precipitated silica
which, by adsorbing water onto its hydrophilic surface, helped the
dispersion of the water and also acted as a nucleation agent for the
foam. With 5% butane, 2% water and 3% silica, the expansion
ratio reached 35:1 (corresponding to a foam density around 30 kg/
m3) with a well-defined two-peak distribution of cell sizes. Clearly
this technique still relies on a volatile hydrocarbon, but exemplifies
some advantages of combining two blowing agents.
A third paper describing an XPS process [92] starts with a suspension

polymerisation to produce beads of water-containing polystyrene,
using activated carbon as the carrier for the water. These beads are
then fed to an extruder and carbon dioxide injected into the melt to
act as the primary blowing agent – the activated carbon holds the
water so that it is not driven off in the extruder, and can contribute
to the expansion of the sheet so that lower densities can be reached
than are possible with carbon dioxide alone. The addition of around
3% of (wet – water content is not reported) activated carbon colours
the sheet grey, and also possibly helps the improved insulation
performance as described in Section 2.3.
Another approach that may have potential for the future is the use of
Expancel expandable microspheres [93]. These have a diameter in
the range 10–40 Mm and have a polymeric shell enclosing a volatile
fluid such as a blowing agent. Once incorporated in a polymer matrix
and heated above the softening point of the shell, the microspheres
release their volatile contents to expand the matrix (although clearly
this must also have been softened by the heat) and expansion ratios of
up to 60 times are claimed. Although the microspheres are expensive,
this approach may have potential in allowing the use of blowing
agents that are not soluble in polystyrene.
35
2.6 Developments in Making or Processing EPS Beads
2.6.1 Extrusion Processes for Bead Making
As mentioned in Section 2.1, the traditional process for producing

expandable beads is via suspension polymerisation, which results
in spherical beads of a range of sizes. Advances in process control,
special additives and general ‘know-how’, usually proprietary to
each manufacturer and jealously protected, can reduce the spread
of sizes, but it is always a commercial challenge to find outlets for
all the size ranges in the proportions that are generated. This is
particularly true of the more specialised products such as coloured
products, ‘high-temperature’ beads incorporating polyphenylene
oxide and resilient grades such as Arcel, where there may simply
not be a commercial outlet for the oversize or undersize beads. In
recent years extrusion processes have been developed which allow
beads to be made in the desired size range with little waste [94, 95].
There are a number of methods for generating a homogeneous melt
of polymer and impregnating it with the blowing agent (closely
following the development of XPS processes), but the key step is the
micropelletisation. Desired bead sizes are usually in the range 0.5–2
mm – although the upper end of this range is close to what can be
achieved by conventional die-face pelletisers, the very small sizes
are much more difficult, especially where the melt already contains
pentane. The first method for obtaining fine beads was developed
in the 1980s [96], using an approach where thin extruded strands
were drawn down before cooling and cutting. This resulted in ‘beads’
that were cylindrical rather than spherical, but small sizes (1 mm or
so) were achievable. More recently, underwater microgranulators,
with the water pressurised to keep the blowing agent in the beads
until they are cool enough not to expand, have been developed. One
major US/European manufacturer of such systems is Gala, but other
manufacturers also produce such pelletisers.
Polystyrene is melted in an extruder (usually a twin-screw type,

but the melt can be supplied direct from a reactive polymerisation,
36
via static mixers and melt pumps) and any desired additives
compounded into it. Blowing agent can be pumped into the (sealed)
extruder barrel and mixed into the polymer in a mixing zone, then
the melt fed (sometimes via a ‘cooling extruder’ which can be a
single-screw type, or directly via a melt pump – either ensures a
steady flow of melt at a consistent pressure) to the inlet of the
micropelletiser. This has a die with a large number of very fine
holes arranged in clusters round an annular face, and fed through
a number of ‘pots’ which pass through the heated body of the
die. A multi-knife cutting head rotates against the die face at high
speed under a flow of pressurised cooling water. To illustrate the
challenges, a bead of 1 mm diameter has a mass of around 0.5 mg,
so that a process running 300 kg/h must cut that throughput into
some 10 million beads every minute. Die design is a critical part of
a reliable process, and although there is much commercial secrecy,
some approaches have been described [97-99]. The beads that result
are egg-shaped rather than spherical, but close enough to be able
to be processed in the same way as beads made by conventional
suspension polymerisation.
Extrusion allows incorporation of additives such as colorants, fire

retardants, property modifiers, etc., which could interfere with
a suspension polymerisation, so it is likely to grow in popularity
for making specialised grades of EPS. It is also now practicable
to construct a continuous process line to start from styrene
monomer, going through a polymerisation reaction step, thence
to a compounding stage to add the blowing agent, nucleators and
other modifiers, followed by micropelletisation. Sulzer AG took out
a patent for a ‘monomer to beads’ production line in 1994 [100],
and there are now increasing numbers of such lines in operation.
An application by BASF [102] also points up the advantages of the
extrusion route when seeking to blend polymers – it claims to be
able to produce foamable beads from blends of polystyrene with,
for example, styrene–butadiene block copolymers (for resilience),
styrene acrylonitrile (for solvent and weathering resistance) and
even polypropylene (presumably some kind of compatibiliser is
needed here).
37
2.6.2 Foam Nucleation
Nucleating additives act to nucleate the foaming process by forming

the starting points for the myriad of cells in an expanded bead, and
there are a wide variety of such agents used in EPS manufacture.
The predominant mechanism employed is heterogeneous nucleation,
and the list of typical agents includes finely divided particulate
solids such as talc or chalk, and polyolefin waxes (which, because
they are incompatible with polystyrene, form small droplets inside
the beads). At the start of the pre-expansion process, these finely
dispersed inhomogeneities nucleate bubbles of the vaporised blowing
agent which then expand to create the fine cell structure of the EPS.
The technology of nucleators is fairly well established, and each
manufacturer has a preferred approach which suits its particular
process, so there has not been much published activity in this field. A
recent ANTEC paper [103] describes a theoretical study of nucleation
in the polystyrene/carbon dioxide system and concludes that an ideal
heterogeneous nucleant should have particles with numerous crevices
of small semi-conical angles (a very rugged surface). This is in line
with the qualitative model in which the interfaces between nucleant
and polymer have small voids, into which blowing agent has diffused
– when these voids feel the heating of the pre-expansion process,
they are able to expand quickly and form the nuclei of foam cells.
Subsequently, more blowing agent diffuses into the growing cells and
they can expand further. Some cells coalesce, and blowing agent is lost
from the bead surfaces by evaporation. The foam formation process
is a competition between these mechanisms, and the resulting cell
structure reflects the balance between cell formation and expansion,
coalescence and collapse, and diffusion of blowing agent out of the
bead – this is affected by pre-expansion conditions as well as by the
nucleator and its internal distribution within the beads.
2.6.3 Moulding of EPS
Processing of EPS continues to develop, and moulding machines

have been developed to mould EPS (and expanded polypropylene)
38
into or over metal parts [104]. Techniques have also been devised
(or in one case, borrowed from the brick-making industry [104]) to
increase production rates by use of multiple moulds which can be
the same or different from one another, allowing several parts to be
produced in parallel. Automation of pre-expanders and moulding
machines is likely to become ever more sophisticated, as demand
for process efficiency and consistent quality continues to grow.
An interesting study into the relationships between EPS molecular
weight and density and the quality of ‘lost foam’ castings [105]
shows that demand for efficiency applies to all EPS processes – it
was found that the molecular weight of the EPS controlled the rate
of volatilisation, but that mould filling time also depended on the
density of the foam.
2.6.4 Recycling of EPS
Recycling of EPS is well established and the industry has long met
and exceeded its recycling targets under EC packaging directives.
The most common method of recycling is to grind waste foam
back to its constituent expanded beads, then add a proportion
of them into virgin pre-expanded beads to mould new products
– if the beads are clean they often have very little effect on the
product properties. Waste foam can also be densified by crushing,
allowing relatively economic transportation (a standard 12 m
freight container holds less than 1 tonne of scrap EPS, whereas,
if the foam can be densified to around 300 kg/m3, the same
container will hold 12 tonnes or more). It can then be melted and
reprocessed to a general-purpose polystyrene or modified to have
greater added value. The economics of melt reprocessing are very
sensitive to the price of oil, which not only controls the price of
prime polymer (hence a ceiling on the price of recyclates) but also
the cost of transportation of the scrap material from where it is
generated to where it is recycled – an operation that is profitable
today can become unprofitable tomorrow irrespective of the best
efforts of the recycler.
39
A comprehensive review of densification options and their relative

costs has been published by the Environment and Plastics Industry
Council of Canada [106] – it mentions the challenges from
contamination (which lowers the value of the recovered EPS) and
thermal degradation as well as the costs of densification equipment
and the various disposal routes that may be used – recycling is
frequently not the lowest cost option.
The experimental process using a solvent derived from citrus fruits

which was being developed in the earlier years of the century and is
described elsewhere [107] has not so far come to commercial fruition.
This may partly be as a result of these fluctuating economics, but
also because of the advantages of the regrinding/remoulding route
described above.
Two papers from China report an unusual approach to the reuse of

reground beads which was aimed at improving the fusion of these
beads to one another or with virgin expanded beads. There is no
residual blowing agent present in used beads, so they have little
expansion capacity during moulding. The work explored the use of
adhesives to improve the bead-to-bead fusion during the moulding
process – it was found that product properties could be significantly
improved, although the amount of adhesive needed was quite large
(up to 10% of the EPS weight). A powdered hot melt adhesive worked
better than a sprayed solvent-borne system [108], while measurements
on 100% recycled EPS showed comparable properties to mouldings
made from virgin beads [109]. It appears, however, that this approach
is little used in practice, as the addition of a proportion of recycled
beads to virgin beads is now well established and controlled.
40
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68. B.I. Chaudhary, L.S. Hood and R.P. Barry, inventors; Dow
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50
3
Expanded Polyolefin Moulded
Foams (EPE and EPP) – Materials
with Growing Application
3.1 Key Features of Polyolefin Moulded Foams,

Compared with EPS
As the polyolefin polymers (polyethylene, polypropylene and their
copolymers, in many different variants) together make up the largest
volume production of the synthetic polymers, it is not unexpected
that foaming of these polymers has been widely practised and
studied. It is therefore surprising that the volume of mouldable
beads produced in polyolefins is very much smaller than that in
polystyrene, especially as foamed polyolefins have some significant
property advantages. This disparity is due to the much greater
complexity and cost of producing moulded foam products from
polyolefins, compared with the particular suitability of polystyrene
for the process.
The features of the EPS process described in Chapter 2 are not easily
reproduced in other polymers, for reasons which will be explored
in this and the following chapter. Polyolefins are commodity
polymers that are produced in larger volumes than polystyrene, yet
expandable bead production is very much smaller. In contrast to
polystyrene, extrusion of expanded sheet from polyolefins is much
more widely practised than manufacture of mouldable beads, which
remain niche products for particular applications. This is a direct
result of the differences between these polymers and polystyrene
in relation to foaming and these differences must be considered in
order to understand the reasons for the way moulded polyolefin foam
technology has developed.
51
The first key difference from EPS is that there are no blowing agents
that can be impregnated into the beads and held there at ambient
pressures for later expansion, in the way that pentane functions in
EPS. Instead, once impregnated with blowing agent, the beads must
be expanded immediately, or held under high pressure. Expanded
beads have a high bulk, so that transporting them (and the finished
products) is costly. Clearly, producing the beads on the same site as
moulding the finished products would eliminate that cost, but those
finished products could then require transporting over long distances
to the customer – small-scale production units for expandable
polyolefin beads are not economically attractive.
Secondly, the melt rheology (particularly in extension) of common

polyolefin grades differs from that of polystyrene (which thickens
on extension, helping to stabilise the foam cells) so that the foam
cell structure is also more difficult to control. There have been
developments in this area which will be discussed in Section 3.2.
The third area of difference arises when the beads are expanded and
moulded. Polystyrene is amorphous with a Tg value around 100 °C,
while the polyolefins are semi-crystalline – their Tg values lie below
room temperature, but their crystalline melting points lie in the range
110–140 °C (polyethylenes) or 150–170 °C (polypropylenes). Because
of these higher melting/softening points, high steam temperatures
and pressures are needed for polyolefins, and the process window is
very narrow – a few degrees wide, just below the crystalline melting
point. Further, because of the slow crystallisation of polypropylene,
expanded polypropylene (EPP) products often require post-ageing
in an autoclave before they are fully stable. This all adds cost and
complexity to the process, and further handicaps these polyolefin
bead foams in the marketplace.
On the positive side, polyolefins are far more ductile than polystyrene,
so their foams are also much tougher and more resilient. This is
particularly useful for protection against repeated impacts, so the
automotive industry has long been a major area of application as
well as transport packaging.
52
Expanded Polyolefin Moulded Foams (EPE and EPP) –
Materials with Growing Application
Polyethylene bead foam processes were developed by BASF in the

1970s [1] and those for polypropylene by Japan Styrene Paper (JSP)
in the 1980s [2], and a description of these processes can be found
in the literature [3]. These processes differ in several key aspects
from those for EPS – these differences add significant cost and have
restricted the market penetration of polyolefin bead foams.
There are essentially three main production approaches for making

mouldable expandable polyethylene (EPE) beads, all of which
begin with an extrusion process (suspension polymerisation is not
possible as it is for polystyrene) and a die with a multiplicity of
very small holes (as in Section 2.6.1). The blowing agent can be
injected into the melt before the die, so that the strands expand
immediately and are cut to size at the die face – polyethylene beads
may then be crosslinked, for example by electron beam irradiation,
to stabilise their structure. Alternatively, polyethylene beads may
be extruded and pelletised into microbeads which are impregnated
with a crosslinking agent such as dicumyl peroxide in a suspension
in water, then crosslinked by heating. Finally the blowing agent is
impregnated into the beads before they are cooled, then expanded by
steam. More recently, the JSP process [2], which can also be applied
to suitable grades of polypropylene, was developed. Here, extruded
microbeads are produced and suspended in water in an autoclave,
where a blowing agent is impregnated into them under conditions of
elevated temperature (close to the melting point) and pressure. The
beads are cooled before depressurisation, and can retain the blowing
agent for an hour or more. They must, however, be expanded by heat
(usually steam) within a short time, then allowed to cool and the
pressures inside and outside the beads to equilibrate. This prepuff can
then be transported to the moulding site and may be stored almost
indefinitely, as the blowing agent has been almost entirely lost.
The blowing agents used can be organic solvents such as butane, or

hydrochlorofluorocarbon (HCFC) (formerly CFC) – pentane is less
commonly employed. The critical factor is that these blowing agents
diffuse into, through and out of polyolefins much more quickly
than pentane does through polystyrene. A 2007 conference paper
53
[4] discusses the relative diffusion rates of n-pentane in polystyrene

and polypropylene – although the maximum solubility in the two
polymers is not very much different (around 25 wt% in polystyrene
and 17 wt% in polypropylene), n-pentane diffuses through
polypropylene roughly two orders of magnitude faster. This means
that polypropylene takes up pentane quickly, but also loses it very
quickly, and storage of pentane-impregnated beads of polyolefins
is not practicable. The same pattern of diffusion applies to other
volatile blowing agents. This diffusivity issue also affects foaming
behaviour – when a spherical bead containing a volatile blowing
agent is heated, necessarily from the outer surface, two processes
compete. The blowing agent can diffuse out of the bead surface or it
can vaporise at internal nucleation sites, creating the cells that form
the foam structure. As heating and vaporisation continue, the cells
will grow and can coalesce as their walls become thinner, but the loss
of blowing agent from the bead surface continues – this can lead to a
‘skin–core’ structure where the cells at the bead surface are relatively
small compared with those in the interior, depending on the relative
rates of cell formation, growth and coalescence, and blowing agent
loss. Generally speaking, polyolefin foams tend to have coarser cell
structures than EPS foams, because of their different rheological
properties, in particular in extensional flow. Prefoaming times are
shorter than for EPS, again because of the higher diffusivity, so that
uniform expansion is harder to achieve.
As mentioned previously, and as described in more detail in

Section 3.4, moulded polyolefin foams do have some advantageous
properties, which lead to their use in a range of applications. What
is also important here is the difference in utility between extruded
foam sheet products and moulded bead products. The bulk of foamed
polyolefin products are in the form of extruded sheet, for which the
processes are relatively straightforward, but the foam structure tends
to be less uniform than in bead foams and more likely to have open
or connected cells. In contrast, sheets moulded from beads are more
isotropic and have greater cushioning and resilience than extruded
sheet, and can easily be made in significant thicknesses. Naturally,
moulded bead products can also be made to specific shapes without
54
waste, and this is of benefit in packaging applications. Although

the market data for 1997 [5] do not separate bead products from
extruded sheet and ‘plank’ polyolefin foams, given that the entire
polyolefin foams market in that year was well below 10% of that
for EPS, it is clear that polyolefin bead foams (EPO) were, although
growing faster than EPS, still restricted to niche applications. A
private source has indicated that in 2005 in Europe, some 1.5 million
tonnes of EPS were produced against only around 26,000 tonnes
of EPP and EPE (beads) combined. Data presented by Borouge (the
joint venture that manufactures Borealis’ range of polyolefins) in
its publicity for the Daploy foamable polypropylene grades suggest
that low-density extruded polypropylene sheet was growing at 20%
per year but was only at around 30,000 tonnes in 2005. Whatever
the precise figures, it is clear that EPO command much smaller sales
volumes than EPS.
3.2 Developments in Materials for EPP and EPE

Manufacture
The polyolefin family comprises a range of polymers and copolymers
with widely varying properties, and a number of them have
been exploited as foams and foamable beads. This runs from the
softest ethylene-vinyl acetate (EVA) to the stiffest (polypropylene),
although for foamable bead production, polypropylene and various
polyethylenes predominate. Foams based on low-density polyethylene
(LDPE) or linear low-density polyethylene (LLDPE) are soft and
have relatively poor creep and compression set performance,
while EPP is harder and stronger, but presents some specific
processing challenges.
When a polymer is foamed, the primary mode of deformation is

extensional – once cells are nucleated and begin to grow, their
walls are stretched (and simultaneously thinned). Polystyrene is an
‘extension thickening’ material – as it is stretched the melt becomes
more resistant to further stretching, so that the process is to some
extent self-stabilising. LDPE can also behave in this way, because of
55
its branched chains (polystyrene is not usually branched, but steric

hindrance from the bulky side groups creates the same rheological
effect in the rubbery phase) and can be foamed reasonably well.
As the chains become more linear (and crystallinity increases),
so the melt rheology of polyolefins tends more to the ‘extension
thinning’ pattern, and once growing, cells tend to grow and quickly
coalesce as their walls have less (melt) strength to stabilise them.
The crystallinity of polypropylene is also a challenge to foaming
– the material must be expanded at a temperature close enough to
the crystalline melting point to allow the chains to move over one
another, but not so close that the melt has no tensile strength – so it
was clear that special grades or blends were required for a successful
EPP process. The early EPP manufacturers used random copolymers
of propylene and ethylene which have limited crystallinity (and
therefore limited mechanical properties), and were also limited in the
minimum density that could be achieved. There is also an approach,
for which Kanegafuchi (Kaneka) obtained a US patent [6] in 1998,
in which a proportion of the crystallinity is present as the (lower
melting point) B-form, promoted by the use of specific nucleating
agents. This was claimed to reduce the temperature necessary for
fusion of the beads and to widen the process temperature window.
There were also applications filed in Europe and at the World
Patent Office, but these were abandoned before their examination
was completed.
Over time polymer manufacturers have seen the value of higher melt
strength (also very useful in thermoforming) and have developed
special grades to meet this need. The logical approach was to make
polypropylene with a degree of branching, and a paper presented at
ANTEC in 2001 [7] by workers from the University of Toronto and
Borealis GmbH reported significant improvements in foamability
by blending so-called ‘high melt strength’ (HMS) branched
polypropylene into linear polypropylene. Not only did the cell density
increase (showing less cell-wall breakage) with the proportion of
HMS polypropylene, but also the minimum foam density and the
temperature at which it was reached fell, although it was reported
that the crystallisation temperature did not change. This work was
56
done in a sheet extrusion process rather than beads, but the same
principles were clearly applicable to bead making.
A paper presented at ANTEC in 2005 by a representative of JSP

[8] discusses the impact of the newer metallocene types of catalysts
developed for polyolefin synthesis on the foamability of the resulting
polymers. The original Ziegler–Natta catalysts used for polyolefin
synthesis produce essentially linear chains without branches,
while metallocenes can yield chains of tailorable and controlled
stereoregularity with narrow molecular weight distributions for
predictable and reproducible material properties. One focus of this
paper is on the opportunities arising from this ability to tailor the
properties of EPP, especially in automotive applications. As the foam
expands, so the polymer chains in the cell walls become biaxially
oriented and also tend to form oriented crystalline structures, so that
their strength and stiffness are enhanced by comparison with the
random copolymers which can only crystallise to a limited extent.
The final section of the paper outlines the innovative ‘porous EPP’
(PEPP) product in which the individual beads are in the form of
hollow cylinders, or pipes. When moulded, the material retains a
high level of porosity because of the connections between the spaces
within these cylinders. This porosity is particularly useful for sound
absorption, while the closed-cell nature of the foam provides good
mechanical properties and cushioning.
Papers presented at conferences in 2005 [9] and 2006 [10] reported

more on the HMS grades from Borealis GmbH and developed the
themes of high melt strength and controlled crystallisation kinetics
in foaming behaviour. The first [9] described two Borealis grades, a
homopolymer WB130HMS and a newer copolymer WB260HMS.
These were extrusion foamed either alone or in blends with linear
polymers, showing that the controlled long-chain branching in the HMS
grades improved elongational viscosity and foamability. The copolymer
grade was claimed to give softer foams than the homopolymer, but
without sacrificing processability. Blends with up to 50% of linear
polypropylene, selected to obtain the desired mechanical properties,
were shown to be easily expanded to densities down to 80 kg/m3.
57
In the paper presented the following year at the next conference

in the series [10], four different types of polypropylene were
extrusion foamed using butane, with talc as the foam nucleator,
and the influence of chain branching, degree of copolymerisation
and butane level on foaming (maximum expansion, cell structure
and mechanical properties) was explored. It was found that the
HMS grades from Borealis were able to reach much lower foam
densities (down to 20–25 kg/m3) over a wider process temperature
and butane content range than two linear grades, a copolymer
and a homopolymer. Copolymers yield a softer foam but with a
wider processing window than homopolymers. A second paper at
this conference [11] looked at the effect of repeated recycling on
the foamability of LDPE expanded with a chemical blowing agent,
azodicarbonamide, and concluded that elongational viscosity,
particularly the reduction in elongational yield strength arising
from damage to the polymer from repeated extrusion, was key to
the foaming performance.
By 2008, another polymer manufacturer, SABIC, had entered the

fray, and its work on high melt strength in polyethylenes has been
described [12]. It was pointed out that too high a melt strength can
be a disadvantage, as it limits the degree of expansion which can be
achieved – the pressure of the blowing agent must be able to stretch
the cell walls and make the cells grow. The control of molecular
weight and chain morphology made possible by developments in
catalysis allows polyethylene grades to be optimised for foaming
to lower densities and with more uniform cell structures and better
insulation performance.
Another approach, claimed in a recent Chinese patent [13], is to blend

up to 10% or so of both an LDPE and a homopolymer polypropylene
into a random polypropylene copolymer and to impregnate the
resulting beads with pentane. Reportedly, the beads may be readily
expanded to foam densities of 50 kg/m3 (many applications now call
for much lower densities, in the range 10–30 k/gm3) but the process
is claimed to work at low pressures and with low-cost equipment.
Only an abstract is available in English, so to study the details of the
58
description of the prior art and the claims would require a translation
from Chinese.
A final comment on materials development is that as the polyolefin

beads are produced by extrusion, a wide range of additives can
be incorporated into them to obtain specific properties. These can
include fire retardants, colorants, antistatic or conductive additives,
nucleating agents (almost always included), etc. – the formulator is
not limited, as he or she often is for EPS, to additives that do not
interfere in the suspension polymerisation process. Fire-retarded EPO
foams are able to meet the stringent requirements of the aerospace
industries, among others [14].
3.3 Developments in Processing of EPP and EPE

The processes for impregnating, expanding and moulding polyolefin
beads have been the subject of considerable development effort, not
least because of their cost and complexity in comparison with EPS.
For example, in the early 1990s, BASF developed the ‘pressure and
temperature’ (PAT) system in order to reduce the density increase
during moulding [14] (see later for further discussion).
Impregnation of beads with blowing agent was originally (and

can still be) carried out in a water-suspended slurry in a reactor at
elevated temperature – for EPP this is typically at 130–160 °C – and
with elevated pressure of the blowing agent, since for polyolefins the
amount of blowing agent taken up is proportional to the applied
pressure (Henry’s law). BASF patented a continuous impregnation
and expansion process in 1998 [15], in which the beads were
suspended in water as a slurry and the slurry was then pumped into
a pressurised system of pipes into which the blowing agent such as
butane was injected at high pressure (20 MPa). The slurry and gas
were heated (typically to around 115 °C, approaching the softening
point of the beads) so that impregnation was accelerated. The volume
of the pipework system and the slurry flow rate were designed to
allow sufficient time for the beads to be fully impregnated. Finally,
59
the slurry was pumped through an orifice into an expansion vessel

where the blowing agent flashed into vapour and the heat-softened
beads expanded. The blowing agent was recovered for re-injection
or to be burnt to raise steam for the heating process. The patent
does highlight the importance of keeping oxygen out of the system
by blanketing the mixer where the slurry is first made with an inert
gas, as the blowing agent is highly inflammable and at high pressures
and temperatures there is a significant risk of explosion.
As micropelletisation methods were developed, so it became possible

to inject blowing agent into the extruder, and underwater pelletisation
under pressure can even permit the beads to be prevented from
expanding at the die, and cooled fast enough to retain the blowing
agent for a time (although never for long, as discussed in Section
3.2). Alternatively, the beads may be allowed to expand immediately
after cutting, although this does demand good process stability and
large-volume pipework to convey the expanding and expanded beads
away from the extruder and die. BASF has obtained patents on the
process of taking microbeads of polypropylene (and blends with other
polypropylene types, or other polymers) and impregnating them in a
reactor at high temperature (150 °C is stated to be best) and pressure
for several hours, before cooling the reactor (under pressure) to below
50 °C and discharging the cooled beads. The patents [16, 17] claim
that the beads are then expandable for a period of at least an hour
– steam at 130–160 °C (0.2–0.45 MPa) is used for the expansion
step. Although this is hardly comparable with the months-long
shelf life of EPS beads, it does permit some flexibility in the layout
and operation of the processes. The blowing agents claimed include
pentane, hexane, heptane, 3,3-dimethyl-2-butanone and 4-methyl-
2-pentanone, and the nucleation of the foam is expedited by a wax
and/or talc. A later patent [18] claims the use of a coating on the
beads to prevent caking during expansion, although the makeup of
that coating is much as used in the EPS industry – a metal stearate
(calcium in this case), glycerol tristearate and an antistat. This patent
mentions the use of a pressurised underwater pelletiser to produce
impregnated beads as an alternative to the reactor process for later
impregnation of microbeads.
60
One feature of EPP materials is that an unexpected melting peak

sometimes appears during differential scanning calorimetry scans,
at around 150 °C. This is explained [19] in terms of a terpolymer of
propylene-co-ethylene-co-1-butene recrystallising at the expansion
temperature (around 150 °C), forming more perfect crystals than
usual. On cooling after complete melting, these do not reappear until
the material has been annealed for more than 24 hours. The formation
of these crystals is ascribed to self-nucleation during the expansion,
which is much faster than homogeneous nucleation. It is clear that bead
expansion, with a combination of heating, stretching and desorption
of the blowing agent (changing the degree of plasticisation), is a
highly dynamic process which can generate unexpected morphology
in semi-crystalline polymers – this will be seen later in the discussion
of expanded polylactic acid (Section 4.2).
Expansion of a foam comprises three main phases – nucleation,

growth of the bubbles once they have reached a critical size and
finally coalescence or stabilisation of the cells as the internal pressure
of blowing agent is no longer sufficient to continue stretching the
material of the walls (perhaps because the walls have become stiffer
through orientation or cooling, or there is no longer sufficient fresh
blowing agent diffusing into the growing cells). This process has been
much studied, and a comparison has been done [20] of modelling
and experiment in polypropylene/carbon dioxide expansion, with a
focus on the effect of the rate of the pressure release on the number
of cells and their growth. It was shown that there is a maximum in
the nucleation rate with pressure release rate as the growing bubbles
compete to consume the gas liberated, but that the bubble growth
rate increases with pressure release rate.
Numerical simulation has also been used to explore the moulding

process in which the expanded beads are filled into a mould, and then
steam is applied to fuse the bead surfaces and create a monolithic
moulding. Subsequent ageing may be required, especially for EPP
as the crystallisation of polypropylene is slow, in order to obtain
dimensionally stable mouldings. Work has been reported by a team
at Tokyo University [21, 22] simulating the processes of steaming,
61
depressurising, cooling and ageing which make up the moulding

cycle, and thereby calculating the stresses on the mould.
As mentioned previously, as the expanded beads contain no residual

blowing agent, they have no expansion power and mouldings tend to
have a higher density than the prepuff because the steam compresses
them to some extent. The PAT system [14] overcomes this to some
extent by prepressurising the prepuff before moulding, using air at
0.3–0.4 MPa and 70–80 °C for several hours. This creates an internal
pressure in the beads which resists compression by the steam, and
may even permit some expansion during moulding so that low
density can be maintained. This can be done in a batch process or
made semi-continuous by using a large pressurising vessel supplying
a smaller dosing tank which feeds the moulder. The process of Nova
Chemicals [23, 24] referred to in Section 2.5.3 appears to be quite
similar in approach and can in principle be applied to beads of several
different polymers.
An article from 2005 [25], although oriented mostly to EPS, describes

how moulding of particle foam articles has been developed to include
the ability to overmould metal parts, or to mould foams into them.
See Section 2.6.3 for more details.
3.4 Development of Applications for Expanded

Polyolefin Bead Products
The major application area for EPO is in packaging, where their
ability to absorb shock and retain their cushioning properties over
multiple drops is far superior to that of EPS (see the discussion in
Section 2.4). The cost of a package is often far smaller than the value
of the product it is protecting, and when sustained rough treatment is
anticipated in transit, EPO foams have unmatched performance. The
author knows of an example where products such as plasma screens
were shipped to the UK by sea from the Far East in EPP packaging,
then unpacked and repacked in EPS for distribution within Europe,
there being a saving of space/unit and therefore transport cost by
using EPS on the less rigorous last lap.
62
Another and growing area of application especially in Europe is in

the automotive field. As the issues around disposal of ‘end-of-life’
vehicles have become more important, European car manufacturers
in particular have striven to reduce the number of different polymers
used in their vehicles, so that the polymeric part of the scrapped
vehicle is less mixed and therefore more easily recycled. Polypropylene
is often the preferred solution for internal, under-the-bonnet and
bumper components, where a solid polypropylene skin may cover
an energy-absorbing EPP foam layer (usually of fairly high density
for optimum stiffness and strength) all carried on a steel armature.
EPE foam finds application in sound-deadening within assemblies
such as doors, and for soft cushioning tasks such as carpet underlays.
‘Porous EPP’ [8] is also intended for such applications, and other
variants of Arpro (the trade name for JSP’s EPP) are tailored for
specific roles in automotive interiors [26].
A niche but potentially large future market area for EPP foam is as an
underlayer in synthetic sports surfaces [27] – a sheet of EPP provides
the necessary level of cushioning between the hard substrate and the
synthetic turf, while having sufficient toughness and resistance to
compression set to have an adequate service life.
Although many applications of EPO are relatively small in volume

[27, 28], there are many niches where the special properties of these
foams fulfil the demands of the application better than other foams
or alternative design solutions.
Because EPO are often used in roles where their protective

performance is critical (because of their relatively high cost, they tend
to be employed where their resilience and ductility are important),
there has been effort devoted to testing and modelling of cushioning
performance. Impact absorption is a compressive process at high
strains and strain rates – this region can be hard to access using
common testing equipment. Even drop testers (see Section 2.4) cannot
easily explore the strain rates found in, for example, automotive
accidents. A Canadian paper [29] reports compression testing carried
out at rates up to 2500/s and compares the performance of EPS,
63
EPP and polyurethane foams. The results are also compared against
a common constitutive foam model and show that, above around
1000/s, strain rate dependence becomes very marked. Another study
[30] explores the effect of multiple compression cycles on EPS and
EPE, and compares their performance against simulations using finite
element analysis. EPE (and EPP) is significantly more resilient to
multiple loadings than EPS – the deformation of EPS quickly leads to
breakage of the cell walls of the foam, as the matrix polymer is quite
brittle, while polyolefins have much greater ductility and ‘absorb’
deformation by flexing and yielding without breaking – the cell
structure therefore remains more or less intact and the cushioning
power of the air inside the cells is retained.
A special type of EPP is manufactured by Brock (USA), in which the

beads are not fused by steam but glued together with a polyurethane
adhesive. This creates a very open texture, through which water
can be poured – the porosity is of the order of 25%. This product
is particularly aimed at the application discussed above in synthetic
sports surfaces, where good drainage can be very important. Work
has been reported [31] that aimed to compare these foams with
conventional EPP for application in protective cycle helmets (where
the impermeability of EPS presents ventilation issues for the wearer).
Sadly for the investigators, the conclusion of their study was that the
permeability of the bonded foam was insufficient to provide good
ventilation and the compressive and impact-absorbing properties
were a little poorer than those of a conventional EPP.
In conclusion, it is likely that EPO will continue to find new

applications where their resilience and ductility add value, and
although these may begin as small-volume niches, at some point
they may grow to be much more significant. The application as
an underlayer for synthetic sports surfaces is a good example, or
growing displacement of other materials such as polyurethane or
polyvinyl chloride foams in the automotive market. As world trade
grows, high-performance transport packaging for delicate products
can only increase in importance (and many countries have far worse
road surfaces than those to which Europeans are accustomed).
64
EPS will continue to hold its leading position as a packaging foam,

although EPO and biodegradable foams (see Chapter 4) are likely to
gain increasing shares of this very important market in the coming
years.
References
1. F. Statsny, R. Gaeth and G. Treischmann, inventors; BASF,
assignee; US3616365, 1971.
2. K. Hirosawa and S. Shimida, inventors; Japan Styrene Paper

Corporation, assignee; US4379859, 1983.
3. Polymeric Foams and Foam Technology, 2nd Edition, Eds.,

D. Klempner and V. Sendijarevic, Carl Hanser Publishers,
Munich, Germany, 2004, Chapter 8.
4. X. Zhang, Z. Zhu, C.B. Park, E.K. Lee, N. Chen and H.E.

Naguib in Proceedings of SPE ANTEC 2007, Cincinnati,
OH, USA, 2007, p.3057.

Rapra Technology, Shawbury, UK, 2001.
6. Y. Munakata and K. Senda, inventors; Kanegafuchi Kagaku

Kogyo Kabushiki Kaisha, assignee; US5716998, 1998.
7. H.E. Naguib, J.X. Xu, C.B. Park, A. Hesse, U. Panzer and N.

Reichelt in Proceedings of SPE ANTEC 2001, Dallas, TX,
USA, 2001, p.1623.
8. S.R. Sopher in Proceedings of SPE ANTEC 2005, Boston,

MA, USA, 2005, p.2577.
9. M. Stadlbauer, R. Folland and P. de Mink in Proceedings

a Rapra Technology Conference - Blowing Agents and
Foaming Processes, Stuttgart, Germany, 2005, Paper No.10.
65
10. J. Wang, C.B. Park, M. Stadlbauer, R. Folland and W. Pirgov

in Proceedings of a Rapra Technology Conference - Blowing
Agents and Foaming Processes, Munich, Germany, 2006,
Paper No.19.
11. E.T. Kabamba and D. Rodrigue in Proceedings of a Rapra

Technology Conference - Blowing Agents and Foaming
Processes, Munich, Germany, 2006, Paper 20.
12. J. Krist and P. Sengupta in Proceedings of a Rapra

Technology Conference - Blowing Agents and Foaming
Processes, Berlin, Germany, 2008, Paper No.25.
13. W. Zhang, S. Zhang, T. Liu, H. Yin, J. Shao, M. Lu, L.

Zhang, S. Duan, Y. Lu, X. Wang, K. Li, H. Zhang and L.
Chen, inventors; China Petroleum and Chemical, assignee;
CN101104716(A), 2008.

15. T. Hall and Y. Trivedi, inventors; BASF Corporation,

assignee; US5753157, 1998.
16. C. Maletzko, K. Hahn, I. de Grave, G. Ehrmann and F-J.

Dietzen, inventors; BASF AG, assignee; US6448300, 2002.
17. C. Maletzko, K. Hahn, I. de Grave, G. Ehrmann and F-J.

Dietzen, inventors; BASF AG, assignee; US6476089, 2002.
18. C. Maletzko, V. Keppeler, K. Hahn and D. de Grave,

inventors; BASF AG, assignee; US6864298, 2005.
19. J.B. Choi, M.J. Chung and J.S. Yoon, Industrial and
Engineering Chemistry Research, 2005, 44, 8, 2776.
20. K. Taki, Chemical Engineering Science, 2008, 63, 14, 3643.
66
21. S. Nakai, K. Taki, I. Tsujimura and M. Ohshima in

Proceedings of SPE ANTEC 2006, Charlotte, NC, USA,
2006, p.2726.
22. S. Nakai, K. Taki, I. Tsujimura and M. Ohshima, Polymer

Engineering and Science, 2008, 48, 1, 107.
23. M.F.J. Berghamns, K.C. Bleijenberg, J. Teubert and

A.C.G. Metsaars, inventors; Nova Chemicals, assignee;
EP1654304A2, 2005.

A.C.G. Metsaars, inventors; Nova Chemicals, assignee;
WO2005019310/A2, 2007.
25. J.H. Schut, Plastics Technology, 2005, 51, 4, 68.
26. High Performance Plastics, 2008, August, 5.
27. Plastics Engineering, 2002, 58, 52.
28. Advanced Materials and Processes, 2006, 164, 4.
29. S. Ouellet, D. Cronin and M. Worswick, Polymer Testing,

2006, 25, 6, 731.
30. U.E. Ozturk and G. Anlas, Journal of Polymer Engineering,

2007, 27, 8, 607.
31. N.J. Mills and A. Gilchrist, Journal of Materials Science,

2007, 42, 3177.
67
68
4
‘Sustainable’ Polymers –
The Future?
4.1 Why Sustainable Polymers?

As the twenty-first century unfolds, many of the assumptions
of our twentieth-century lives are being challenged by changing
circumstances and by new thinking. The finite nature of fossil fuel
supplies has come into sharper focus, leading to a search for alternative
raw materials to produce many of the materials we need – polymers
in particular. There has also been an increasing awareness of the
potential environmental consequences of the growth in lightweight
plastics packaging – from one hand have come demands for such
packaging to biodegrade rapidly once discarded, from another for
easier and more efficient recycling, and there is not as yet any sign of
consensus on the optimum way forward for the packaging industry. It
is, however, clear that there is a significant interest in using polymers
that can be made from renewable raw materials (biomass of various
kinds, from algae to wood), whether the packaging is recyclable or
biodegradable once it has fulfilled its primary purpose. The use of
such polymers can be seen as reasonably ‘carbon-neutral’ over their
lifetimes, though there is still energy used to create the polymers,
process them and transform them into useful packaging products.
Life cycle analysis (LCA) is often called in to promote the ‘green’
credentials of particular materials – this remains a contentious (and
expensive) arena in which to participate.
To date, no mouldable particle foam products from renewable sources

have been commercialised in Europe (though see Section 4.2), and
the potential size of the market is very difficult to estimate. However,
if even 5% of the expandable polystyrene (EPS) used for packaging
69
was replaced by foam from renewable sources over the next 10 years,
volumes would become significant and require large investments in
polymer production capacity.
Polystyrene can, in principle, be manufactured from renewable

sources, as styrene may be obtained from several trees and shrubs,
most notably Liquidambar orientalis [1]. It is, however, extremely
unlikely that there could be sufficient monomer available from these
plants to supply even the EPS demand, let alone the rather more
solid polystyrene manufactured every year. In order to be realistically
‘sustainable’, economics and scale require that such a polymer must
be made from widely grown plants, preferably not required for food
use (because the supply of food crops is under increasing pressure
from a growing world population), and that the yield of polymer
is reasonably high and efficient in the energy used to manufacture
and process it.
Over the past few years, a wide range of sustainable polymers has
been promoted as potential solutions to these issues, and it remains
unclear which of them will be among the winners and losers – some
may find specific niches while some may succeed on a larger scale
and others fall by the wayside [2]. Long-established materials such as
starch and cellulosic polymers have come under fresh consideration,
together with polyhydroxyalkanoates (PHA), polylactic acid (PLA)
and other more exotic polymers (Nylon 12, for example, is made from
castor oil). There has also been an announcement [3] that Braschem
SA of Brazil is to produce a fully renewable linear polyethylene
derived from sugar cane, although this is intended for packaging film
production at present. Producers and users of mouldable particle
foams are also keenly interested in this developing area – if, for
example, governments legislate (or large customers decree) to require
packaging to be sustainable or degradable then cost constraints that
presently apply may become much less important and the ability to
deliver a product that works much more critical.
The issue of how post-use foam packaging can best be handled in

an environmentally acceptable manner is still a subject of much
70
‘Sustainable’ Polymers – The Future?
debate [4], and it is possible that legislation will dictate (therefore

potentially differently in different countries) how the material must
behave. For example, a foam material that begins to degrade as
soon as it is exposed to ultraviolet light and moisture (e.g., when it
is discarded as litter) may quickly cease to be a visual affront, but as
well as the potential for degradation before it is desirable (while it
is still in use as packaging), it is then lost to any potential recycling.
There are already masterbatches available which can trigger so-
called bio-oxo-degradation (e.g., see product literature for d2w,
Total Degradable Plastics Additives or Biobatch), although these
are intended and marketed as a means to make synthetic polymers
(often polyolefin films and bags) ‘disappear’ once discarded. There
is no reason why similar technology should not be used to accelerate
the degradation of bio-based polymers – by their nature these tend
to biodegrade, although sometimes very slowly – and it may be that
there will be a market for such pro-degradants even in the sustainable
polymers field.
Biodegradability was earlier seen as a positive benefit of bio-based

materials, and remains so in some niche applications such as the
medical field, but has actually proved to be a handicap in many
markets. As long ago as 1997, it was concluded [5] that the growth
prospects for biodegradable polymers would most likely depend on
legislation to restrict the disposal of organic materials into landfill
– this would affect both bio-based and synthetic polymers and
foams. Increasingly, ‘sustainability’ is seen as more important than
biodegradability for packaging, as collection for re-use, recycling
or incineration becomes better established – the idea of using a
package once and then allowing it to decompose in the environment
is viewed as less environmentally responsible. Composting may be
an acceptable way to use biodegradability in a beneficial way – at
least the raw materials and energy put into making a package are
recovered to some extent.
Compostability is still therefore seen as desirable, as collection and

recycling costs for low-density and often contaminated items such
as post-use foam packaging can be prohibitive, and there are now
71
standards which lay down the requirements for materials to be

acceptable into the wide variety of composting processes already in
operation around the world. Because composting conditions vary,
from heap systems (self-heating when they are large enough) to
pressurised retorts, and the timescale of the process can vary with the
operator, some polymers may be regarded as compostable in some
systems but not in others. There are now standards such as EN 13432
[6], ISO 14855 [7] and ASTM D5338 [8] which have established
test specifications and criteria for the assessment of compostability
and biodegradability. These standard test methods are oriented
towards industrial-scale composting plants where temperatures
are relatively high (55–60 °C) – some authorities such as Vincotte
(Belgium) also offer certification for compostability in much cooler
domestic composting.
Recycling is an alternative to disposal by composting, and can, as

with EPS (see Section 2.6.4), take several routes. Waste foam may
be disintegrated to the individual expanded beads, then remoulded,
or may be remelted and reprocessed to beads or other products.
The viability of each route will depend on the degree to which the
polymer chain length has already been degraded in service and in
the recovery process (although polyesters such as PLA and PHA can
have their chain length rebuilt by using suitable chain extenders in
a melt process).
In the following sections, four of the candidate polymer classes will be

reviewed and recent developments discussed. As already mentioned,
it is still far from clear how the market will develop, or even what
constraints will drive it, but we may be sure that cost will remain a
major competitive issue – there are materials solutions other than
mouldable foams to all packaging issues, and their relative costs will
also help to winnow the field.
The important issues surrounding any candidate for mouldable foam

production include:
• The cost of the polymer and its processing,
72
• Selection of blowing agent(s) and their interaction with the

polymer,
• Temperatures for processing and in service, and
• Whether the polymer is recyclable or degradable or compostable

after use.
Each of the polymer types will be considered against these criteria

and to what extent recent reported work allows us to judge their
potential for finding suitable applications in the near future.
The cost of a packaging product moulded in particle foam depends

to a large extent on the base cost of the polymer – the subsequent
processes do add cost, and a material which is expensive to process
will carry a handicap, but a rule of thumb in the plastics industry
is that the product cost is usually between 1.5 times and twice the
polymer cost. Accordingly, a material that is expensive to synthesise
(e.g., more than twice the cost of polystyrene) will tend to be regarded
with disfavour, and alternative packaging solutions are likely to
become competitive against it. One of the factors driving the interest
in sustainable polymers is, however, the volatility in the price of
crude oil (which determines the cost of synthetic polymers) and the
certainty that the long-term trend is to higher oil prices as oil fields
dry up and world production declines. There are many contending
voices in the debate over how soon the so-called ‘peak oil’ (maximum
output) will occur, though few doubt that it will be sometime in the
near to medium term – some would argue that the world is already
at that point. As oil prices increase, so the cost of producing bio-
based materials will also be affected, as energy is needed for their
synthesis and processing, but it is anticipated that such increases
will be smaller than the increases in the price of synthetic polymers.
Over the next few years, therefore, we can expect the competitive
position of sustainable polymers to improve, although not without
excursions – the world recession of 2009 lowered oil prices to a
third of the peak reached in 2008. Such instability is not helpful to
companies considering investments in sustainable polymer capacity,
73
and it will not be a surprise if the number of players in this field suffers
significant attrition in the next few years. What is more important
when considering the options for foams made from sustainable
polymers is the comparative costs of the candidates – here PLA and
starch-based materials have a clear advantage over polyalkanoates
and cellulosics. As will be seen below, PLA-based materials have seen
by far the greatest amount of effort in recent years.
Blowing agents are, as we have seen in previous chapters, a

vital component of a mouldable particle foam system. The ideal
combination is, as with EPS, a volatile plasticiser for the polymer,
which is well retained in the beads at ambient temperatures. After
pre-expansion, if some of the blowing agent remains in the beads
for later use in the moulding process, to expand and fuse the beads
together, that is even more desirable. This is, however, only likely
to work when the polymer has a Tg value well above ambient
temperature, and a good affinity for the blowing agent. As suspension
polymerisation is not available as a route to the production of suitably
sized (0.5–1.5 mm) beads, all of these polymers would most probably
need to be extruded as microbeads and impregnated with a blowing
agent (in the extruder or subsequently) before pre-expansion and
later moulding.
Processes for EPS and EPO rely on steam as the medium for heat
transfer to the beads – it has a high heat capacity and can be controlled
in temperature over quite a wide range, by varying the pressure or
diluting with air. Existing equipment for expansion and moulding
has been developed and tuned for use with these types of beads – if
a new bead material requires a significant redesign of the process
equipment then that will add to its costs and make it less likely to
be adopted.
As all of the candidate polymers are to some degree crystalline (there

is so far no bio-based analogue of polystyrene with its amorphous
character and conveniently located Tg), process temperatures for
foaming and moulding tend to be quite critical, and typically lie
just below the melting point of the polymer. The (usually slow) rate
74
of crystallisation during and after the steps of pre-expansion and

moulding will also affect these process steps, and may require control
by the use of nucleants or co-monomers.
The issue of recyclability or compostability or degradability has been

discussed above – this will be a constraint that may vary between
different applications and/or territories, as legislation and customer
preference are likely to be the decisive factors.
The development of particle foams in these polymers is not as yet very

advanced, but production of extruded expanded sheet has made much
more progress. Technologically this is a less demanding application
– chemical blowing agents can be used, or a physical blowing agent
can be injected into the melt in the extruder just before the die and
need not be retained in the melt since expansion occurs immediately
it emerges from the die and is depressurised. The discussion of the
literature which follows will, therefore, necessarily include reference
to such sheet products and consider how the techniques described
may, or may not, be applicable to mouldable beads.
4.2 Polylactic Acid (PLA)
4.2.1 Production and Properties of PLA Polymers
In recent years interest in polymers of lactic acid (2-hydroxypropanoic

acid) has been increasing quite markedly, especially as the cost of
the material now appears to be competitive with some of the oil-
based polymers. Initially PLA was seen as a low-volume, high-value
polymer mostly for medical applications (such as fibres for degrading
sutures, or temporary scaffolds that disappear over time in the body).
The position changed in 2002 when Natureworks LLC (initially
a joint venture between Dow and Cargill) commissioned a large
production facility (nameplate capacity of 140,000 tpy) for lower
cost PLA in the USA, and there are now smaller volume suppliers
in Asia. In 2008, two European investments in PLA production
75
facilities were announced, including one for Synbra Technology BV

targeted specifically at foamable bead production [9]. The material
cost is indicated as being comparable with polyethylene terephthalate
(PET) or somewhat higher – still not comparable with EPS costs, but
low enough to make PLA the most popular sustainable polymer for
investigation, based on its cost and balance of properties. As more
suppliers come on stream, so the cost is likely to fall, and as more
experience is gained with it, so will the processing costs and hence
the cost of products made from the material.
PLA can be produced from a very wide variety of plant types,

including corn starch, sugar beet and sugar cane, potatoes and
other biomass (which need not necessarily be a food crop). The
carbohydrates in a suitable feedstock are fermented to lactic acid
by lactobacillus bacteria under conditions arranged to optimise the
yield and purity of the product. Direct polymerisation of lactic acid
to usefully high molecular weights is not practicable as the water
eliminated as each monomer unit adds to the chain tends to break
the chain back down by hydrolysis – only low-molecular weight
oligomers are achieved. This problem is overcome by catalytically
cracking the oligomers down to the cyclic dimer, lactide, and
removing the water. The high-molecular weight polymer can then be
produced in a ring-opening polymerisation reaction, often catalysed
by tin octoate, although other catalysts are used. A fuller account
of the technology as it stood in 2007 can be found elsewhere [10].
PLA polymers are also described as polylactides – there is as yet no
firm consensus over nomenclature.
As lactic acid is a chiral molecule (see Figure 4.1), in which the methyl
group can be either on one side of the chain backbone (‘looking’ from
the double carbon–oxygen bond) or on the other, there are potentially
many types of ‘PLA’ which can be produced. By controlling the mix
of lactides (L–L, L–D, D–D) fed into the ring-opening polymerisation
process, polymers can be made with all L-lactic acid units in their
chains (PLLA) or with all D-lactic acid units (PDLA), or with the
chains comprising a random mixture sometimes referred to as P(DL)
LA. Most of the useful grades are strongly biased towards PLLA
76
with limited proportions of the D-isomer – the higher the D-content

the lower the crystallinity and thereby the heat resistance. Generally,
polymers with D-contents below 5% crystallise well, whereas if it is
above 10–12% the polymers are fully amorphous – a fuller account
of the relationship between composition and properties of PLA
polymers can be found elsewhere [11].
L-Lactic acid
D-Lactic acid
Figure 4.1 L- and D-Lactic Acids, showing the chirality of the

molecules
The properties of PLA polymers are in some ways comparable with

those of polystyrene or amorphous polyethylene terephthalate (A-PET),
even though PLA is semi-crystalline. They are usually transparent and
stiff, relatively brittle in unmodified form, with a high specific gravity
(1.25–1.29). Tg is rather low, around 58 °C, while the crystallinity and
crystalline melting points depend on the degree of stereoregularity –
pure PLLA is reasonably crystalline and has a melting point around
170–180 °C, but as the content of D-lactic acid units in the polymer
increases, so the crystallinity is reduced and the crystals melt at lower
temperatures. The rule of thumb is that for each 1% of D-units the
melting point falls by 4 °C. There is, however, a specific crystalline
77
form, the so-called stereo-complex, where a mix of equal parts of L-

and D-chains can co-crystallise in a specific crystal morphology with
a high melting point at around 230 °C. In general, PLA polymers are
slow to crystallise and often require nucleation to achieve tolerable
crystallinity after processing. The low Tg together with this slow
crystallisation has restricted the material’s application. Although it
can be thermoformed quite easily, the resulting products have limited
heat stability and service temperatures above 40–50 °C can cause
shrinkage and distortion. Much effort has been expended on attempts
to control crystallisation behaviour so that, for example, extruded
sheets of PLA are amorphous enough to be easily thermoformed but
can be persuaded to crystallise quickly to a level that gives the formed
product adequate heat resistance. Typical nucleating agents for PLA
crystallisation include talc (yielding translucent or opaque parts) or
ethylene-bis-stearamide (EBS) wax for greater transparency.
4.2.2 Processing of PLA-based Beads – A Trend Towards

Carbon Dioxide
As PLA is made from renewable raw materials, it has recently been

seen as preferable that the blowing agents used to foam it should be
also – this suggests alcohols or carbon dioxide (CO2) as the most
obvious candidates. Other agents have been tried (see also Section
4.5 below) but the bulk of recent foam development work appears
to have been focused on CO2. PLA, particularly when CO2 is used
to expand it, presents some unusual demands in processing, as will
be explained further below.
There have been many patents and patent applications filed in

respect of foamed PLA in the past 15 to 20 years – a search carried
out in 2007 found some 85 filings in Japan alone, with considerable
overlaps – and it would be impractical to attempt to summarise them
all. The following account is therefore an attempt to identify some
key documents and the teaching contained within them about the
challenges of working with PLA and how they have been addressed
with more or less success.
78
Commercial PLA foam mouldings have remained elusive, although

there have been announcements of imminent launches. For example,
in 2005, both Unitika and Kaneka announced in Japan that they
were about to introduce mouldable PLA foam bead products
[12, 13]. In 2008, the Biopolymer Network of New Zealand was
awarded an International Bioplastics Award [14] for their 2006
development of mouldable PLA foam beads, said to have been the
result of a collaboration between three Crown Research Institutes
in New Zealand and an Australian packaging group, Alto. A patent
application covering this work was filed in August 2008 and is
discussed in Section 4.2.4. Further information on the current status
of these three product introductions is difficult to find, but it is clear
from these and from a recent announcement in Europe [9] that
moulded PLA foam packaging will be in service in different parts of
the world before very long.
Some of the earliest patents of interest were granted to DuPont in

1992, for foamed extruded sheet products [15]. The blowing agents
referenced included CO2 and nitrogen, but hydrofluorocarbons (made
by DuPont) were favoured. This patent claimed the benefits of using
star-shaped polymers from a special polymerisation process, and extra
benefit could be gained by crosslinking the polymer. Expansion was
achieved by extrusion or by placing the sheet, containing the blowing
agent, in a mould and heating so that it expanded to fill the mould.
Mitsui Toatsu claimed a process for extrusion-foamed sheet in a
1995 patent [16] which introduced some of the concepts mentioned
frequently thereafter. The process used a mixture of PLLA (crystalline)
and P(DL)LA (amorphous) polymers, and additives such as chain
extenders and plasticisers were compounded into the melt. A range
of blowing agents such as butane is mentioned in the description
of the invention, although only chemical blowing agents appear in
the claims – interestingly, CO2 is not mentioned as a blowing agent.
The examples show that foamability improved as the proportion of
amorphous PLA was increased.
In 1994, BASF [17] patented a mouldable particle foam in which

the expandable beads were made from an amorphous PLA, and
79
expanded using a mix of methyl formate and pentane as the blowing

agent. These expanded beads were then fused during moulding
by means of finely powdered, unexpanded PLA mixed with them
before moulding, to act as an adhesive, as the crystallinity developed
during expansion inhibits bead fusion. A similar approach was
described by Kanebo in a Japanese patent application of 2001 [18],
where the preferred adhesives were polybutylene succinate (PBS) or
polycaprolactone (PCL). Another member of Kanebo’s long list of
2001 patent applications [19] claims the use of blends ranging from
crystalline (5% D-form) to amorphous (60% D-form) PLA. There
is also a chain extender, plasticisers such as glycerol, erythritol or
pentaerythritol, talc as foam nucleator and a volatile blowing agent
such as isopentane or butane. The blowing agent is impregnated
into the beads after they have been made by an extrusion process.
Methanol or ethanol or acetone mixed with the blowing agent are
claimed to act as foaming assistants. These patents highlight one of
the difficulties when trying to mould pre-expanded beads of PLA –
there is little expansion power in the beads and it is difficult to heat
their surfaces sufficiently to fuse them without damage to the cell
structure, or even collapsing the beads. In general, as with expanded
polypropylene (EPP), moulding expanded PLA results in an increase
in density compared with the pre-expanded beads, and ways to
minimise this effect have been much sought after.
4.2.3 Processing of PLA-based Beads –Interactions

Between PLA and Carbon Dioxide
As the emphasis has shifted from the biodegradability of PLA

foams to their sustainability, CO2 has become the favoured blowing
agent, and the majority of recent patents and applications focus on
it. The use of CO2 brings its own difficulties – it is a gas at normal
temperatures, freezes/sublimes at 78.5 °C (it does not liquefy except
at high pressures) and has its critical point at 31 °C. Generally,
therefore, it is stored as a liquid under pressure and must be either
injected into the barrel of an extruder as a supercritical fluid or
impregnated into pre-made beads close to room temperature but
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at moderately high pressures. It does have reasonable solubility in

the amorphous regions of PLA, so that, given time, more than 10
wt% can be absorbed, depending on the applied pressure. The rate
of diffusion is, however, quite high, so that absorbed gas can be lost
quite quickly once the pressure is released and the beads exposed to
atmosphere – they can lose sufficient gas to be unusable within an
hour or so.
Sheet extrusion foaming of PLA by CO2 injected into the extruder

upstream of the die is relatively straightforward, and there have been
numerous patents filed to cover this type of process, recent examples
being to Coopbox of Italy [20] and Natureworks [21]. The process
of CO2 extrusion foaming of PLA, on its own and in blends with
thermoplastic starch (TPS), has also been studied by a Canadian
team [22] with some interesting findings. Using a laboratory-scale
extruder they melted the polymer components using a crystalline
(low D-content) PLA (which was grafted with maleic anhydride for
blending with a well-dried TPS with glycerol as the plasticiser),
compounded talc into it as a nucleator and injected CO2 upstream
of the die. They found that foaming was very poor until the CO2
level in the melt reached 7%, and that above this level the foam
density, at 20 kg/m3, remained constant as the gas level was raised
as far as 10%. The foams had a significant proportion of open
cells, suggesting that some of the gas escaped before it could be
used to foam the polymer, and that the cell walls were prone to
breaking. The other interesting finding was that the combination of
plasticisation by the CO2 and orientation during expansion allowed
the development of a reasonable degree of crystallisation in the
PLA – this somewhat unexpected behaviour of PLA is discussed
further next.
The effects of absorbed CO2 on PLA were explored in a paper

presented at the ANTEC conference in 2005, by another group
of Canadian researchers [23]. They moulded thin discs of a
(potentially) crystalline PLA from Unitika with a D-content of less
than 2%, but by quenching after moulding ensured that they were
fully amorphous. These discs were impregnated with CO2 for two
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days at room temperature and different pressures, the uptake of

gas was measured and finally the discs were allowed to foam by
releasing the pressure and heating them to temperatures up to 160
°C for a short time – as little as five seconds and temperatures in the
range 90–100 °C appeared to be optimal for good foam structure.
The solubility of CO2 in PLA rises fairly linearly with applied
gas pressure, while the diffusion coefficient rises exponentially.
Interestingly, they found that above about 2.1 MPa impregnation
pressure, the PLA began to crystallise at 25 °C, and that the level of
crystallinity then rose with pressure to a plateau of 24% above 3.5
MPa. As a result, the foaming generated from lower impregnation
pressures was softer and had better cell structure. At the higher
pressures, the increased diffusivity and increased polymer stiffness
arising from the crystallinity meant that the gas escaped more
quickly or was used to nucleate foam cells, with the result that the
foam structure was finer but less uniform.
Another interesting study was published in 2007 by a team from

the University of Thessaloniki, Greece, reporting experiments
on the foaming of PLA (this time with a D-content of 12%, so
amorphous) impregnated with supercritical CO2 and comparing it
with polystyrene [24]. This work was again carried out on discs of
the two polymers, placed in a pressure vessel filled with supercritical
CO2 (at up to 40 MPa) and held for four hours, followed by release
of the pressure at a controlled rate. The temperatures used for the
PLA lay between 35 and 55 °C, while for polystyrene they were
higher, 80–100 °C. The impregnation pressures and pressure release
rates were varied and the density and cell structure of the foaming
that resulted were quantified. The faster the pressure was released,
the more numerous but also the smaller the cells – the foam density
increased with the rate of pressure drop, as more gas was used to
create new cells than to grow the existing ones. The effect of higher
temperature was, as would be expected, to reduce foam density – the
cells grew faster because the gas was able to diffuse into them more
quickly. Although the conditions used in this study do not appear
to relate very closely to real process conditions, the work does cast
some light on the dynamics of foaming.
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It is clear from the previous discussion that the interactions between

PLA and CO2 make the use of CO2 as a blowing agent far from simple.
The gas plasticises the polymer, reducing its already low Tg (results
[22] suggest that Tg falls below 25 °C with around 8% CO2), but
the gas diffuses through it quite quickly so is not well retained. The
promotion of crystallisation by the combination of this plasticisation
and the biaxial orientation which develops during expansion means
that, after expansion, beads of crystallisable grades of PLA can have
a significant crystallinity. Although this boosts heat resistance, which
is desirable in the finished product, it also reduces the ability of the
beads to expand and fuse together during the moulding process. Fully
amorphous PLA has quite poor heat resistance, with a maximum
service temperature around 40 °C, a little too low for even the
majority of packaging applications. PLA with some crystallinity has
better temperature stability, so that companies wishing to market
foamed PLA products have to find a way to impregnate their beads
with a controlled level of CO2 then expand and mould the beads to
a product with good fusion and mechanical properties – how they
have achieved that is discussed next.
4.2.4 Processing of PLA-based Beads – Review of Recent

Patents and Patent Applications
The great bulk of patents and applications on the topic of foamable

PLA beads come from Japanese companies, most of them filed only in
Japan, so that only the abstracts are available in English. The exceptions
are JSP Corporation, which has filed in Europe and the USA, and
the Biopolymer Network of New Zealand, which has recently filed a
world patent application – much can be learnt from the descriptions
in those documents. Filings by other Japanese companies will also be
reviewed in less detail – since 2003, Kanebo Ltd, Unitika Ltd, Sekisui
Corporation, Kanegafuchi Chemical Industries (Kaneka) and Achilles
Corporation have also made applications which appear relevant.
JSP’s first application dates back to 2003 [25] and claims an expanded
bead containing at least 50 mol% of lactic acid units (allowing for
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copolymers or blends with other polymers, although none of the

examples have any other polymers in their makeup). The principal
focus of the description and claims is on the crystallinity of the beads,
in the expanded state, where it should not be too high. As amorphous
but potentially crystalline PLA is heated, it can undergo an exothermic
‘cold crystallisation’ process at 80–90 °C – as this coincides with
typical prefoaming temperatures, it can limit the expansion and
interfere with bead fusion in the later moulding step, but also brings
improved heat resistance to the moulded product. The description
emphasises that the conditions under which the beads are extruded,
impregnated and then expanded are critical to the control of the
crystallinity, especially the temperature at which the blowing agent
is impregnated and the duration of the heating during expansion.
Both crystallisation speed and maximum crystallinity of the material
can also be controlled by blending crystalline (higher L-content) and
amorphous (higher D-content) grades of PLA, and the examples
cover a range of compositions from 100% of the crystalline grade to
50% – the best results appear to be found at 50%, but many other
factors are varied including impregnation and expansion conditions
and also the post-ageing of the mouldings. Talc is used as a nucleator
for both crystallisation and foaming.
The blowing agents mentioned in this patent include a list of organic

agents such as propane, butane, pentane, hexane and haloethanes, but
it is stated that inorganics such as air, nitrogen, argon and CO2 are
better from the cost and environmental standpoint, particularly CO2,
and all the examples use it. Impregnation of the beads is carried out
under pressure in an autoclave, either ‘dry’ or suspended in water, at a
temperature below the final Tg of the impregnated polymer – there is
a formula to determine the optimum temperature based on the desired
CO2 content, which yields values below 40 °C. The impregnation
pressure is in the range 0.5–10 MPa, applied for up to 12 hours, to
charge the beads with up to 20% CO2 (the examples range from 6
to 14%). The expansion is best carried out using a mixture of steam
and air, at a temperature around 60–70 °C. The expanded beads are
then repressurised with air or CO2 before moulding using steam, as
this improves the fusion. Finally, the mouldings are aged for up to
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24 hours at 60–70 °C to complete the crystallisation process and

optimise heat resistance.
A 2006 filing [26, 27] demonstrates further refinement of the

technology. Again, the description covers blends of crystalline
and amorphous PLA grades, possibly also copolymers and blends
with other polymers such as biodegradable polyesters similar to
BASF’s Ecoflex (see also Section 4.3.2). The account of the prior
art describes how the use of high-pressure steam for moulding,
necessitated by the high crystallinity of the expanded beads, can
damage the amorphous regions of the beads and cause shrinkage
and an uneven surface. The solution to this problem includes the
careful control of crystallinity as laid out at length [25] previously,
but also the use of a polyolefin wax, preferably a polyethylene, of
closely defined molecular weight and crystallinity, as a nucleating
agent to promote a fine cell structure in the expanded beads. Carbon
dioxide is again the preferred blowing agent, preferably impregnated
into a suspension of the beads in warmed water as before, to a level
between 5 and 15%. Another co-blowing agent may be used, such
as isobutane, although this is not in the examples.
There is also a claimed benefit from incorporation of a plasticiser

as well as a ‘fusion bonding improver’, flame retardants, antistatic
agents, etc. There is a long list of useful plasticisers, although the most
suitable is stated to be glycerin diacetomonocaprylate – the function of
the plasticiser is to lower Tg of the polymer by a few degrees, thereby
improving the secondary expandability and fusion during moulding.
Interestingly, the plasticiser is optimally applied to the outer surface
of the beads during the CO2 impregnation process. This ensures
that the plasticiser penetrates the surfaces of the beads, and helps
during expansion to create what is claimed to be an advantageous
cell structure where a 300 Mm layer at the surfaces of the beads has
larger cells than the core. The expansion, repressurisation to an
internal pressure of 0.05–0.2 MPa and moulding processes are as
in the previously discussed patent [25], but there is in this patent no
need for a post-ageing of the mouldings.
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In the examples, where moulded densities down to 50 kg/m3 are

reported, a range of polyethylene waxes are compared – such waxes
are also used as nucleators in EPS. Most of the examples were made
with 20% crystalline PLA and 80% amorphous PLA (both from
Mitsui Chemicals), although later examples were at higher levels of
the crystalline grade. In all cases the processing of the beads was the
same, as the main purpose of the examples was to explore the effect
of the different nucleators. The impregnation with CO2 was carried
out at 30 °C at a pressure of 3.0 MPa, falling gradually to 2.5 MPa
over three hours – this gave a concentration in the beads of around
5–6%, which proved sufficient to expand them down to 40–50 kg/m3.
Despite the extensive description of their benefits, plasticisers were
not used in the examples. The beads were expanded at 80 °C for
one to two minutes, and after repressurisation with air at 0.2 MPa,
moulded with steam at 0.02 MPa, yielding mouldings with densities
from approximately 50 kg/m3 upwards.
The Biopolymer Network application [28] takes a very different

approach, using liquid CO2 for impregnation, at a moderately low
temperature (10 °C appears optimal) but high pressures (in order
to maintain the CO2 in the liquid state). In this process, PLA beads
(which are claimed not to require nucleation) are immersed in liquid
CO2 at around 10 °C and a pressure of 6 MPa for a period of 30
minutes to 4 hours. Under these conditions, the beads can absorb
30% or more CO2 – the pressure is then released and the beads cooled
to 20 °C and stored for a period (which can be as long as a month).
During the first day or so of storage, the CO2 concentration falls by
some two-thirds, then settles and falls only slowly thereafter – the
gas is also claimed to redistribute itself within the beads, and this
ageing process is said to be important for foamability.
Following the storage period, the beads contain 8–12% CO2 and
can be expanded at a temperature in the range 50–70 °C – some of
the examples were expanded in hot water. The pre-expansion yields
a prepuff that can then be moulded immediately (no need for the
maturing process which is typical of EPS) or stored (again in a freezer)
for moulding at a later date. Moulding is carried out at temperatures
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up to 110 °C, although the claims cover both the case where the
moulding is effected at or above the pre-expansion temperature and
the case where it is done at or below the pre-expansion temperature,
and the examples are similarly various. What is made clear is that
the pre-expansion should not exhaust the expansion potential of the
beads, and that enough CO2 should remain to drive further expansion
during moulding.
The claims make no reference to whether amorphous or crystalline

PLA is desirable, although they do cover the possibility of using
blends with other polymers such as EVA or synthetic polyesters such
as PBS, and also fillers such as talc, chalk and ground pine bark. The
description and examples do explore the amorphous–crystalline PLA
balance and although all the subsequent examples use amorphous
PLA, the first reports successful expansion and moulding of blends
with up to 50% of a crystalline grade. The description does, however,
observe that the more crystalline the PLA, the less effective the process
is usually found to be – presumably this is why the blends exemplified
all had at least 50% of an amorphous grade, and the beads might
be expected to have little or no crystallinity. This is unsurprising, in
the light of the accelerating effect of absorbed CO2 on crystallisation
discussed in Section 4.2.3. Unless the low temperatures prevent it,
these high CO2 levels would accelerate any potential crystallisation,
making the beads much harder to expand. If the beads do remain
amorphous (and the application does not discuss the development
of crystallinity during the processes), the heat resistance of foamed
objects made by this process will not be high. Amorphous PLA has
a long-term service temperature limit close to 40 °C, so foamed
amorphous materials would also be very limited in terms of the
ambient temperature range they could tolerate without undergoing
softening, shrinkage or distortion.
Kanebo has three 2006 applications in Japan [29-31]. The summary

of the first [29] indicates that the use of an ‘aprotic’, non-aqueous
dispersion medium improves the gas impregnation process, and also
refers to the expansion process being carried out at between 10 and
35 °C above Tg of the PLA polymer. Moulding is best carried out by
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preheating the expanded beads to 10 °C below Tg to 30 °C above Tg,

then moulding them at between 30 and 60 °C above Tg. The English
summary of the second application [30] is very general, claiming
that use of 0.5–10% of additives including a plasticiser allows the
volume expansion ratio to be controlled. The objective of the third
application [31] is to provide antistatic mouldings at an expansion
ratio of 30, by incorporating 1–3% of a secondary alkanesulfonic
acid sodium salt into the PLA.
Unitika’s applications are mostly in Japanese and the English

summaries are often so brief as to give little idea of the technical
content of the application, but there are two applications available
in English that provide more details [32, 33]. Both are oriented
principally towards foamed sheet products of relatively high density,
but reveal a preference for crosslinking the PLA using a peroxide
and an ester of methacrylic acid. The more general application
[32] covers a wide range of applications including blow mouldings
and injection mouldings, but does have one example that describes
foamable beads which can be expanded to a ratio of 45 using butane,
impregnated into the beads at 10 MPa and 130 °C. The compositions
include nucleating agents (which promote crystallisation as well as
foaming) and ‘foaming aids’ such as calcium or magnesium stearate,
or stearic acid. The purpose of the invention described in the other
application [33] is to reduce the water vapour permeability of a (CO2)
foamed PLA sheet which can be thermoformed into containers, by
incorporating a wax (candelilla or paraffin wax) and low-density
polyethylene (LDPE).
Sekisui Plastics’ recent intellectual property appears to take a different

approach to the moulding of foamed articles, that of foaming the
beads in the mould, to expand and fuse them at the same time. A
2007 Japanese application [34] claims a benefit from using water
as the heating medium, at 60–100 °C. A world patent application
filed in 2008 [35] describes a die-face pelletising system for cutting
beads as they expand from the die – this produces roughly spherical
expanded beads, which further expand isotropically during the
moulding process and fuse together strongly. It is not clear from the
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abstract how much expansion is achieved at the die and how much
more during moulding, nor what blowing agents or other additives
are required.
Two very recent applications [36, 37] from Kanegafuchi/Kaneka

also relate to an in-mould foaming process for PLA beads initially
foamed using a hydrocarbon blowing agent. These expanded beads
are then pressurised with CO2 for a short period (0.5–10 minutes at
0.1–2 MPa pressure) before moulding. This appears to be a step back
from using CO2 as the only blowing agent, as others have done in
recent times – perhaps the shelf life of beads between impregnation
and expansion is considered too short.
Achilles Corporation claims to have extended shelf life (before

expansion) by using cyclopentane as a foaming aid in beads
impregnated with one of the common hydrocarbon blowing agents
(isobutane, n-butane, isopentane, n-pentane) [38].
In conclusion, then, we can say that the various challenges faced in

producing mouldable foam beads from PLA, especially when CO2
is used as blowing agent, have been tackled in different ways by a
number of workers. That moulded articles from foamed PLA remain
scarce is perhaps an indication that the costs of producing them are
not yet competitive – perhaps that will change in the near future.
4.2.5 End-of-life Aspects of PLA Foam Products
PLA of a useful molecular weight is insoluble in water, and takes water

up only slowly from its surroundings. Once water does penetrate
the material, it can break down the polymer chains by hydrolysis of
the ester linkages, principally in the amorphous phase – the broken
chain ends include carboxylic acid groups which catalyse further
degradation. In general, this process is rather slow, and although
products made from PLA can decompose in industrial composting
systems when mixed with other wastes, if there is too much PLA
present the composting process can be excessively prolonged.
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There have been problems, for example when large numbers of

PLA drinking cups were collected from outdoor events and proved
slow to break down. Foamed PLA can be expected, by virtue of its
lower density and open structure (once the cell walls begin to break
down), to compost faster than solid items, but each type of product
may need to be tested and shown to be compostable before it can
be granted certification.
Recycling of PLA is entirely practicable – waste material may be

remelted and reprocessed into new products. Predrying is important
to reduce hydrolysis during processing, or chain extenders may be
added to rebuild the molecular weight. It is likely that recycling
of PLA packaging products will be preferred wherever possible,
including where used foam packaging can be economically collected,
just as for EPS.
Incineration of waste, including plastics, is now common practice

in Europe, and where the energy is recovered by using the heat of
combustion to generate electricity is a reasonably carbon-neutral
means of disposal for the renewable polymers discussed in this
chapter. It is certainly better than burial in landfill, where organic
materials such as waste plastics tend to break down anaerobically
and release methane, a short-lived but potent greenhouse gas.
There is in principle, no reason why foamed PLA (or PHA or

cellulosics) cannot be used for long service life applications such as
insulation boards, though it is hard to see how this could be achieved
for TPS because of its high water absorption. With suitable flame
retardants and antibacterial additives, or a coating of some kind to
exclude water, it should be possible to retain integrity for many years,
though this would require demonstration and certification to satisfy,
for example, construction standards. It might appear counterintuitive
to use an inherently biodegradable material for a long-life product,
but as oil prices increase it may eventually be cost-advantageous to
use sustainable polymers instead of EPS, and there are numerous other
biodegradable materials such as wood widely used in construction.
At the end of life such materials can then be recycled, incinerated or
perhaps treated in some way to accelerate their biodegradation.
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4.3 Starch and Starch-based Foams
4.3.1 Production and Properties of Starch-based Polymers
Starch is an inexpensive and widely available plant-derived polymer,

which is hygroscopic. Water plasticises the polymer, and in excess
dissolves it – this renders it processable but places limitations
on its usefulness in applications where durability is important
(construction, and even much protective packaging). Improvement of
the serviceability of TPS has therefore been a long-running research
interest, although to date most applications have been where its rapid
breakdown by water is an advantage, such as in disposable hygiene
products, golf tees and fast-food packaging.
Starch is a polymer of D-glucose, with two types of repeat units, linear

amylose and branched amylopectin (see Figure 4.2), the proportions
affecting the properties of the polymer. In its raw form it consists
of hydrophilic crystalline beads some 15–100 Mm in diameter, with
a melting point above its decomposition point around 250 °C.
The crystalline structure can be broken down in a gelatinising or
destructuring process, using water and other plasticisers, heat and
shear, so that a melt-processable form, TPS, results. It is essentially
amorphous in nature and is readily plasticised by water – adjustment
of the water content allows the processing behaviour to be controlled
to suit the application [39]. In the main, useful TPS grades are at
least 70% (linear) amylose.
The properties of TPS are quite poor – it softens at a temperature

that depends on the content of water and other plasticisers, but
is usually between 60 and 120 °C. Films made from pure TPS
are hard and brittle and much of the development work done
on starch-based polymers has had the objective of improving
the mechanical, thermal and durability properties without losing
the cost and biodegradability advantages. There are a number of
commercially available blends such as Novon (Warner-Lambert
and Chisso Corporation), Mater-Bi (Novamont) and Plantic
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(Plantic Technologies and Du Pont) with properties tailored to

particular applications.
Amylose
Amylopectin
Figure 4.2 Structures of amylose and amylopectin, the component

repeat units of starch
4.3.2 Processing of Starch-based Foamable Beads
Water contained within TPS beads can be used successfully as an

environmentally friendly and cheap blowing agent. If the material
is heated quickly, the water boils and foams the material rather than
being driven off. A long-established and popular use is for loose
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fill packaging ‘beans’, easily disposed of by dissolving in hot water

once their useful life is over [40]. In order to make useful moulded
products, the challenge is to produce foamable beads which can be
easily moulded (fused), and also to improve the durability of the
moulded products, discussed in more detail in Section 4.3.3.
A patent application filed in 1998 [41] from the Institute for

Agrotechnical Research (ATO) at the University of Wageningen
in The Netherlands describes a method for producing relatively
thick moulded parts in a single step which combines expansion
and moulding. Granules of TPS are conditioned to a water content
around 15%, then coated with a plasticiser which also acts as an
adhesive. The granules are place into a mould and there heated using
microwave energy. This heats the water to steam which expands the
starch and, with the aid of the adhesive, fuses the beads into a single
foamed piece. There is no record of this application proceeding to
granted status – the method is clearly only practicable with a high-
power microwave oven and non-metallic moulds.
Using water as the blowing agent for starch has the disadvantage that
the concentration of water must be tightly controlled before expansion,
as it affects the rheology of the material as well as providing the
driving force for the expansion. If the water concentration is too high,
the material may have insufficient melt strength to sustain a good
cell structure, too low and it may not be able to expand sufficiently.
This makes the processing of the material inherently unstable and
unpredictable. Further, employing the conventional EPS processes,
using steam to expand and mould foamed TPS risks damage to the
foam structure (‘burning’ of the beads) as the temperature of the
steam will usually be above the softening point of the material. BASF
has addressed this issue by using more conventional blowing agents,
in beads made from starch-based blends [42] which have more heat
and moisture resistance. This patent claims blends of a biodegradable
copolyester with starch or a cellulose-derived polymer, expanded
using one of propane, butane, pentane, methanol, ethanol or propanol
as the blowing agent. The copolyester is the condensation product of
a C2–C12 alkanediol or a C5–C10 cycloalkanediol with a mixture of an
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aliphatic or cycloaliphatic C2–C20 dicarboxylic acid and an aromatic

dicarboxylic acid. The blowing agent is injected into the barrel of
an extruder before the blend is pelletised under water and under
pressure (as in Section 2.6.1) to produce cooled expandable beads
for later expansion and moulding in conventional EPS equipment.
As there are no examples it is not entirely clear which copolyester
is intended, although BASF offers such a product with the trade
name Ecoflex, to be used alone or as a modifier for biodegradable
polymers such as PLA. It is a synthetic polymer, not bio-based,
but is certified as being biodegradable. The claimed compositions
range from 1 part copolyester to 9 parts starch or cellulosic, to the
converse – it is not stated in the text where the optimum composition
(processing as well as service properties) may lie, as this will depend
on the chosen application. Ecoflex is a soft and flexible polymer, so
the properties of blends with TPS or cellulosic polymers depend on
their proportions – more Ecoflex improves toughness and ductility
and, in general, foamability.
A 2006 paper written by a team of collaborators from the University

of Pisa, Italy, and the Agriculture Research Service of the US
Department of Agriculture [43] reports work on making foamed
sheets from a blend of unmodified potato starch, polyvinyl alcohol
(PVOH, a synthetic degradable and water-soluble polymer) and
corn fibres, a waste product from the fermentation of corn (maize)
to make ethanol. These ingredients were mixed together with water
at room temperature to make a batter. This was then injected into a
steel tray mould and baked at 200 °C for two to three minutes. The
batter foamed during the baking to yield plates whose mechanical
properties were measured. The conclusions were that corn fibres did
not improve mechanical properties, but did not interfere with foaming
and improved the water resistance of the foamed material. PVOH also
improved the water resistance and mechanical properties. Clearly this
work was not aimed at making expandable beads, but it does show
the types of starch blends being studied for foaming performance.
A blend system that was aimed towards expandable beads is described

in a paper from the US Agricultural Research Service [44]. The
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formulations of the blends included as plasticisers for the starch,

sorbitol, glycerol, ethylene vinyl alcohol (EVOH) and water, extruded
into pellets or ground into particles. On heating at 190–210 °C for
more than 20 seconds at atmospheric pressure, the beads expanded
to low densities. As the water concentration was raised from 10 to
25%, so the foaming temperature fell by more than 20 °C. All of the
additives except the EVOH acted to reduce the foam density, and
wheat or potato starches gave lower densities than corn starch. There
is no mention of moulding the expanded beads, although it would be
expected to be feasible as for the other systems described here.
4.3.3 End-of-life Aspects of Starch-based Foam Products
As mentioned previously, starch itself is hydrophilic and readily

absorbs water from the air, so its biodegradation by bacterial enzymes
tends to be rapid. This affects the serviceability of starch-based
materials, which can even deteriorate in use, before their packaging
task has been fulfilled. This is naturally undesirable, and shows that
there is always a balance to be struck between degradability and
durability, dependent on the application, and that great care needs
to be taken in material selection and testing before ‘green’ claims
can be made with safety.
In order to obtain more useful properties and greater durability,

many blends have been made with other sustainable polymers, such
as PHA (Section 4.4), cellulose acetates (Section 4.5) and PCL. In
addition to the blends discussed above, starch has also been blended
with oil-based polymers including polyolefins and even expandable
polystyrene [45] in order to reduce their cost and accelerate their
disintegration in the environment (not always with demonstrable
success). If the starch domains are fully encapsulated by a more
hydrophobic polymer, degradation can be significantly delayed [5] as
the enzymes are unable to reach the starch. There was an enthusiasm
for supermarket carrier bags made from starch-filled polyethylene in
the early 1990s, but it was eventually shown that such bags could
remain virtually intact for many years even after burial. Again, any
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product made from a starch blend must be designed and tested to

show that it meets the requirements.
Recycling of starch-based polymers is unlikely to be a preferred

option, not least because of the variety of plasticisers and blend
additions present in the different grades – waste material could be very
mixed in nature and challenging to process. As starch-based materials
are essentially sold for their biodegradability, composting (or burning
for energy recovery) will be the most attractive disposal route.
4.4 Polyhydroxyalkanoates (Including

Polyhydroxybutyrate (PHB) and Copolymers)
4.4.1 Production and Properties of PHA Polymers
PHA polymers are true ‘biopolymers’, as they are synthesised within

the bodies of bacteria grown in special digesters, and subsequently
extracted from the biomass. The polymer can make up to 80% of the
biomass, stored by the bacteria as an energy reserve. These polymers
have been of interest (though sadly not sufficiently to make them
profitable volume materials) for a number of years and ownership
of the technology has changed hands several times since ICI first
marketed Biopol in 1990. One current manufacturer is Metabolix
(as Mirel) which has a 50,000 tonnes per year plant in Iowa, USA,
while other companies are reportedly also investing in PHA capacity
[2]. Cost remains a severe handicap [46], and has to date inhibited
the introduction of these materials into the very cost-sensitive foam
packaging market – Mirel prices were quoted in 2008 [47] at more
than $4.4 per kg, far above the price of oil-derived polymers such
as polystyrene or polyolefins. As for all potential applications of
‘sustainable’ polymers, legislation or customer diktat can change the
economics to some extent, but it appears that unless the production
costs of PHA reduce significantly with increased scale (for other
applications), they are unlikely to become a major player in the
near future.
96
Figure 4.3 Structures of polyhydroxybutyrate (PHB),

polyhydroxyvalerate (PHV) and the copolymer, PHBV
The composition of a PHA copolymer – polyhydroxybutyrate-

co-hydroxyvalerate (see Figure 4.3), with 5–12% of valerate
units randomly incorporated along the chains – is controlled by
manipulation of the ‘food’ (mostly glucose) supplied to the bacteria.
Tg of pure PHB is 5 °C and its melting point is 170–180 °C – the
presence of the hydroxyvalerate (HV) units acts to lower the melting
point, increase impact strength and flexibility and reduce tensile
strength. The copolymers are crystalline, although as the HV content
rises so the rate of crystallisation reduces, and nucleants are routinely
added to accelerate crystallisation during processing. Plasticisers are
also used to improve processability and flexibility.
The properties of PHA vary with the composition, but generally

speaking the more common grades resemble polyolefins – at
mid-range HV contents they are tough like polypropylenes, at
higher levels they are softer and more like polyethylenes. This has
led to applications in packaging such as films and bottles where
their degradability brings added value sufficient to offset their
high cost.
97
4.4.2 Blowing Agents and Processing of PHA Foamable

Beads
Kaneka Corporation, also known as Kanegafuchi, has been active

in the technology of foaming biodegradable polymers, and has
filed two patents in recent years on expandable PHA. In the first
of these [48], solid beads of poly(3-hydroxyalkanoate) (Kaneka’s
patent writers prefer this version of the chemical name for PHA
copolymers) are formed, then suspended in a blowing agent in a
sealed vessel, pressurised and heated to start the expansion. The
blowing agent is preferably dimethyl ether, diethyl ether or methyl
ethyl ether – all have low boiling points and will impregnate the
polymer. Once the beads are sufficiently saturated with ether and
heated to a temperature not far below their melting point, the vessel
is opened and the beads complete their expansion. The patent goes
into much detail about the necessity for controlling the valerate co-
monomer level and having two crystalline melting points, and much
less detail about the way the beads are first produced. Moulding of
the expanded beads into shaped products is discussed without much
detail – they are first prepressurised with air (as in EPP moulding),
then fused with steam.
The second Kaneka patent [49] follows much the same lines, but
additionally claims benefits from the addition of an isocyanate
compounded into the polymer (as a chain extender). A wider range
of blowing agents is also claimed, including isobutane and pentane.
There are no details of the bead-making process, and again the
moulding process is barely discussed. In the given, the temperature in
the impregnation vessel is 120–130 °C, close to the polymer melting
point, and the pressure is held at 2.5 MPa for an hour.
The importance of controlling crystallisation behaviour is emphasised

by a joint 2008 patent application from Kanegafuchi Chemical
(Kaneka) and the Tokyo Institute of Technology [50]. The text of
this patent is in Japanese, but the English abstract reveals that it is
claimed that there is a need to accelerate crystallisation in PHA in
order to improve processability. This applies to all melt processing –
98
injection moulding, blow moulding, fibre spinning, extrusion foam

moulding and bead foam moulding are all quoted – and is achieved
by the use of a sugar alcohol (galactitol) as a nucleating agent.
Differential scanning calorimetry traces shown in the abstract have
melting curves of PHB and PHBV (the valerate used as co-monomer)
with no nucleant, with 2% hexagonal boron nitride and with 2%
galactitol – clear differences are visible, with the galactitol increasing
the size of the melting peaks but also their peak temperature.
4.4.3 End-of-life Aspects of PHA Foam Products
When PHBV articles are exposed to microbially active environments,

enzymes begin to attack the surface of the polymer, eventually
breaking it down into carbon dioxide and water in aerobic
conditions, or carbon dioxide and methane in anaerobic conditions.
In composting conditions it may take a reasonably long time for solid
parts to decompose fully, but foamed material can be expected to
degrade rather more quickly. As with all thermoplastics, PHA are
potentially melt reprocessable, although their heat stability is limited,
and temperatures above 180 °C should be avoided.
4.5 Cellulosic and Other Sustainable Polymers

Cellulose-based polymers were the first commercial thermoplastics,
developed in the middle of the nineteenth century (cellulose acetate,
cellulose acetate butyrate, cellulose nitrate) and still find a range of
applications. They are obtained by acidic digestion of plant-derived
cellulose, followed by further treatments to render the materials
processable and reasonably durable. They tend to be expensive (more
than three times the cost of polystyrene) which severely limits their
market share.
The raw material, cellulose, is a polysaccharide which makes up a

significant proportion of the cell walls of many plants. Cotton fibres
can be as much as 90% (dry weight) cellulose, while wood is closer to
50%. Pure cellulose is believed to be essentially polyanhydroglucose
99
(C6H10O5)n, with linear chains, extensively hydrogen bonded, which

prevents it from being water soluble and gives it the ability to
crystallise (see Figure 4.4).
Cellulose
Figure 4.4 Structure of cellulose (anhydroglucose)
Cellulose acetates are nowadays the most commonly used cellulosic

polymers, produced by the reaction of acetic anhydride on wood or
cotton linters (the short waste fibres remaining after textile-grade
fibres have been removed) to yield materials with a range of degrees
of substitution (DS; acetylation of the anhydroglucose base unit)
typically between 1.7 and 2.5. Pure cellulose has DS = 0 and cellulose
triacetate has DS = 3. In general they have a high crystalline melting
point (around 200 °C) which must be reduced by plasticisation to
improve processing. As the materials are hard, tough and transparent,
they still find reasonably wide application in sheet and film form
for packaging and adhesive tapes, and are also moulded into such
decorative items as combs, toothbrush handles, etc. The rate of
biodegradation depends on DS, faster at lower levels, and at DS =
2.5 the polymers are very slow to degrade, because of the slow rate
of attack by deacetylase and cellulase enzymes [5]. Certainly, few
commercially available cellulosic materials decompose fast enough to
be certified compostable – one objective in their original development
was to prevent rapid deterioration and render them serviceable for
durable products. The reader is referred elsewhere for an example
of a more comprehensive description of the technology of cellulosic
polymers [1].
100
An early Japanese patent to Teijin Ltd [51] describes a method of

producing a biodegradable foam moulding using expanded cellulose
acetate. Foamed beads are made by extruding a mixture of cellulose
acetate and water through a fine-hole die at temperatures above 120
°C, then cutting the strand to form beads which expand immediately.
These beads are then coated with 3–50 wt% of a low melting point
(around 60 °C), biodegradable polymer, PCL, and the beads fused by
heating them in a mould. This is a similar approach to that which can
be taken with other polymers that are difficult to fuse once expanded
(see Sections 2.6.4 and 3.4), but does add to the cost and density of
the moulded product.
The BASF patent [42] discussed in Section 4.3.2 also claims the
use, in expandable beads, of cellulosic polymers in a blend with a
biodegradable copolyester. This does not fully meet the need for
sustainability, as the copolyester is a synthetic polymer derived from
oil, and even if the product is practicable and economic, it may not
be easily accepted if full sustainability is mandated by governments
or customers.
A wide-ranging presentation [52] was made by workers from the

Fraunhofer Institute for Chemical Technology at a symposium in
2006, hosted by Gala GmbH, makers of underwater pelletising
systems. Part of their paper described a project, supported by the
state government of Baden-Württemburg, on foamable biodegradable
materials. Successfully mouldable (fusible) foamed beads were
produced from cellulose acetate using pentane as blowing agent – less
success was met with PLA, as the foam nucleation was poor and the
beads expanded with just one (large) cell in each. This demonstration
study was not intended to develop commercial products, and it
appears that the high cost of the cellulosic base material is likely to
discourage any industrial development at present. The biodegradation
of cellulosics tends to be very slow, unless the polymer has been
‘primed’ using a plasticiser which also promotes degradation –
compounds such as Bioceta (currently produced by Mazzucchelli
1849 SpA) can meet compostability standards.
101
Although there are a variety of other bio-based or biodegradable

polymers now available, such as the PCL mentioned previously
and PVOH (a synthetic but degradable polymer), there has been
little interest in using them in foamable beads. Cost (principally),
processability and control of their degradation behaviour have tended
to inhibit their exploitation. As mouldable particle foams come a long
way down the hierarchy of applications to be explored when new
polymeric materials are introduced, it is unlikely that such materials
will appear as foamable beads in the near future.
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106
5
Concluding Remarks – What
Forces Will Drive Development in
this Field?
It is always very dangerous to attempt prediction, certainly in any

detail – as the history of the plastics industry shows, the unexpected
should be expected at every turn. The course of recent events has
only confirmed that volatility is increasing, and companies involved in
the mouldable particle foam industry will need courage to plan their
strategies through the coming years and make the most profitable
investments in future capacity. There are, however, some general
principles which will influence the way in which this industry (and the
wider plastics industry) is able to develop and compete in the future.
It must be borne in mind that moulded foam products are only one
approach to the requirements for protective packaging, insulation,
etc. – alternative technologies may be able to take advantage of
developments to displace existing applications of moulded foams,
or new opportunities may arise. This chapter has no references as
there is such a wide variety of forward-looking material available,
with very many different starting points, scenarios and messages – I
leave it to the reader to review as many as possible, choose those
which appear most credible and then to try to make the best decisions
about the future.
The critical factors that are likely to influence foamable bead

producers and processors are largely the same as they have
always been, although the balance between them is likely to
continue to change with events. Important drivers are the costs
of raw materials, investment in production capability, transport
of products to customers and disposal of products at the end of
their service life – but the most important will be the performance
of these products when compared in cost-effectiveness with the
107
alternatives. For example, if the price of crude oil rises sharply

and remains high, biomass-derived sustainable polymers should,
although not unaffected by the higher costs of energy for processing
and transport, become more competitive even in the absence of
legislation driving their adoption. If brominated fire retardants are
proscribed, much of the construction insulation market may be lost
to expandable polystyrene (EPS) unless acceptable alternatives can
be found which are not excessively costly. Unless customers continue
to select particle foams as their preferred solutions for packaging,
protection, insulation and so on, the industry will wither away,
however its technology develops.
The most likely driver of change over the medium term will be the
increase in the price of crude oil as production peaks and begins to
decline, although it is almost inevitable that political and economic
instabilities will impose strong fluctuations on the rate of that
increase. Those instabilities and fluctuations will also have an impact
on the investment decisions made by the companies active in this
industry – some will be bold and perhaps lose their shirts, some
will be more cautious and maybe miss golden opportunities. It is,
however, possible to see where technological development effort could
be most usefully directed to give the industry the best options to face
the coming challenges (not forgetting that some of these challenges
will be new and unexpected).
The EPS industry faces the likelihood of increasing raw material and
energy costs, increased restrictions on its emissions and increasing
costs for transport both of its products and of the products for which
EPS is used as packaging. It is therefore likely that development which
enables further reduction of foam density (and therefore product
weight), while retaining or improving performance, will be fruitful, as
will reduction of volatile organic compounds (VOC) emissions during
manufacture and processing of EPS. Lower densities will of course
have an impact on the costs of recovery and recycling, activities which
may increasingly be mandatory. As alluded to above, fire performance
may become a critical issue for the insulation market – perhaps the
Xire technology (see Section 2.2) or something comparable to it will
108
Concluding Remarks – What Forces Will Drive
Development in This Field?
enable growth in a different direction, or a different solution will be

found to the challenge of flame retardation.
The polyolefin particle foams, EPE and expanded polypropylene

(EPP), are likely to continue to find new markets into which to grow,
where their cushioning and durability can be exploited. Increasing
transport costs for expanded beads (or if the beads are moulded
in fewer locations, the transport to the customer) could drive
development of small-scale impregnation and expansion equipment,
so that relatively dense beads can be transported to a site close to the
end-user, then expanded and moulded as needed. It is even possible
that, as this technology seems likely to be needed for the processing
of polylactic acid (PLA) beads (the front-running sustainable foam
material), there will be some useful spin-off back to the polyolefin
foam processors.
The ‘sustainable’ polymers present a very interesting prospect, but,

as their history shows, there can be unexpected turns in the road. In
the late 1990s, biodegradability was seen as a ‘unique selling point’
which would solve the perceived end-of-life issues for foam packaging
products and enable biodegradable polymer foams to gain a market
foothold from which to grow. As the trend away from the ‘throwaway
society’ mentality has led to the establishment of better collection
and recycling infrastructure for waste packaging, so the emphasis has
shifted to a focus on raw material sources and their sustainability –
renewability is the new unique selling point for these polymers. At
present PLA polymers, alone or in combination with other polymers,
appear to be leading the field, largely based on their relatively low
cost and the wide variety of biomass that can be used to produce
them. This situation may change – there is active research going on
into all kinds of materials formerly considered ‘exotic’, oriented
around the availability of biomass which is not in competition with
food uses. Some feel that as the world’s population continues to
grow, anything edible is more likely to be eaten rather than turned
into polymers. Cellulose is an extremely common plant material,
but not so far exploited to the full – perhaps new methods can be
developed to process it to useful products. Whichever foam system
109
using sustainable polymers is adopted, its process technology will be

different from that of EPS, and can be expected to drive innovations
which will open up new opportunities and ways of organising the
industry to meet customers’ needs.
The future will, therefore, present the particle foam technologist with
new challenges and opportunities. These may be similar to those
which have already been addressed, and for which the solutions have
been described in this update, or they may be completely new. Of one
thing we can be certain, there will always be a drive to fulfil existing
needs in a cheaper and ‘smarter’ fashion, and to meet new needs as
quickly and efficiently as possible. Without such progress, the industry
will be left behind and wither away, so there will continue to be ample
scope for the technologist who can invent, adapt and improve.
110
A
bbreviations for Mouldable
Particle Foam
A-PET Amorphous polyethylene terephthalate

ASTM American Society for Testing and Materials
ATO Agrotechnological Research Institute
CFC Chlorofluorocarbon(s)
CO2 Carbon dioxide
DIN Deutsches Institut für Normung (German Institute for
Standardisation)
DMPP Dimethylphenylphosphonate
DOPP 9,10-Dihydro-9-oxa-10-phosphaphenanthrene 10-
oxide
DS Degree of substitution
EBS Ethylene-bis-stearamide
EPE Expanded polyethylene
EPO Expanded polyolefin
EPP Expanded polypropylene
EPS Expandable polystyrene
EVA Ethylene-vinyl acetate
EVOH Ethylene vinyl alcohol copolymer
HBCD Hexabromocyclododecane
HCFC Hydrochlorofluorocarbon(s)
HMS High melt strength
HV Hydroxyvalerate
ISO International Standards Organisation
JSP Japan Styrene Paper
111
LCA Life cycle analysis

LDPE Low-density polyethylene
LLDPE Linear low-density polyethylene
NAFTA North American Free Trade Agreement
P(DL)LA Poly (D,L) lactic acid
PAT Pressure and temperature
PBS Polybutylene succinate
PCL Polycaprolactone
PDLA Poly (D) lactic acid
PEPP Porous expanded polypropylene
PET Polyethylene terephthalate
PHA Polyhydroxyalkanoates
PHB Polyhydroxybutyrate
PHBV Polyhydroxybutyrate-valerate
PHV Polyhydroxyvalerate
PLA Polylactic acid
PLLA Poly (L) lactic acid
PPE Polyphenylene ether
PPO Polyphenylene oxide
PVOH Polyvinyl alcohol
RDP Resorcinol diphosphate
REACH Registration, Evaluation, Authorisation and Restriction
of Chemicals
SMA Styrene-maleic anhydride
Tg Glass transition temperature
TPP Triphenyl phosphate
TPS Thermoplastic starch
TPY Tonnes Per Year
VOC Volatile organic compounds
WEPS Water-expandable polystyrene
XPS Extruded polystyrene (foam)
112
A
uthor Index
A
Abe, T 43
Ajioka, M 103
Allen, R B 49
Allmendinger, M 42, 45, 47, 48, 49
Andreas, W 49
Angelopoulou, A G 104
Anlas, G 67
Aoyama, T 106
Araya, A 43
Arduini-Schuster, M 44
Aw, H D 50
Aw, H S 50
B
Barry, R P 47
Bastioli, C 103
Batscheider, K-H 44
Berghmans, H 48
Berghmans, M 43, 48, 67
Berrios, J 105
Biglione, G 49
Bleijenberg, K 43, 48
Bleijenberg, K C 48, 67
Boukami, S 42
Braun, F 43, 44, 105
Brydson, J A 102
Buijk, C M G 43
113
C
Cai, Z 48
Carlier, C 47
Casalini, A 45, 46, 49
Champagne, M F 48
Chaudhary, B I 47
Chen, L 66
Chen, N 65
Chiellini, E 105
Chiou, B-S 105
Chiou, N-R 48
Choi, J B 66
Chung, M J 66
Cigna, G 49
Cinelli, P 105
Cink, K 103
Cronin, D 67
Culkova, A 47
D
Daniel, T 48
Datko, A 45, 49
Daum, M 46
Day, M 104
de Grave, I 66
de Mink, P 65
de Swart, H J 43
Dehnert, P 47
Delaviz, Y 48
Der Hovanesian, M 105
Dietzen, F-J 42, 43, 45, 47, 48, 49, 66
Douay, D 47
Duan, S 66
114
Author Index
E
Eaves, D 5, 41, 50, 65, 66
Eberstellar, R 44
Ehrmann, G 42, 45, 47, 48, 49, 66
Enamoto, K 103
Erbay, E 46
Ezdesir, A 46
F
Favis, B D 103
Feil, H 105
Felisari, R 45, 46
Fiordelisi, F 103
Fischer, J 43, 44
Folland, R 65, 66
Ford, T M 103
Francis, T 43, 46
Frigiero, G 45
Fuminobu, H 106
G
Gaeth, R 65
Galewski, J-M 47
Gan, J 43
Gendron, R 48
Ghidoni, D 45, 46
Gilchrist, A 67
Gilead, D 105
Glenn, G M 105
Glenz, W 5
Gluck, G 42, 43, 44, 48, 105
Gougeon, B 41
Grave, D de 66
Green, J R 49
Guo, Z 48
Gupta, A P 103
115
H
Hahn, K 42, 43, 44, 45, 47, 48, 49, 66
Hall, T 66
Haraguchi, K 104
Harclerode, W H 47
Hayashi, T 47
Henn, R 43, 44
Hesse, A 65
Hirokado, N 104
Hirosawa, K 65
Hirose, K 106
Hiroshi, N 103
Hiroyuki, M 106
Hohwiller, F 43, 44
Holoch, J 45, 47, 48, 49
Holtman, K M 105
Hood, L S 47
Hu, X 104
Huang, Z 105
Huneault, M A 103
Husemann, W 44
I
Imam, S H 105
Inoue, Y 106
Irving, D W 105
Isao, K 46
J
Jager, J 45
Jönsson, L 49
Jung, D C 47
K
Kabamba, E T 66
Kaempfer, K 44
116
Author Index
Kannah, K 47
Katsunori, N 104
Keisuke, O 105
Keitaro, S 105
Keller, A 43
Kelusky, E C 46
Kemperman, W P T 43
Keppeler, V 66
Keulen, G 43
Kim, M C 47
Kim, S G 48
Kim, S R 47
King, B 43
Kitahara, Y 103
Klamczynski, A K 105
Klement, E 5
Klempner, D 65
Klodt, R-D 41
Knutsen, J C 47
Kono, K 47
Kovarik, J 47
Krist, J 66
Krupinski, S M 47
Kuhn, J 44
Kumar, V 103
Kurcharikova, I 47
L
Lamprecht, J 43, 44
Landa, A 43
Lanfredi, R 45
Lanzani, F 103
Laun, M 45, 49
Lauzon, M 102
Lawton, J W 105
Lee, E K 48, 65
Lee, K-M 48
117
Lee, L J 48
Lee, S G 50
Lemstra, P 48
Leung, S N 49
Levchik, S V 41
Li, H 103
Li, K 66
Lia, X 104
Liu, T 66
Liu, Y 105
Lopez, P 46
Lu, M 66
Lu, Y 66
Lye, S W 50
M
Makoto, Y 106
Maletzko, C 66
Masamichi, K 46
Mat, J Z 47
Matsumoto, T 104
Matsuoka, F 104
Metsaars, A C G 67
Michimiro, H 104
Mihai, M 103
Mills, N J 67
Miyagawa, T 106
Moore, G F102
Moreira, A 46
Movilli, W 103
Mronga, N 44
Muhlbach, K 49
Munakata, Y 65
N
Naegele, D 43, 44
Naguib, H E 48, 65, 104
118
Author Index
Naioki, N 105
Nakai, S 67
Namikawa, H 47
Nangeroni, J 103
Nawaby, A V 104
Nehls, B 43
Nelissen, L 48
Noordegraaf, J 43, 45
O
Ohara, H 47
Ohshima, M 67
Ohta, H 104
Oogi, Y 104
Orts, W J 105
Ouellet, S 67
Ozturk, U E 67
P
Pallay, J 48
Panayiotou, C 104
Panzer, U 65
Paquet, A N 41
Park, C B 48, 49, 65, 66
Pavlicek, J 47
Pekich, B J 47
Pinkert, R 47
Pirgov, W 66
Platt, D K 105
Polasky, M E 48
Ponticiello, A 45, 46
Priddy, D B 41
R
Randall, J R 103
Rathbun, M 43
119
Rego, J M 43
Reichelt, N 65
Reiger, J 46
Rensen, P F M 43
Riethues, M 5, 43, 49
Rinaldi, R 49
Rodrigue, D 66
Roesch, J 44
Ruch, J 42, 45, 47, 48, 49
S
Sandler, J 43
Sands, M 50
Sanford, F L 49
Sasaki, H 104
Saunders, S M 102
Schellenberg, J 47
Schennink, G G J 105
Scherzer, D 42, 43, 44
Schiers, J 41
Schmeid, B 42, 43, 45, 47, 48, 49
Schouren, P W M 43
Schueneman, H H 46
Schuler, P 46
Schut, J 103
Schut, J H 49, 67
Scott, G 105
Sei, Y 103
Senda, K 65, 106
Sendijarevic, V 65
Sengupta, P 66
Shah, S 104
Shao, J 66
Shey, J 105
Shi, X 105
Shimida, S 65
Shinichi, F 104
120
Author Index
Shinko, Y 103
Shinohara, M 104
Shiv Kumar, S 50
Simonelli, A 45, 46
Smeets, E P W 43
Smith, J C 103
Snijders, E 48
Song, G I 47
Sopher, S R 65
Spinu, M 103
Stadlbauer, M 65, 66
Statsny, F 65
Sterzel, H-J 103
Suh, K W 41
Sunal, G 46
Suzuki, K 103
T
Takaaki, H 104
Takayoshi, K 103
Taki, K 66, 67
Taskiran, I 46
Tetsuo, K 104
Tetsuya, O 104
Teubert, J 48, 67
Tokiwa, T 104
Toshiyuki, I 104
Treischmann, G 65
Trivedi, Y 66
Trn, N J 47
Troitzsch, J 42
Tsujimura, I 67
Tsunahiro, N 103
Tzivintzelis, I 104
121
U
Ueda, K 104
Uyanik, N 46
V
Van Leuven, R A H 105
Vannini, C 103
Vink, D 103
Vo, C V 42
Volz, W E 47
Voss, J C 47
W
Wagner, F 45
Walter, B 106
Wang, J 66
Wang, X 66
Warzelhan, V 43
Wassmer, K-H 43, 44
Wassner, E 43, 46
Watanabe, T 103
Weil, E D 41
Wiman, J V 47
Witt, M R J 104
Wong, A 49
Wood, D 105
Worswick, M 67
X
Xu, F 105
Xu, J X 65
Y
Yamaguchi, A 103
Yang, J 48
122
Author Index
Yeh, S-K 48
Yin, H 66
Yoon, J S 66
Yoshihito, Y 104
Youngson, C G 43
Yu, S 105
Yukikage, M 106
Z
Zach, J 47
Zamperlin, L 45
Zavodska, V 47
Zhang, H 66
Zhang, L 66
Zhang, S 66
Zhang, W 66
Zhang, X 65
Zhu, Z 65
123
124
S
ubject Index
A
Ageing 9, 62
Agglomeration 7
Amylopectin, structure of 92
Amylose, structure of 92
Antistatic mouldings 88
B
Bead foam moulding 99
Bead-making process 36, 98
Biodegradability 71
Blow moulding 88, 99
Blowing agents 31
C
Cellulose 109
Cellulosic polymers 99, 100, 101
Chlorofluorocarbons 11
Coating, hydrophobicising 18
Copolymerisation 22, 58
Crystallisation 61, 78, 83, 84, 85, 97, 98
Cold 84
Cushioning performance 23, 24
D
Dewatering 7
Differential scanning calorimetry 61, 99
125
Dimethylphenylphosphonate 13
Dihydro-oxa-phosphaphenanthrene oxide 14, 15
E
Ethylene vinyl alcohol 95
Ethylene-bis-stearamide wax 78
Ethylene-vinyl acetate 55
Expanded polyethylene 55, 64, 109
Mouldable beads 53
Expanded polyolefin 62, 63, 65, 74
Bead products 62
Moulded foams 51
Expanded polypropylene 52, 55, 56, 61, 63, 80, 98, 109
Expanded polystyrene 2-4, 7, 10-17, 19, 21, 23, 25-28, 31, 32,
38, 40, 52, 54, 55, 59, 60, 62, 64, 65, 69, 74, 86, 90, 93, 94,
108, 110
Beads 7, 23, 36
Blowing agents 27
Industry 28, 60, 108
Low-pentane developments 28
Moulding 38, 39
Packaging 23
Unexpanded beads 7
Extruded foamed sheet 15, 34
Extruded polystyrene process 35, 36
Extrusion 8, 13, 17-21, 31, 37, 51, 58, 99
F
Fibre spinning 99
Fire retardation 12
Foam moulding 9, 101
Foam nucleation 38
Foam products 10
Foaming 1, 31
Assisting agent 29
In-mould 89
126
Subject Index
G
Gas impregnation process 87
Gelatinising 91
Ground stabilisation 1
H
Hexabromocyclododecane 11, 13, 14, 17
High melt strength 56
Hydrochlorofluorocarbon 11, 53
Hydrolysis 76, 90
Hygroscopic 91
I
Impregnation 34, 59, 84, 85, 86, 98
Injection moulding 9, 26, 88, 99
J
Japan Styrene Paper Process 53
K
Knudsen Effect 20
L
Life cycle analysis 69
Linear low-density polyethylene 55
Lost wax process 3
Low-density polyethylene 55, 58
M
Macroinitiator 23
Melt process 72, 98
Melt rheology 52
Metal casting 3
Micropelletisation 31, 37, 60
Mouldable bead foams 3
127
Mouldable particle foam industry 1, 107

Moulded expandable foams 3
Moulded polylactic acid foam packaging 79
Moulding 9, 22, 26-28, 30, 32, 33, 34, 40, 53, 59, 62, 74, 75, 79,
83, 84, 86, 87, 89, 94, 95, 98,
O
Olefinic oligomer 19
Olefinic polymer 26
P
Particle foam industry 1
Pelletiser 36, 60
Polylactic acid 76, 81, 83
Recycling 90
Plasticisation 29, 30, 32, 34, 83
Plasticisers 80
Plastics foam industry 1
Plastics packaging 69
Plastics processing 9
Polybutylene succinate 80
Polycaprolactone 80, 102
Polydimethylsiloxane prepolymer 22, 23
Polyethylene bead foam processes 53
Polyethylene terephthalate 76
Amorphous 77
Polyhydroxyalkanoates 70, 96
Polyhydroxybutyrate 97
Polyhydroxybutyrate-co-hydroxyvalerate 97
Polyhydroxyvalerate 97
Polylactic acid 70, 109
Polymeric matrix 20
Polymers, sustainable 96, 109
Polymerisation 7, 8, 10, 18, 21, 25, 27, 31, 33, 36, 37, 76
Suspension 7, 8, 18, 19, 31, 35, 36, 37
128
Subject Index
Polyolefins 20, 25, 27, 51, 53-57, 59, 97

Foams 3, 55
Moulded foams 51
Particle foams 109
Polymers 51
Wax 30, 38
Polystyrene 10-12, 20-22, 25, 28, 30-33, 35, 36, 51-53, 55, 56,
70, 73, 82
Water-expandable 33
Polyvinyl alcohol 102
Prefoaming 9
Prepuff 62
Beads 9
R
Recycling 40, 69, 71, 96
Resorcinol 14
Resorcinol diphosphate 15
S
Self-nucleation 61
Sheet extrusion foaming 57, 81
Styrene-maleic anhydride 23
T
Thermal insulation 1
Thermoforming 56
Thermoplastic polymers 1
Thermoplastic starch 81, 90
Triphenyl phosphate 13, 14
V
Volatile organic compounds 27, 28, 108
129
W
Waste packaging 109
Z
Ziegler-natta catalysts 57
130
Published by iSmithers, 2009
Moulded particle (bead) foam products are ubiquitous, in packaging and

construction, from drinking cups to motorway foundations. The industry
which started with expanded polystyrene (EPS) has grown spectacularly and
now also includes expanded polypropylene and expanded polyethylene, and
its technology and machinery has become so specialised that it is seen as an
almost isolated branch of the plastics industry.
This update summarises the present status of particle foam technology and
how specific challenges have already driven its development. This includes
the potential threats to the fire retardants and blowing agents which have
been used for many years.
The potential for particle foams made from ‘renewable’ polymers such as
starch, polylactic acid, polyhydroxyalkanoates and cellulosics is also covered.
For each of these, existing technology is reviewed, together with the issues
for research and development.
This update is written by a plastics technologist who works in the EPS

industry. It will be of interest to both relative newcomers and those who
already have long experience but wish to know more technical detail about a
fascinating branch of plastics technology.
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK

Telephone: +44 (0)1939 250383
Fax: +44 (0)1939 251118
Web: www.rapra.net

Update On Mouldable Particle Foam Technology

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Update On Mouldable Particle Foam Technology

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Update on Mouldable

Particle Foam Technology

Smithers Rapra Update

iSmithers – A Smithers Group Company

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

©2009, Smithers Rapra

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

Typeset by Argil Services

2. Expandable Polystyrene (EPS) – A Mature Technology? ....... 7

3. Expanded Polyoleﬁn Moulded Foams (EPE and EPP) –

3.1 Key Features of Polyoleﬁn Moulded Foams,

4. ‘Sustainable’ Polymers – The Future? ................................. 69

4.4.2 Blowing Agents and Processing of PHA

5. Concluding Remarks – What Forces Will Drive

Abbreviations ........................................................................... 111

Author Index............................................................................ 113

Subject Index............................................................................ 125

This Update attempts to place the technology in context, beginning

knowledge and one I had never expected to understand. I must

Particle foams form a signiﬁcant part of the plastics foam industry,

The term ‘mouldable particle foams’ describes an industry which

The foaming of thermoplastics, particularly polystyrene, has been

were later developed for making sheets of foamed polystyrene, and,

Although the technology of EPS manufacture and moulding can

Other polymers have also been produced as mouldable beads,

in foam products which degrade quickly in the environment, should

The main applications of moulded expandable foams are in protective

The construction industry uses a great deal of EPS insulation within

Other applications exploit the water resistance and low density of

The applications of mouldable bead foams are therefore many and

course of addressing the issues that are currently driving development,

I have mostly drawn on ‘hard copy’ publications such as journal

guarantee that the product or process has been commercialised, or

2. D. Eaves, Polymer Foams, Trends in Use and Technology,

3. W. Glenz, Kunststoffe, 2007, 10, 82.

4. M. Riethues and E. Klement, Kunststoffe, 2005, 10, 74.

5. E. Klement, Kunststoffe, 2004, 10, 80.

2.1 Brief Description of the Product and Processes

Unexpanded EPS beads are typically 0.1–2 mm in size, and the

More recently, extrusion processes have been developed which yield

The pre-expansion process involves using steam to heat and agitate

pressure, or shorter steaming time), but ultimately result in a

The machinery used for processing of EPS has developed to match

• Polymerisation can be carried out economically in relatively

• The blowing agent is well retained inside the beads at ambient

• Steam at relatively low pressures is an ideal medium for expanding

• Polystyrene is a stiff glassy polymer at ambient temperatures,

• EPS is easily and widely recycled. Foam products may be

• The blowing agents used are mostly ﬂammable organic solvents,

• Because polystyrene is a glassy polymer, EPS has quite poor ductility

These strengths and weaknesses will be explored further as we

2.2 Developments in (Non-Halogen) Fire Retardation

There is a wide variety of tests used to assess the ﬁre performance

tests is different from the others to some extent, and correlation of

As with solid polystyrene compounds, the ﬁre retardants most

diphosphate (RDP), TPP, DMPP, etc., with polyphenylene oxide

Kanegafuchi Chemical Industries (also known as Kaneka Corporation)

ﬁre-resistant and retain their integrity in a ﬁre situation, rather than

2.3 Developments in Insulation Performance of EPS

The transfer of heat through a panel of foamed EPS is usually

density shows a minimum around 25–30 kg/m3. As it is economically

A number of additives have been found to improve L, by increasing