Guidance on the Process

for Selecting Alternatives

to HCFCs in Foams

Sourcebook on technology options for

safeguarding the ozone layer and the
global climate system
phase-out of hcfs in the flexible and rigid foam sector
 Guidance on the Process for Selecting Alternatives
to HCFCs in Foams
Sourcebook on technology options for Safeguarding the
Ozone Layer and the Global Climate System

Prepared by:

Caleb Management Services Ltd

The Old Dairy, Woodend Farm

Cromhall, Wotton-Under-Edge

Gloucestershire, GL12 8AA

United Kingdom

July 2010

Copyright © United Nations Environment Programme, 2010

This publication may be reproduced in whole or in part and in any form for educational or non-profit
purposes without special permission from the copyright holder, provided acknowledgement of the source
is made. UNEP would appreciate receiving a copy of any publication that uses this publication as a
source.

No use of this publication may be made for resale or for any other commercial purpose whatsoever
without prior permission in writing from the United Nations Environment Programme.

Disclaimer

The designations employed and the presentation of the material in this publication do not imply the
expression of any opinion whatsoever on the part of the United Nations Environment Programme
concerning the legal status of any country, territory, city or area or of its authorities, or concerning
delimitation of its frontiers or boundaries. Moreover, the views expressed do not necessarily represent
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UNEP Job number: DTI/1281/PA

2

I ACKNOWLEDGEMENTS
This publication was produced by the
UNEP Division of Technology, Industry and
Economics (DTIE) OzonAction Branch as
part of UNEP’s work programme as an
Implementing Agency of the Multilateral
Fund for the Implementation of the Montreal
Protocol.
The project was managed by the following
team in the OzonAction Branch, UNEP
DTIE, France:
Mr. Rajendra Shende, Head
Mr. James S. Curlin, Interim Network and
Policy Manager
Mr. Ruperto De Jesus, Programme Assistant
This publication was written by:
Mr. Paul Ashford, Managing Director, Caleb
Management Services Limited
Prof. Miguel Quintero, Consultant
with support from
Dr. Jason Yapp, Senior Consultant, Caleb
Management Services Limited
Ms Hookyung Kim, Project Officer, Caleb
Management Services Limited
The quality reviewers were:
Dr. Mike Jeffs, Consultant
Mr. Bert Veenendaal, Principal, RAPPA Inc.
Mr. Bob Russell, President, RJR Consulting
Other reviewers were:
Dr. Ezra Clark, Programme Officer, OzonAction
Branch, UNEP DTIE, France
Mr. Etienne Gonin Project Coordinating
Consultant, EC JumpStart Project, OzonAction
Branch, UNEP DTIE, France
Dr. Janusz Kozakiewicz, Associate Professor,
Head of Ozone Layer and Climate Protection
Unit, ICRI, Poland
Design:
Mr. Andrew Laver, Creative Director, UK Design
UNEP DTIE Foam Sourcebook - 2010
II GLOSSARY Ridge National Laboratory
ABS – Acrylonitrile-butadiene-styrene PFC – Perfluorocarbon
CAR – Climate Action Reserve PIR – Polyisocyanurate
PU OCF – Polyurethane One Component
CDM – Clean Development Mechanism
Foam
CEIT – Countries with Economies in Transition
PUR – Rigid Polyurethane
CFC – Chlorofluorcarbons
RAC – Refrigeration and Air Conditioning
CHP – Combined Heat and Power
s-HFCs – Saturated HFCs
COC – Polyether(C-O-C stretch)
SME – Small Medium Enterprises
COOC – Polyester(C-O-O-C stretch)
SNAP – Significant New Alternatives Program
DME – Dimethyl Ether
SROC – Special Report on Ozone and Climate
Executive Committee – Executive Committee
(IPCC/TEAP, 2005)
of the Multilateral Fund of the Montreal
Protocol TDI – Toluene diisocyanate
FTOC – The UNEP Foams Technical Options TEWI – Total Equivalent Warming Impact
Committee TLV – Threshold Limit Value
FUA – The functional unit approach u-HFCs – Unsaturated HFCs
GEF – The Global Environment Fund VCM – The Voluntary Carbon Market
GWP – Global Warming Potential VCS – The Voluntary Carbon Standard
HC – Hydrocarbons VOC – Volatile Organic Compounds
HCFCs – Hydrochlorofluorocarbons XPS – Extruded polystyrene foams
HFC – Hydrofluorocarbons
HFO – Hydrofluoroolefin – an alternative name
for unsaturated HFCs
HIPS – High Impact Polystyrene
HPMP – HCFC Phase-out Management Plan
IOC – Incremental Operating Costs
IPCC/TEAP – Intergovernmental Panel
on Climate Change, the Technology and
Economic Assessment Panel
ISF – Integral skin foam
ISO – International Standards Organisation
ITH – the Integrated Time Horizon
LCA – Lifecycle Assessment
LCCP – Lifecycle Climate Performance
LVC – Low volume ODS consuming country
MCII – The Climate Indicator under
development at the MLF secretariat
MDI – Methylene Di-phenyl Di-isocyanate
MF – Methyl Formate
MLF –United Nations Multilateral Fund for the
Implementation of the Montreal Protocol
NCO – Polymers containing isocyanate groups
ODP – Ozone Depletion Potential
ODS – Ozone Depleting Substances
OEL – An occupational exposure level
OH – Hydroxyl
World Bank/OORG – The World Bank’s Ozone
Operations Resource Group
ORNL – the US Department of Energy’s Oak
3
III Why this sourcebook is important
At the Meeting of the Parties that fittingly took
place in Montreal in October 2007 to celebrate
the establishment of the Montreal Protocol
on Substances that Deplete the Ozone Layer
20 years earlier, the Parties entered into an
agreement which has taken the Protocol
community into a new phase of activity.
Noting that the projected on-going use of
hydrochlorofluorocarbons (HCFCs) was likely
to place additional and avoidable ozone
and climate burdens on the atmosphere,
the Parties, in Decision XIX/6 (see full text
in Annex 10-3), created a framework within
which the phase-out of use of HCFCs could be
accelerated over and above the 2016 freeze
and final phase-out in 2040 originally foreseen
within the Beijing Amendment. The new steps
introduced as a result of the Decision imposed
an earlier freeze, together with a step-wise
country-level reduction in the intervening years
leading to a phase-out of HCFC use in most
applications by 2030.
For many, the step was clearly necessary
in view of the rapid growth in consumption
of HCFCs in developing (Article 5) countries
as existing HCFC uses continued to grow
in importance (e.g. commercial refrigeration)
and chlorofluorocarbon (CFC) phase-out
requirements necessitated the selection of
interim HCFC-based technologies, often on
economic grounds.
4
In practice, the Decision has created a
number of precedents, perhaps the most
important of which is the fact that Decision
XIX/6 is the first under the Montreal Protocol
to explicitly address climate concerns in its
framework. Although it does not mandate
technology choices that are optimal from a
climate perspective, the Decision identifies and
allocates the responsibilities for consideration
of the climate component of technology
selection. In doing so, it also requires the
development of appropriate methods for
assessing climate impacts, not only at product
level but also at enterprise level, since the
Montreal Protocol continues to provide its
technology transition support to the enterprise
itself or to the government agencies managing
national transitions.
With the ozone obligations from Decision XIX/6
mandated, and the climate components (as
well as other environmental effects) requiring
assessment and prioritisation, there is now a
more complex set of criteria to be managed
than has ever been the case before. It is
not always the case that what is the best
for ozone is best for climate and therefore
value judgements need to be made, not
only at enterprise level, but also at national
compliance level. The introduction of HCFC
Phase-out Management Plans (HPMPs) by the
Executive Committee of the Multilateral Fund
for the implementation of the Montreal Protocol
(Executive Committee) aims at ensuring that
the overall objectives of Decision XIX/6 are
achieved. However, to be fully effective, these
need to straddle the whole phase-out period
from 2010 to 2030. This is not possible, at
the enterprise level and much of the high-level
planning needs to be completed at sectoral
level, at the very least. A list of possible
legislative and policy options that may facilitate
HCFC phase out is included in the booklet
published recently by UNEP that can be found
at
http://www.unep.fr/ozonaction/topics/hcfc.asp
The two main sectors using substantial
quantities of HCFCs currently are the
refrigeration and air conditioning (RAC) sector
on the one hand and the foam sector on the
other (see pie chart). The current HCFC usage
patterns themselves are only part of the story,
since these will change with time depending
on the availability of alternative technologies. In
addition, factors such as the emission profiles
through the lifecycle of the products and
equipment using HCFCs affect overall climate
impact and all vary considerably between
sectors. As a consequence, all of these factors
need to be considered in parallel in order to
build up the full climate picture (see Section
3). In practice, however, both consumption
and emissions from the RAC sector are likely
to dominate the consumption and emissions
patterns for the foreseeable future.
Even though the RAC sector will remain the
primary focus for major climate benefits,
the foam sector is still a critical part of
 UNEP DTIE Foam Sourcebook - 2010

most HPMPs, since these are driven by

consumption criteria only. Accordingly, this
Sourcebook provides guidance to the foam
sector itself, and those operating both in it
and with it, regarding the factors to be
considered when choosing alternative
technologies within the framework of Decision
XIX/6. The guidance also gives consideration
to methods of quantifying and potentially
financing climate benefits, although notes
that not all alternative technologies are, by
definition, favourable to climate.

This Sourcebook builds on earlier technology

and policy materials, developed by UNEP
OzonAction to assist the foam industry in
Article 5 countries to phase out CFCs, and
seeks to continue and further develop that
same capacity-building and information
sharing service.

Estimated Consumption of HCFCs in Developing Countries in 2010

(~445,000 tonnes)

Foams 21% Other 2%

Refrigeration and
AC 77%

Source: IPCC/UNEP data

5
Contents

6
 UNEP DTIE Foam Sourcebook - 2010

I ACKNOWLEDGEMENTS 3 6 DECISION-MAKING PROCESS 48

II Glossary 3 6.1 ESTABLISHING TECHNICAL FEASIBILITY
& ECONOMIC VIABILITY 49
III WHY THIS SOURCEBOOK IS IMPORTANT 4
6.2 EVALUATING SAFETY ASPECTS &
1 INTRODUCTION 8
ENVIRONMENTAL IMPACT 50
1.1 T
 HE CHALLENGE OF ACCELERATED HCFC
6.3 ASSESSING COST EFFECTIVENESS
PHASE-OUT 9
AND PRACTICALITY 51
1.2 G
 UIDANCE ON THE USE OF THIS
6.4 SUMMARY DECISION TREE 51
SOURCEBOOK 10

2 THE INTERFACE BETWEEN OZONE 7 REVIEW OF SPECIFIC FACTORS INFLUENCING THE

DEPLETION & CLIMATE CHANGE 12
2.1 M
 EASURING IMPACTS – ODP, GWP AND
CARBON INTENSITY 13
SELECTION OF ALTERNATIVE TECHNOLOGIES AT
APPLICATION LEVEL 54
7.1 PU RIGID 55

2.2 D
 ECISION XIX/6 AND THE FRAMEWORK 7.1.1 PU RIGID – Domestic Refrigerators
FOR MITIGATION 15 & Freezers 61

2.3 P
 OTENTIAL BENEFITS FOR BUSINESS
AND THE ENVIRONMENT 16
3 METHODS OF QUANTIFYING CLIMATE
IMPACT 18
7.1.2 PU RIGID – Other Appliances 63
7.1.3 PU RIGID – Transport and Reefers 65
7.1.4 PU RIGID - Boardstock 67
7.1.5 PU RIGID – Continuous Panels 68

3.1 L
 IFECYCLE APPROACHES BASED ON 7.1.6 PU RIGID – Discontinuous Panels 69
DIRECT EMISSIONS ONLY 19 7.1.7 PU RIGID – Spray 70
3.2 L
 IFE CYCLE APPROACHES ALSO 7.1.8 PU RIGID – Blocks 72
CONSIDERING ENERGY 20
7.1.9 PU RIGID – Pipe-in-Pipe 73
3.3 H
 YBRID APPROACHES (e.g. Functional
Unit & Climate Indicators) 21 7.1.10 PU RIGID – One Component Foam 74
7.2 PU FLEXIBLE FOAMS 75
4 FOAM MANUFACTURE AND EXISTING
7.2.1 PU FLEXIBLE – Integral Skin (Automotive) 79
FLUOROCARBON TECHNOLOGIES 24
7.2.2 PU FLEXIBLE – Integral Skin (Automotive) 80
4.1 AN INTRODUCTION TO FOAM TYPES25 25
7.3 PHENOLIC 80
4.2 F
 OAM MANUFACTURE AND THE ROLE
OF BLOWING AGENTS 29 7.3.1 PHENOLIC – Boardstock 83

4.3 P
 OINTS IN THE SUPPLY CHAIN WHERE 7.3.2 PHENOLIC – Blocks 84
CONSUMPTION OCCURS 7.4 THERMOPLASTIC FOAMS 85
(fully formulated polyol issue) 31
7.4.1 EXTRUDED POLYSTYRENE – Board 89
4.4 R
 EASONS FOR ORIGINAL SELECTION OF
CFCs & HCFCs 32 7.4.2 POLYOLEFIN FOAMS 90
4.5 R
 EASONS WHY HFCs ARE POTENTIAL
REPLACEMENTS FOR HCFCs 34 8 FUNDING STRATEGIES 92

4.6 W
 HY HFCs CAN BE SUB-OPTIMAL 8.1 FUNDING THE OZONE COMPONENT 93
SOLUTIONS FOR CLIMATE 35 8.2 Climate Co-Funding Opportunities within
the Montreal Protocol Framework 95
5 GENERAL REVIEW OF ALTERNATIVE
BLOWING AGENTS 40 9 CONCLUSIONS 96
5.1 H
 YDROCARBONS (both directly added
and pre-blended) 41 10 ANNEXES 100
5.2 LIQUID CARBON DIOXIDE 42 10.1 SOURCES OF INFORMATION15 101
5.3 IN-SITU CARBON DIOXIDE (water blown foams) 42 10.2 CONTACT DETAILS OF BLOWING AGENT
5.4 O
 xygenated Hydrocarbons (Methyl Formate, & OTHER PROVIDERS 103
Methylal and Dimethyl Ether) 42 10.3 Full text of Decision XIX/6 106
5.5 C
 hlorinated Hydrocarbons (Methylene
Chloride, Trans-1,2 di-chloroethylene and
2-chloropropane) 44
5.6 Saturated HFCs 45
5.7 Unsaturated HFCs (HFOs) 46

7
Section 1.
Introduction

“Decision XIX/6 is the first Montreal Protocol

decision to take active account of climate in
its language”

8
 UNEP DTIE Foam Sourcebook - 2010

Section 1.
Introduction
1.1 The Challenge of Accelerated
HCFC Phase-out
The Beijing Amendment of the Montreal
Protocol, negotiated in 1999, set out the
commitment of countries operating under
Article 5 of the Protocol (developing countries)
to freeze their consumption of HCFCs at 2015
levels ahead of final phase-out in 2040. This
commitment was made alongside a more
accelerated commitment of non-Article 5
countries (developed countries) to substantially
phase down their use of HCFCs by 2015 and
finally phase-out the small remaining ‘tail’ of
use by 2030.
It was envisaged that, by the time technology
transitions out of HCFCs in Article 5 countries
were required, the non-HCFC technology in
developed countries would already be well
established. However, what was not fully
foreseen was the fact that the backdrop
for transition in Article 5 countries would be
significantly different than for non-Article 5
countries in at least two respects:
I. The preponderance of small, medium
enterprises (SMEs) in Article 5 countries would
make it impossible to take advantage of the
economies of scale available in non-Article 5
countries
II. By the time technology transition was being
contemplated in Article 5 countries, the impact
on climate of a number of HCFC alternatives
would be fully understood and would need to
be taken into consideration
Indeed, the concern over the climate impact
of HCFCs themselves was to become
another critical factor in the policy debate.
Rapid growth in HCFC use, particularly in
the consumption of HCFC-22, became
increasingly evident through the early years
of the 21st century, leading to predictions
that much of the inadvertent climate benefit
gained from the Montreal Protocol could be
lost through increased emissions of HCFCs.
It was in this spirit that Parties met at the 19th
Meeting of the Parties to the Montreal Protocol
in Montreal in 2007 to address this issue.
Decision XIX/6 was the result of that
deliberation and was the first Montreal Protocol
decision to take active account of climate
in its language, while avoiding any binding
commitments which might be considered
as global climate legislation based around
consumption rather than emission control.
The Parties concluded that, in addition to
efforts to reduce consumption by promoting
good servicing practices in the refrigeration
sector, the most effective way of avoiding the
climate impact of rapid growth in HCFCs was
to accelerate their phase-out by advancing
the freeze in production/consumption to 2013,
based on the consumption in years 2009 and
2010, while introducing phase-down steps in
the subsequent years of 2015, 2020, 2025
and 2030. The ‘old’ and the ‘new’ regimes are
shown in the graphic below.
However, what became self-evident during
the finalisation of the decision was that
these additional climate benefits would be
contingent on the use of HCFC substitutes
that displayed lower climate impacts. This had
not been considered as a significant factor
when the bulk of HCFC phase-out had taken
place in non-Article 5 countries and had led
to technology transitions which were often no
better in their climate profiles than the HCFCs
they replaced. Recognising this reality, Parties
were keen not to repeat this pattern in Article 5
countries but equally believed that they would
have some influence on the outcome through
the funding mechanisms available under the
Montreal Protocol (primarily the Multilateral
Fund).
In order to highlight this opportunity, the
Parties included within the Decision language
that required the Executive Committee of
the Multilateral Fund to ‘give priority’ to
cost-effective projects and technologies that

Montreal Protocol HCFC phase-out schedule for Article 5 countries

Percentage of
2009-10 Baseline

140%

120%
Old
Base
100%
Annual Growth Rate: 5%
80%

60%

40%
New
Base
20%

0%
2008 2012 2016 2020 2024 2028 2032 2036 2040
Year
New A5 HCFC Measures
Old A5 HCFC Measures

Source: UNEP/Caleb
9
minimise other impacts on the environment,
including on the climate, taking into account
global warming potential, energy use and other
relevant factors’. One of the key aspects of
this language is that it includes not only the
global warming potential of the substitute itself
but also the lifecycle implications resulting from
energy use. This will be explored further in
Section 3.
As a consequence, the Parties had set a very
challenging timeline for HCFC phase-out, with
all the legal compliance issues that this entails,
while making the selection of alternatives
more demanding than it had hitherto been in
non-Article 5 countries. As stakeholders began
to assess this, there was a growing realisation
that the priorities, both in terms of sectoral
phase-out and technology choice might not be
aligned to achieve both ozone compliance and
maximum climate benefit simultaneously.
In an effort to approach the subject holistically,
the Executive Committee of the Multilateral
Fund introduced the concept of an HCFC
Phase-out Management Plan (HPMP) which
would be established for each Article 5 Party
seeking to comply with Decision XIX/6. This
would focus primarily on the early steps to
accommodate the 2013 freeze and the 2015
reduction of 10% of HCFC consumption.
However, it would also need to consider the
overarching plan to meet the later phase-out
objectives, while minimising climate impact.
To plan at this level over such a long period
is proving to be a major challenge and this
Sourcebook is an attempt to assist foam
sector stakeholders in assessing the relevant
aspects.
In addition, further analysis of HCFC
consumption in Article 5 countries revealed
that the bulk of consumption was limited to
just a few countries which had significant
manufacturing capacity for refrigeration
10
equipment and/or foams. For other countries,
HCFC consumption might be limited to
servicing activities in the refrigeration sector.
The challenges of meeting specific phase-
down targets would be very different in
these countries and might lead to different
priorities, projects and programmes. This is
an issue that is largely beyond the scope of
this Sourcebook, since phase-out in the foam
sector will take place at the manufacturing
enterprises themselves or, where fully
formulated polyols are used, in combination
with their suppliers.. Nevertheless, care is
needed to see the foam sector strategy as part
of a larger HPMP and to realise that the pace
of that strategy may be heavily influenced by
the on-going HCFC needs in other areas.
A further factor may be the ‘worst first’
component of the Decision which states that:
11. To agree that the Executive Committee,
when developing and applying the funding
criteria for projects and programmes, and
taking into account paragraph 6, gives priority
to cost-effective projects and programmes
which focus on, inter alia:
(a) phasing-out first those HCFCs with higher
ozone depleting potential, taking into account
national circumstances
….and may predicate against HCFC-141b
(see Section 7).
1.2 Guidance on the use of this
Sourcebook
This Sourcebook is primarily intended to
provide overarching guidance to National
Ozone Units, Implementing Agencies and
Project Proponents on the processes
and techniques used to select alternative
technologies. It does this by outlining the key
factors to be considered and the principles
that need to be applied to assess their
significance. In Section 7 of the document,
the state of technology development in each
foam sector and the alternatives currently
available are outlined. However, this is not
done to provide definitive recommendations,
but to offer real-life examples of the decision
processes in action. These decision-processes
are themselves outlined in Section 6.
The authors would stress that it would be
impossible to provide definitive guidance
on technology selection in a Sourcebook of
this type, since it would very rapidly become
outdated. Readers are therefore encouraged
to use this Sourcebook alongside other
sources of information such as the regular
reports of the UNEP Foams Technical
Options Committee (FTOC), publications by
the Implementing Agencies (e.g. those from
the Ozone Operations Resource Group of
the World Bank), National Ozone Units, the
outputs from Regional Workshops and Industry
Conferences/Publications.
UNEP DTIE Foam Sourcebook - 2010

11
Section 2.
The interface between
ozone depletion and
climate change

“Knowledge of the key environmental benefits

of technology selection has been shown to
provide a significant competitive advantage in
the foam sector”

12

Section 2. The interface
between ozone depletion
and climate chnange
2.1 Measuring Impacts - ODP, GWP
and Carbon Intensity of Energy Use
The scientific inter-relationship between ozone
depletion and climate change is complex -
partly because it occurs at a number of levels
simultaneously and partly because there are
feedback loops whereby changes on one
side lead to changes on the other. These
inter-linkages are extensively explained in
the IPCC/TEAP Special Report on Ozone
and Climate (SROC, 2005) and it is not the
purpose of this Sourcebook to repeat those
arguments here. Responsible technology
selection, while phasing out HCFC use, can
create a substantial overall climate benefit even
when the offset of increased ozone levels (a
greenhouse gas in its own right) is taken into
account. The Montreal Protocol community
has underpinned this principle by making clear
that compliance with HCFC phase-out targets
will not be compromised for reasons of climate
protection as Decision XIX/6 is implemented.
In order to help policy-makers and other
stakeholders to assess the competing claims
of the alternatives in this complex scientific
environment, a series of metrics have been
introduced to provide guidance on the
comparative impacts of options on both the
ozone layer and on climate. These include,
ozone depletion potential (ODP), global
warming potential (GWP) and carbon intensity
of energy, each of which will be considered in
turn.
Ozone Depletion Potential (ODP)
This measure of assessing the damage that a
given substance could do to the stratospheric
ozone layer was first introduced by the UNEP
Scientific Assessment Panel in the years
running up to the instigation of the Montreal
Protocol in 1987. In simple terms, the impact
of all substances is compared to a baseline
centred on CFC-11 and CFC-12, which
are both considered to have an ODP of 1.
This process is usually called normalisation
and is a common technique for this type of
comparative analysis. Therefore HCFC-141b,
the HCFC most commonly used as a foam
UNEP DTIE Foam Sourcebook - 2010
blowing agent, has an ODP of 0.11 because even though they have measurable ODPs. The
a molecule of HCFC-141b is likely to do reason for this is that they are not considered
only 11% of the damage in its stratospheric sufficiently significant by policy-makers to have
lifetime that would have been done by a any bearing on the environmental outcome.
molecule of CFC-11. It can be noted that all Enterprises could well be best served,
ozone depleting substances controlled by therefore, by using terms such as ‘controlled
the Montreal Protocol have either chlorine under the Montreal Protocol’ or ‘not controlled
or bromine atoms, or sometimes both, in under the Montreal Protocol’, when referring to
their molecules. This is often combined with their blowing agents. It should be further noted
fluorine. Therefore, if a molecule contains that compliance with the Montreal Protocol is
fluorine but not bromine or chlorine atoms, it measured in terms of avoidance of controlled
can be recognised as not controlled by the substances, not avoidance of ozone depleting
Montreal Protocol. substances (ODS).
In practice, substances with lower ODPs often
have shorter atmospheric lifetimes than those
they replace. However, assessing precise
atmospheric lifetimes can be complex and it
may be necessary occasionally to revise ODPs
based on new scientific evidence. This can
create particular issues for policy-makers who
normally require certainty to implement policies
which need to be consistent over a number of
years. Hence, there is sometimes an ‘official’
value (as stated in the Annexes of the Montreal
Protocol) and a latest scientific value, which
might be marginally different. Enterprises are
encouraged to always use the official value in
their assessments.
In some instances, the atmospheric lifetime of
a substance can be so short that, even though
it might contain chlorine or bromine, it is
unlikely to reach the stratosphere at all. These
substances therefore have no ozone depleting
potential in practice. However, this does not
mean that there are no circumstances under
which a stray molecule might get to the
stratosphere. Care should therefore be taken in
using terms such as “zero-ODP”, even though
they are widely used in marketing literature
and, unfortunately, as a requirement in a
number of product and building codes. Better
terminology would be negligible ODP, but this
seems to be rejected in practice because it is
less emphatic.
Stakeholders should also note that there are
a number of short life-time substances that
are not controlled under the Montreal Protocol
13
Global Warming Potential (GWP)
The metric described as Global Warming
Potential (GWP) has a lot of similarities with
ODP in that it is a comparative assessment
of climate impact which is normalised against
carbon dioxide (CO2 = 1). Many other parallels
exist with ODP. For example, it is quite
common for substances to have an official
GWP (often based on the Assessment Reports
of the Inter-Governmental Panel on Climate
Change) and a latest scientific GWP. Therefore
care needs to be taken in deciding which one
to use.
Since the climate impact of a substance is
also dependent on its lifetime, decisions have
to be made about the period over which the
comparison is made. Carbon oxide itself
is a relatively long-lived molecule (50-200
years, depending on the circumstances) and
therefore a comparison over 100 years has
become accepted as something of a standard
for policy-making purposes. The selected
period is known technically as the Integrated
Time Horizon or ITH. The approach taken
under the Kyoto Protocol in adopting a ‘basket
of gases approach’ to target setting required
clear GWPs for each of the gases involved and
these were quoted in the Second Assessment
Report on the basis of a 100 year ITH. This has
also become the basis for most carbon trading
activities globally. However, the debate goes
on about whether different time horizons would
be more appropriate.
The level of contribution to global warming
that can be attributed to a substance is
primarily based on the ‘space’ it occupies
in the radiative spectrum. This is referred to
Carbon Intensity of Energy Use
Decision XIX/6 requests the Executive
Committee of the Multilateral Fund to
include energy use in its consideration of
technology options. This may arise from
primary consumption of fuel or from the use
of fuels to generate electricity. Where primary
consumption occurs (e.g. in the transport
sector or in the direct burning of gas, coal or
oil) the values of carbon intensity are relatively
consistent globally. The following graphic
illustrates the point for a number of fuels and
bio-fuels:
However, where fuels are used to generate
electricity, the mix of fuels will have a bearing
on the overall carbon intensity of the electricity
consumed. This can vary substantially
by country/region and will be influenced
significantly by the amount of renewable
energy (e.g. hydro) available. For large portions
of the refrigeration, air conditioning and
appliance sectors, electricity is the key source
of energy and hence knowledge of the carbon
intensity of local electricity is required.
Cooking Oil and Tallow 13
In practice, the first determination that needs
to be made is in respect to the contribution
of energy efficiency impacts on overall energy
consumption. Once this value is available it can
be combined with information on the carbon
intensity of the supply to assess the overall
impact on carbon emissions. This means that
the adoption of the same technology may
have different impacts in different regions. It
may even mean that the relative ranking of a
range of technologies changes by region. An
example would be where a particularly energy
efficient technology is deployed in a region with
very high ‘renewables’ content in its electricity
supply. In such a region, the impact of its use
would be much less significant than in a heavily
coal burning environment.
Tables exist (see below) giving average carbon
intensities for electricity in specific countries
and regions, but care needs to be taken with
these to ensure that they are representative of
the particular supply being drawn on by the
project and its manufactured products.

technically as its degree of radiative forcing. Oilseed Rape (UK) 55

It so happens that chlorine and fluorine Oilseed Rape (Ukraine) 59

containing compounds (CFCs, HCFCs and Oilseed Rape (Poland) 45

HFCs) occupy a particular part of the spectrum Oilseed Rape (Germany) 47

that is otherwise uncluttered. This means that Oilseed Rape (France) 46

Oilseed Rape (Finland)
their impact is considerably higher than would 52
Biodiesels
Oilseed Rape (Canada) 54
normally be expected and leads to a high
Oilseed Rape (Australia) 63
GWP. This subject is covered more specifically
Soy (USA) 55
in Sections 4 and 5.
Soy (Brasil) 73
The main impact of the GWP of a gas is Soy (Argentina) 42
experienced only when it is released. Therefore Palm Oil (Malaysia) 38
efforts to reduce releases will either delay or, Palm Oil (Indonesia) 38
at best, totally avoid the climate impact of Natural Gas 62
that gas within the lifecycle of the product Diesel 86
or equipment in which it is being used. For Gasoline 85
foams, the main points of potential release are Coal 112
during foam manufacture and at end-of-life. 0 20 40 60 80 100 120
In general, there is little emission during the Gram of Carbon Dioxide produced per Megajoule of energy (UK Government figures)

use phase – particularly from insulating foams,

where retention of blowing agent is critical Data taken from http://www.dft.gov.uk/pgr/roads/environment/rtfo/govrecrfa.pdf
performance.

14
 UNEP DTIE Foam Sourcebook - 2010

2.2 Decision XIX/6 and the
Framework for Mitigation
The metrics outlined in Section 2.1 are
essential tools in assessing the potential for
compliance with the ozone requirements of
Decision XIX/6 and quantifying the climate
impact of technology options throughout the
lifecycle. Methodologies for achieving this
quantification will be covered in more detail
within Section 3. However, it is important
to note in the interim a few key aspects of
the Decision XIX/6 framework for emissions
mitigation.
The assessment of climate impact requires a
number of key pieces of information to make it
possible. These include:
• The ODP (if any) of the alternative and • The fuel mix used to generate electricity
confirmation that it is not a controlled in the country/region considered and the
substance under the Montreal Protocol resulting carbon emissions occurring during
generation.
• The GWP of the alternative based on a
100 ITH. The challenge is to use a method that is
sufficiently robust to be reliable but not so data
• The likely emissions profile of the
intensive as to be impossible to use. This is the
substance through the lifecycle of the
subject matter of Section 3.
manufactured product/equipment
• Details of any mitigation actions that may
be taken to minimise emissions (e.g. special
treatment at end-of-life)
• The carbon intensity of any primary fuels
consumed

Carbon intensity of electricity production for selected countries’

Country Grams of carbon per kilowatt hour Country Grams of carbon per kilowatt hour
1 Estonia 328.9 26 Czech Republic 206.8
2 Moldavo 314.2 27 Singapore 206.7
3 Kazkstan 309.0 28 Lebanon 200.3
4 Qatar 300.4 29 Romania 198.5
5 Poland 286.1 30 Bahrain 187.4
6 China 259.9 31 Trinidad and Tobago 185.3
7 Turkmenistan 245.8 32 Cote d’Ivorie 184.6
8 Indai 240.7 33 Algeria 183.4
9 Senegal 237.1 34 Kuwait 182.6
10 Malta 234.7 35 Morocco 180.3
11 Bosnia and Herzegovina 232.0 36 Jordan 179.0
12 Cyprus 231.5 37 Ireland 178.7
13 Belarus 229.9 38 Zimbabwe 175.8
14 South Africa 229.7 39 Libya 172.6
15 Serbia and Montenegro 227.6 40 Kenya 170.0
16 Oman 222.8 41 Indonesia 166.8
17 Togo 222.2 42 Hungary 166.3
18 United Arab Emirates 220.7 43 Nicaragua 166.1
19 Greece 220.1 44 Denmark 165.6
20 Israel 215.7 45 Latvia 162.0
21 Australia 215.6 46 Russian Federation 158.8
22 Cuba 214.9 47 Bulgaria 154.8
23 Azerbaijan 212.8 48 Bangladesh 152.2
24 Brunei 208.4 49 Iran 151.8
25 Uzbekistan 207.1 50 Iraq 148.8

Source: UNIDO

15
 2.3 Potential Benefits for Business
and the Environment
Many enterprises reviewing these data
requirements will be beginning to wonder
whether the investment of time and effort is
proportionate to the outcomes that might be
obtained. However, in the case of the foam
sector, the experience from enterprises in
developed countries has been that knowledge
of the key environmental benefits of technology
selection has provided a significant competitive
advantage in the market place. This has been
particularly important for insulating foams
where it has been critical to understand
the upsides of improved thermal insulation
performance against the potential downsides
of direct greenhouse gas emissions.
The Fourth Assessment Report of the Inter-
Governmental Panel on Climate Change
(AR4) provided some important new analysis
on the critical role of buildings in the fight
against global warming. Buildings and the
appliances used in them account for over
GtC02 -eq / year
7 7
6 6
5 5
4 4
3 3
2 2
1 1
0 0
<20 <50 <100 <20 <50
Energy Supply Transport
potential at potential at
<US$100/tC 02-eq: <US$100/tC 02-eq:
2.4-4.7 Gt C02-eq/yr 1.6-2.5 Gt C02-eq/yr
Source: IPCC Fourth Assessment Report
16
40% of total CO2 emissions per year and the buildings themselves, as building energy
use of appropriate insulation levels in both standards and sustainability requirements are
new and existing buildings would contribute being imposed. It seems therefore inevitable
substantially to reducing this footprint. Not only that these issues will become mainstream in all
would such measures be productive in terms global markets, to the extent that they have not
of the quantity of savings, but they would also already done so. Enterprises could therefore
be more cost-effective than a large number benefit significantly from the assessments
of competing policy options. The following required as part of the technology transition
graphic illustrates these findings: process.
With such market upsides potentially available,
there is a clear incentive to ensure that foam
products are positioned to take advantage. If
part of the argument used to justify the greater
use of thermal insulation in general, and foam
in particular, is based on the environmental
benefit, it stands to reason that specifiers will
want to understand the environmental profiles
of the products they are buying from ‘cradle-
to-grave’.
There has been a substantial surge in the
level of environmental assessment being
now applied to building products. In some
instances, this is also being extended to the
7 7 7 7 7
6 6 6 6 6
5 5 5 5 5
4 4 4 4 4
3 3 3 3 3
2 2 2 2 2 Non-OECD
EIT
1 1 1 1 1
OECD
0 0 0 0 0 World
<100 <20 <50 <100 <20 <50 <100 <20 <50 <100 <20 <50 <100 <20 <50 <100
US$/tC 02-eq
Buildings Industry Agriculture Forestry Waste
potential at potential at potential at potential at potential at
<US$100/tC 02-eq: <US$100/tC 02-eq: <US$100/tC 02-eq: <US$100/tC 02-eq: <US$100/tC 02-eq:
5.3-6.7 2.5-5.5 Gt C02-eq/yr 2.3-6.4 Gt C02-eq/yr 1.3-4.2 Gt C02-eq/yr 0.4-1.0 Gt C02-eq/yr
UNEP DTIE Foam Sourcebook - 2010

17
Section 3.
Methods for quantifying
climate impact

“the impact of technology choice on energy

consumption will be an additional source of potential
climate contributions”

18

Section 3.
Methods for quantifying
climate impact
Section 2.2 has already made reference to the
fact that quantitative assessments of climate
impact need to take account of activities that
occur throughout the lifecycle of the products
and/or equipment manufactured as a result of
the implementation of a project.
However, when assessing technology
transition projects at enterprise level, this can
be a relatively complex and uncertain exercise,
since the quantity and scope of products and/
or equipment manufactured by an enterprise
will not be known in full at the point of
investment.
This challenge, however, is not insurmountable
if the primary purpose for quantifying the
climate impact of a measure is to compare
technology options. In such cases, it is
possible to take defined units of manufacture/
production, based on typical demand patterns,
and compare the relative climate impacts
arising from specific technology choices prior
to making a final decision. It is in this context,
that this Sourcebook reviews the options
available for quantifying climate impact.
UNEP DTIE Foam Sourcebook - 2010
3.1 Life Cycle Approaches based on V. If not, how are these diffusion differences
accounted for in the respective emissions
Direct Emissions only (e.g. GWP)
profiles?
It is well known that the direct emissions of
chlorinated and fluorinated substances over VI. Are there any constraints from the
the lifecycle of products and/or equipment can technology choice that would prevent
lead to significant climate impacts. The graph recovery at end of life?
below illustrates the significance of the global
Section 4.6 of this Sourcebook provides tables
warming impacts of common CFCs, HCFCs
illustrating the current default emission profiles
and HFCs, when compared with carbon
for various foam processes and applications
dioxide. If aspects such as initial charge sizes
using liquid and gaseous blowing agents.
and emission profiles are well understood, it is
Annual emission rates are provided for each
possible to make relatively precise estimates
basic lifecycle stage. These tables are typically
of the climate impact of emissions including
used as an initial basis of assessment for
their significance with time. However, even
direct emissions from foams. Where no further
where the focus of attention is only on direct
adjustments are made for items II-VI above,
emissions of refrigerants and/or blowing
the choice of blowing agent from a climate
agents, care must be taken to ensure that the
perspective is generally directly linked to its
comparisons are appropriate. In the foams
GWP, which is why it is sometimes referred to
sector, the following questions might be part
as the GWP method. Although this provides
of a useful checklist to ensure that ‘like is
a temptingly simple basis for evaluation,
compared with like’:
care needs to be taken that all appropriately
I. Do the boiling points of the respective adjustments are made before conclusions are
alternative blowing agents influence the drawn.
losses in production?
II. Does the technology choice involve
co-blowing with another blowing agent?
III. How do the blowing efficiencies of
different technology options impact the
level of blowing agent required in the
respective formulations?
IV. Is the rate of permeation of blowing
agent through the cell walls the same for all
blowing agents?
Refrigerator TEWI Contributors
(Typical for HFC product in USA)
Blowing Agent Refrigerant
Direct GWP Direct GWP
7.2% 0.4%
Power Plant
Emissions
92.4%
Source A.D. Little (2002)
19
 3.2 Life Cycle Approaches also
considering energy (e.g. LCA, LCCP,
TEWI)
For both foam and refrigeration applications,
it is well understood that the impact of
technology choice on energy consumption will
be an additional source of potential climate
contributions. In many applications, the
energy consumption component can be a
dominant factor in the overall carbon footprint
of the product or equipment. An example of
this would be a domestic refrigerator where
the following pie chart illustrates the relevant
components of greenhouse gas emission over
the lifecycle.
Although such graphs rightly draw attention to
the fact that the focus of appliance designers
should be on improving energy efficiency, they
do not automatically lead to the conclusion
that the choice of refrigerant or blowing agent
is unimportant.
Where the choice of blowing agent can
influence the energy efficiency of a refrigerator
significantly, it may be that this effect will offset
the direct emissions from eventual blowing
agent release. However, the level to which this
is the case will depend largely on the sensitivity
of energy efficiency to such choices, which
will in turn depend on the geometry of the
appliance and the levels of insulation used.
In practice, it is often the case that energy
efficiency is only marginally influenced by these
technology choices and, in such situations
the comparative process reverts largely to a
comparison of direct emissions only. This said,
the inclusion of ‘energy use’ within the factors
that must be considered under Decision XIX/6
requires that an appropriate lifecycle model
is used. The following section outlines three
options that have found application for this
purpose.
All three methods featured below - Lifecycle
Assessment (LCA), Total Equivalent
Warming Impact (TEWI) and Lifecycle
Climate Performance (LCCP) - focus on the
performance of individual products or pieces of
equipment. In this respect, they are amongst
the most rigorous analyses available. However,
as will be highlighted, they are data hungry
and often limited in their application because
of their focus on individual installations. They
are of most use where the product/equipment
is mass produced and where the performance
20
is largely independent of the local environment Life Cycle Climate Performance
(e.g. domestic refrigerators). Accordingly,
(LCCP)
such techniques are typically used by product
designers and also academics, seeking to
This method emerged in the wake of the
TEWI experience and explicitly included the
make comparisons and plot trends. However,
earlier climate footprints associated with the
these techniques are of less value in assessing
production of chemicals and other precursors.
climate implications at enterprise or project
The term Life Cycle Climate Performance
level. was used in earnest for the first time in the
Life Cycle Assessment (LCA) 1999 TEAP Task Force Report entitled “The
Implications to the Montreal Protocol of the
Life Cycle Assessment is effectively the
inclusion of HFCs and PFCs in the Kyoto
‘gold standard’ for such comparisons and
Protocol”, in which the comparative impacts
not only includes climate related elements
of a number of technology choices were
but many other environmental impacts. It
assessed.
has been the subject of a large degree of
standardisation around the world and the As with LCA, LCCP remains relatively “data
current LCA principles are set out in detail hungry” despite its climate focus and is best
within the International Standards Organisation applied to situations where there are a large
(ISO) 14040 series of standards. As a result number of replicated units (e.g. domestic
of its comprehensive nature, it is a very “data refrigerators, mobile air conditioners etc.).
hungry” approach and requires substantial Where applications are less well defined and
resources for satisfactory completion. Where are typically specified by their surroundings
the primary purpose of the activity is for (e.g. building insulation or stationary air
technology comparison (as in this instance), conditioning), there is a need for a less
Life Cycle Assessment would normally be complex hybrid approach.
considered as too cumbersome for the
purpose. This has led practitioners to consider
two other approaches which are focused solely
on components relating to climate impact.
Total Equivalent Warming Impact
(TEWI)
Total Equivalent Warming Impact was
first developed and introduced by the US
Department of Energy’s Oak Ridge National
Laboratory (ORNL) in the mid-1990s as a
means of making relevant comparisons of
climate impact for differing technology options.
It was an effective initial tool, but came under
later criticism because it did not fully consider
the footprints associated with the earlier steps
in the manufacturing process (for example,
of the blowing agents themselves). In reality,
this should never have been a criticism of the
method, since every lifecycle comparative
method has to define its boundaries. The
failing was probably in not making them clear
enough to those reviewing the outputs.
This experience highlights a further important
point when developing and using lifecycle
comparison tools - “always be sure to
understand the boundary conditions of the
model (i.e. what is included and what isn’t.)”
 UNEP DTIE Foam Sourcebook - 2010

3.3 Hybrid Approaches (e.g.

Functional Unit and Climate
Indicators)
Hybrid approaches of the type included in this
section are targeted at addressing the more
practical challenges of evaluating the climate
impact of technology choices at enterprise
or project level. This may also extend to the
overall evaluation of HPMPs themselves. This
higher level evaluation (which some have
called ‘climate proofing’) is a critical part
of the objectives of National Ozone Units,
Implementing Agencies and other interested
parties. In practice, hybrid approaches are
expected to be more widely used in the
implementation of Decision XIX/6 than the
more formal methods of LCA, TEWI and LCCP.
However, as pointed out in the sections that
follow, care needs to be taken to maintain
sufficient rigour to give reliable predictions of
climate impact.
In addressing this concern for both practicality
and rigour, and following the negotiation
and finalisation of Decision XIX/6, there
were substantial discussions about how the
language concerning the evaluation of climate
impact might be interpreted in practice. Some
felt that a GWP-based approach would be
sufficient, arguing that LCCP was too complex,
particularly in applications where there were
uncertainties about the use conditions. Others
felt that LCCP was the only way in which the
full text of the Decision could be implemented.
As a potential means of bridging this difference
in view, two new approaches have emerged.
These are the functional unit approach (FUA)
and the Multilateral Fund Climate Indicator
(MCII). Both methods have sought to provide
guidance in technology selection specifically in
the context of Decision XIX6.

21
Functional Unit Approach (FUA)
This approach was originated in the foam
sector and seeks to establish a basis for
comparison of insulation foams in typical
building or appliance applications. In doing
so, it has needed to take account of matters
such as building energy sources, local carbon
intensity values for electricity generation and
local building insulation standards. Since
these vary between residential buildings
and commercial/industrial buildings, it can
be necessary to take into account the likely
split of foam sales to each sector. However,
by considering the fate of a typical unit of
foam (the functional unit), the scenario for a
particular manufacturing plant or enterprise can
be established. As with other techniques, the
fact that the tool is being used for comparative
purposes means that the sensitivity to the
assumptions used is somewhat diminished.
The table below provides an indication of the
type of output obtained using the functional
unit approach when comparisons are made
between the old HCFC-141b technology and a
replacement n-Pentane technology at constant
thickness (constant thermal performance being
the other typical basis of comparison). The
calculations are based on the lifecycle impact
of the annual production of an enterprise
currently using 25 tonnes of HCFC-141b per
year.
It can be seen that the better thermal
performance of HCFC-141b results in less
energy being transmitted through the foam
during its lifetime and hence less CO2 emitted
from power generation. However, the quantity
of n-Pentane used in the foam is reduced
because it has better blowing efficiency and
its lower GWP also contributes to a net saving
of around 4,800 tonnes CO2-equiv. when
compared with the HCFC-141b baseline.
If the comparison had been conducted on
the basis of constant thermal performance,
the n-Pentane option would have required
additional thickness of foam and hence the
embodied energy of the additional foam would
have also needed to have been included in the
comparison.
In a further enhancement of the Functional
Unit Approach an attempt was made to
assess likely differences in cost resulting
from technology choices. This permitted the
calculation of cost per unit of climate benefit
for the first time. However, to do this, the
model needed to assess the cost of a climate
neutral transition (i.e. one with the same
climate profile as the HCFC-141b technology
being replaced). One of the interesting aspects
to emerge from this assessment was that the
climate mitigation costs (measured in US$ per
tonne of CO2 saved) increased dramatically
for technologies requiring significant capital
investment as the size of the plant diminished.
This observation was no more than a
demonstration of the basic principles relating
to economies of scale, first mentioned in
Section 1 and elaborated further in Section 4.5
and elsewhere. Nevertheless, it did highlight
the fact that climate mitigation costs in excess
of US$200/tonne of CO2-equiv. might be
incurred in the most extreme cases. Further
detail on the basis for these analyses is found
in the relevant MLF Executive Committee
publication on the treatment of Environmental
Issues in technology transition (Annex V of
UNEP/OzL.Pro/ExCom/55/47).
Climate Indicators (e.g. MCII)
Although foam scenarios could be relatively
well modelled using the Functional Unit
Approach, a further level of simplification was
seen as necessary for the refrigeration sector.
The UN Multilateral Fund Secretariat took
direct responsibility for this further step and
developed, in conjunction with experts in the
field, a simplified model that essentially limited
the refrigeration and air conditioning sector
to five primary cooling scenarios. This further
level of simplification has been seen to make
the absolute comparative values less reliable
but continues to provide sufficient certainty to
allow for technology-ranking to take place.
As with the FUA, comparison with the
technology being replaced is an important
element of the assessment, since this has
a strong bearing on whether it should be
prioritised in an overall HCFC Phase-out
Management Plan (HPMP) or not. In addition,
the relative climate performance against such
a benchmark can be used to incentivise
or discourage certain technology selection
options. Stakeholders are certainly advised
to review periodically how quantified climate
impacts might be used to assess technology
appropriateness, funding eligibility and levels
of support in future. This Sourcebook will
return to this point in Section 8 where ‘Funding
Strategies’ are considered.

Example of Foam Comparisons using the Functional Unit Approach for Foams (Constant Thickness)

Calculations HCFC-141b n-Pentane

Annual Foam Volume 7,143 m3 7,143 m3
Area of Insulation Created 128,571.17 m2 128,571.17 m2
Energy Transmitted in Lifetime 121722.17 MWh 189345.60 MWh
Carbon equivalent 23127.21 t-CO2-equiv 35975.66 t-CO2-equiv
Energy difference 67623.43 MWh
Carbon equivalent difference 12848.5 t-CO2-equiv
Blowing Agent Losses 25.00 tonnes 16.15 tonnes
Carbon equivalent 17825 t-CO2-equiv 178 t-CO2-equiv
Carbon equivalent difference -17647 t-CO2-equiv

Total Carbon Equivalents 17825 t-CO2-equiv 13026 t-CO2-equiv

22
UNEP DTIE Foam Sourcebook - 2010

23
Section 4.
Foam manufacture
and existing fluorocarbon
technologies

“The characteristics of CFC-11 and CFC-12

were so appropriate for polymeric foams that
they seemed ‘designed-for-purpose”

24

Section 4.
Foam manufacture and
existing flurocarbon
tecnologies
4.1 An introduction to
Foam Types.
Polyurethane Foams (including
Polyisocyanurate)
Polyurethane Foam technologies were
developed as early as the 1930s in flexible,
rigid and semi-rigid forms, and have played a
dominant role in the field of foamed polymers
ever since. This is largely because of the
technology’s basic capacity to produce
materials with a wide range of critical end
properties such as low density, consistent
foam morphology, mechanical strength and
resilience. In most cases, these properties can
be achieved by relatively simple formulation
adjustments, indicating the versatility of
polyurethane chemistry.
Flexible foams, which demonstrate excellent
elastic and deformation characteristics, find
their major applications in the area of furniture
cushioning (bedding, seating, carpet backing,
etc.) and packaging (electronic, computer,
china, equipments). Semi-rigid foams are used
in the automotive industry (dash panel, liner,
visors) and footwear (shoe soles) [Lee, 2006].
However, the largest single application for
polyurethane rigid foam is in thermal insulation,
although similar foams can also be used to
provide structural integrity and buoyancy.
For thermal insulation applications, old and
modern buildings, transport systems and
household appliances all take advantage of the
excellent energy performance offered through
the low thermal conductivity of the foam.
It is in the area of thermal insulation that the
contribution of the blowing agent is at its most
significant, since the gas in the foam cell is
the major contributor to the overall thermal
performance of the insulation. This subject is
explored further in Section 4.2.
A variant of basic polyurethane chemistry is
polyisocyanurate, which has greater rigidity
and provides improved fire performance.
However, it is less resilient and is therefore
not a replacement for polyurethane in all
applications.
UNEP DTIE Foam Sourcebook - 2010
Phenolic Foams
Phenolic foams take the characteristics of
polyisocyanurate a step further and are very
highly cross-linked. This makes them very
rigid (high modulus) and, historically, has led
to unacceptable friability where vibration or
thermal shock is a factor. Nonetheless, more
recent technologies have achieved very fine
cell structures which have both improved
the resilience of the foam and its thermal
performance. Indeed, phenolic foam now
typically delivers the best thermal performance
among the insulating foam types available.
However, this is not the primary reason for its
use. Phenolic foam has made ground primarily
because of its overall fire performance and,
most importantly, low smoke generation.
As with polyurethane and polyisocyanurate,
phenolic foams were historically blown with
CFCs and have progressed through a number
of alternatives which are documented in
Sections 5 and 7.
Extruded Polystyrene
A number of polystyrene foam product types
exist. Expanded polystyrene foams are blown
from beads of polystyrene which already
contain a hydrocarbon blowing agent (typically
pentane). These beads are then expanded
in hot moulds to create blocks and moulded
shapes. For this reason, the foams have been
used more for packaging than for demanding
thermal insulation applications. These foams,
sometimes referred to as bead foams, have
never used CFCs as blowing agents and are
not the subject of this [Sourcebook].
An alternative type of polystyrene foam is
extruded polystyrene foam which, as its
name suggests, is manufactured by an
extrusion process at elevated temperatures.
This product has historically used CFCs and
their substitutes. The nature of the extrusion
process is such that it creates more integral
foams than those generated from beads and
provides better thermal properties as a result.
Some extruded products are manufactured
specifically for construction applications and
are typically referred to as ‘board’, while others
are manufactured for packaging purposes,
sometimes with a thermal component (e.g.
disposable food packaging) and are typically
known as ‘sheet’ products.
25
 The following diagram illustrates the broad range of foam types available and the primary applications for which they are used. It also
highlights those that currently continue to use HCFCs:

open cell rigid PU foam

open cell phenolic foam (incl. floral)
slabstock (bedding etc.)
flaxible PU foam
moulded (furniture)
non-
insulating rigid ISF*
foam integral skin PU foam
semi-flexible ISF*
extruded polystyrene (XPS Sheet)
thermoplastic foam
extruded polyethylene
miscellaneous foams
blocks, pipes & discont. panels
phenolic foam*
boardstock*
thermoplastic foam XPS Board*
refrigerators/freezers*
thermal
insulating water heaters*
foam appliances
commercial refrigeration*
coolers/thermoware*

rigid PU boardstock*
foam
“pipe in pipe”*
panels*

construction/ (cont./discont.)
transportation blocks
in situ applications*
(spray, one component)
Transportation refrigeration*

* May use HCFCs

26

Polyolefin (Polyethylene/
Polypropylene) Foams
Polyolefin foams are processed similarly to
extruded polystyrene foams and have largely
similar characteristics and applications.
They have additional resilience in packaging
applications and are often selected as the
material of choice. Again polyolefin foams
historically used CFCs and have progressed to
other alternatives over the last 20 years.
Non-Foam Insulation Products
A variety of non-foam products are used for
thermal insulating purposes. Although this
Sourcebook is focused on polymeric foams, it
is important to understand that these co-exist
with other insulation types in a competitive
market, where changes in the cost-structure
of foams can have consequences for market
share. The most widespread product is
mineral fibre, which can be based on spun
rock (rock fibre) or glass (glass fibre). The low
UNEP DTIE Foam Sourcebook - 2010
density of these products makes them both The following tables add to the earlier diagram
inexpensive and comparable in embodied in that, while they similarly relate the application
energy, despite the high energy intensity of the areas with the type of foam, they also provide
manufacturing process. However, since they an indication of prevalence of use and a
rely on entrapped air for their thermal insulating comparison with non-foam alternatives. They
properties they are losing ground against the are based on an assessment generated for
more thermally efficient foamed products the IPCC/TEAP Special Report on Ozone
in many markets, particularly in chilled and Climate . In this chapter, after a brief
applications where moisture ingress can result introduction on rigid foam and the role of the
in degradation of properties. blowing agent, the different technology options
will be reviewed by application.
There are a number of other insulation
materials available, often marketed on their
apparent environmental credentials. These
include naturally sourced materials such as
sheep’s wool and recycled materials such
as cellulose fibre. However, none of these
products have broken through to the mass
market.
There are also specialist insulation products
such as calcium silicate, which is particularly
good for high temperatures applications.
27
 Foam Type Application Area

Refrigeration & Tranport Buildings & Building Services

Domestic Other Reefers & Wall Roof Floor Pipe Cold

Appliances Appliances Transport Insulation Insulation Insulation Insulation Stores

Polyurethane Injected P+P 444 44 444 4 44

Boardstock 444 444 4

Cont. Panel 44 444 444 444

Disc. Panel 44 444 444 444

Cont. Block 44 4 444 44

Disc. Block 44 44 44

Spray 44 44 444 4

One Component 44 4 4

Extruded
Board 44 444 444 444 4 44
Polystyrene

Boardstock 444 444

Phenolic One Panel 44 4 444

Disk Block 444 44

Board 4
Polyethylene
Pipe 444

4 4 4 444 444 444 4

Mineral Fibre

4 4 4 = Major use of insulation 4 4= Frequent use of insulation 4= Minor use of insulation

Foam Type Application Area

Transport Comfort Packaging Buoyancy

Seating Safety Bedding Furniture Food & Other Marine &

Leisure

Polyurethane Slabstock 44 444 444 44

Moulded 444 44 44

Integral Skin 444 4 4

Injected/
444
P-I-P

Cont. Block 4

Spray 4

Extruded Sheet 444

Polystyrene
Board 444

Polyethylene Board 44 44

4 4 4 = Major use of insulation 4 4= Frequent use of insulation 4= Minor use of insulation

28
 UNEP DTIE Foam Sourcebook - 2010

4.2 Foam Manufacture and the Role
of Blowing Agents
Both tables shown in Section 4.1 give the first
indication of the wide range of processes that
are available for the processing of polymeric
foams. The challenges relating to technology
selection for each of these processes are
covered in detail in Section 7. However,
this section focuses primarily on the basic
principles surrounding foam manufacture.
In general terms, a blowing agent is present
in a foam formulation to ensure that the
polymer matrix expands prior to solidifying.
This expansion can be created by raising
the temperature of the mix and causing the
blowing agent to volatilise, or by reducing the
pressure to which the mix is exposed (typical
in extrusion processes), or a combination of
both. The amount of blowing agent added
and the processing conditions applied dictates
the final density of the foams generated. For
insulating foams, densities are typically in the
range of 25-40 kg/m3. For packaging foams
the densities will be lower and for comfort
foams they will be lower still – often well below
20kg/m3.
Some products and processes lend
themselves to the selection of blowing agents
which are gaseous at room temperature.
These are typically those products and
processes in which expansion is controlled
by pressure. In some cases, these types of
processes are known as ‘froth foaming’, since
the formulations froth when the pressure is
released. Other processes rely on the blowing
agent being in liquid form for the early stages
of the process, with foam expansion and
curing usually achieved by the application
of heat. The following paragraphs use the
example of polyurethane foam to illustrate the
basic process involved.
Polyurethane rigid foams are prepared by
the reaction under controlled conditions
-reactants ratio, temperature and pressure- of
a “fully formulated polyol” with an isocyanate,
normally polymeric MDI. The term “fully
formulated polyol” describes a blend of polyols
with a variety of additives such as catalysts,
surfactants, water, flame retardants (not
typically in appliances), including the blowing
agent (FTOC, 2001).
A wide spectrum of polyols of different
chemical nature -polyether and polyester-
and molecular architecture -functionality and
equivalent weight- is used. Water is commonly
added to generate CO2 by the reaction with
the polymeric MDI; the polyurea groups which
are simultaneously formed contribute to the
build-up of the polymer skeleton. Optimum
processing characteristics and end foam
properties cannot usually be achieved with a
single polyol and the same holds for catalysts
and the other additives. As a consequence,
in today´s industrial practice, a large number
of formulations has been and continue to be
developed to meet the different application
requirements. The formulation process of
polyurethane rigid foam can be graphically
described as follows:

Network Formation Polyether Polyols

Polyether Polyols Catalysts
Surfactants
Kinetics Control Water
Blowing Agents

Stabilizers +
Polymeric MDI

CO2

29
 The following guide to polyurethane terminology prepared by the UNEP FTOC (2001) is illustrative:
TERM EXPLANATION APPLICATION MAY CONTAIN
Urethane Specific chemical link formed by the
reaction of a hydroxyl (OH) with an
isocyanate (NCO) group
Polyurethane Polymer consisting of a multiple of
urethane linkages formed from the
reaction between a polyol and an
isocyanate
Isocyanate Family of chemicals with typically
two or more NCO groups. Most
common are MDI, P-MDI and TDI
Isocyanate prepolymer Modified isocyanate by reacting
(also called polyurethane prepolymer) excess of this substance with a
polyol. Provides technical effects
that cannot be obtained by
unmodified ones
(Base) Polyol Short chain chemical with two or
more OH groups. Can be polyether
(COC) or polyester (COOC) based
(Base)Polyol blend Blend of two or more base polyols
Blowing agent ubstance used to achieve a cellular
(“foam”) structure
Polyol formulation Polyol or polyol blend plus catalyst(s),
(also called formulated polyol) surfactant(s) plus sometimes other
additives such as fire retardants
Fully formulated polyol As above, plus blowing agent
Polyurethane system Marketing term used to describe a
generally two component package,
consisting of an isocyanate and a
fully formulated polyol
Since a degree of pre-blending occurs within the supply-chain, these terms have become important in the implementation of the Montreal
Protocol itself, since the definition of the ‘point of consumption’ is a critical aspect of Governmental reporting.
30
BOWING AGENT
No
To produce foams, elastomers,
adhesives, sealants, coatings, and Yes
more
As component in the manufacture of No
polyurethanes
Main use is in flexible foam for
moulding, MDI-based slabstock,
Yes
elastomers, including shoe soles
and integral skin foams and one
component (”canister”) foams
Used as a component by self-
formulators, such as system houses, No
slabstock and rigid boardstock
manufacturers
Same as base polyol users, plus No
some appliance manufacturers
To produce rigid and flexible foams
as well as expanded (micro-cellular) Yes
elastomers
Larger polyurethane manufacturers,
such as manufacturers of appliances
and sandwich panels, who add
blowing agent according to No
foaming conditions, including safety
considerations
Smaller polyurethane manufacturers,
such as sprayfoam contractors, with Yes
relatively simple operating conditions
Same as fully formulated polyol
Yes

4.3 Where HCFC consumption
occurs in the foam sector supply
chain (polyols)
When proposing foam sector projects for
funding, it is important to understand the
various related polyol definitions in order to
accurately report the HCFC consumption
related to the project and to make it consistent
with national HCFC data reporting:
• Polyol: Short chain chemical with two or
more OH groups.
• Polyol blend: Blend of two or more polyols.
• Formulated polyol: Polyol or polyol blend
plus catalyst(s), surfactant(s) plus, in
some cases, other additives such as fire
retardants.
• Fully formulated polyol: Formulated polyol
plus blowing agent.
• Polyurethane pre-polymer: Modified
isocyanate by reacting excess of this
substance with a polyol.
• Polyurethane system: Marketing term used
to describe a generally two component
package, consisting of an isocyanate and a
fully formulated polyol.
Historically the Parties of the Montreal
Protocol, when reporting to the Ozone
Secretariat under the requirements of Article
7, have not necessarily considered CFCs or
HCFCs contained in “fully formulated polyols”
to be controlled substances. This has had
consequences for data reporting and the
establishment of national baselines. If the
use (i.e. the point at which ODS finally cease
to be controlled substances by becoming
products or parts thereof) is consistently
reported either at the point at which the “fully
formulated polyol” is being created or where
the “fully formulated polyols” are used, the
consumption (production + imports - exports)
figures are not distorted at the global level.
The only time that “reported consumption”
is distorted is where reporting practices are
inconsistent and consumption is either double-
counted or missed altogether. Accordingly,
it is important that a consistent approach is
adopted. This is also important when it comes
to the appropriate allocation of funding along a
supply chain.
Annex D to the Montreal Protocol itself makes
reference to ‘pre-polymers’ as “products
containing controlled substances”, while
‘polyurethane pre-polymers’ are described as
“use systems to be considered as products”
in Decision I/12. However, there is no explicit
UNEP DTIE Foam Sourcebook - 2010
suggestion that the Parties ever intended to
cover fully formulated polyols under these
references, nor would the relevant technical
definitions support this. Accordingly, the Parties
to the Protocol are currently reconsidering the
implications of adopting a definition which sees
fully formulated polyols as physical mixtures
still containing controlled substances (ODS).
Under these circumstances, trade in fully
formulated polyols is still trade in mixtures
containing controlled substances. This is
fully consistent with the treatment of physical
mixtures in decisions which have focused
primarily on refrigerant blends (e.g. Decision
XIV/7).
Since the significance of reporting practice to
the establishing of national baselines and the
allocation of funding for the projects came to
light, some Article 5 countries have adopted
the policy of reporting the import of ODS
contained in “fully formulated polyols” as part
of their baseline consumption, while others
have stayed with the historical interpretation.
The Executive Committee has made it clear
that the phase-out of HCFC in fully formulated
polyols can be eligible for funding provided that
it is included in the HPMP and that the funding
is proportionate to the processes being
performed.
31
The goal of consistent future reporting will
depend on further considerations by the
Parties. The Parties are currently reviewing
how to resolve this in such a way as to avoid
double-counting at the same time as avoiding
the omission of actual consumption in Article
7 reporting. Readers of this Sourcebook are
encouraged to check with their National Ozone
Unit on the reporting policy that is currently
being adopted within their own countries
in order to confirm that stated baselines in
HPMPs properly reflect their uses and that the
legitimate funding requirements for projects in
the foam sector are met.
4.4 Reasons for Original Selection of
CFCs and HCFCs
For a large proportion of the foams in which
ODS have been used historically, and
particularly those in which HCFCs are currently
used, the blowing agent has two principal
functions:
1. The physical expansion of the foaming
mixture to produce the desired foam
density. In PU rigid foam the expansion is
normally achieved by the combination of two
mechanisms:
• the generation of CO2 as a consequence
of the water/isocyanate reaction
and
• the evaporation of the blowing agent by
the exothermically reaction mixture.
The boiling temperature of the blowing agent
influences how these two mechanisms are
combined in time, which strongly affects the
foam ability to flow. Lower the boiling point,
better the flow (KHUN, 1993). Immediately
after the foam is produced there are usually
two gases simultaneously present in the cells:
carbon dioxide and the selected blowing agent
(HCFC-141b, HFC-245fa, cyclo pentane, etc.).
32
2. Contribution to the thermal insulating When the polymeric foam industry was
performance of the foam. The blowing agent emerging in the early 1960s, CFCs had
should remain in the closed celled foam and already been in use as refrigerants within the
have a low gaseous thermal conductivity plus a refrigeration sector for some years. They were,
low rate of diffusion through the foam (polymer therefore, relatively plentiful, inexpensive and
matrix) so that the good insulating properties offered virtually all of the characteristics listed
are retained for many years. above. In particular, the gaseous thermal
conductivities of the substances were low,
A number of publications have highlighted the
reflecting the thermodynamic properties that
preferable characteristics for a blowing agent.
had also made them suitable as refrigerants.
However, these have changed over time. Prior
Coupled with low toxicity and chemical
to the existing concerns over ozone depletion
stability, CFC-11 and CFC-12 were seen as
and climate change, the list would have
virtually designed-for-purpose and dominated
appeared as follows:
the industry for 25 years. Of course, it was the
• Physiologically non hazardous (low toxicity) chemical stability of CFCs which finally became
their downfall.
• Non flammable
• Chemically/physically stable
• Advantageous boiling point for ease of
handling
• Good solubility in polyols (for polyurethane
systems)
• Commercially available, and
• Economically viable.
As an additional set of characteristics for
thermally insulating foams, the following were
deemed as advantageous:
• Low gaseous thermal conductivity
• Boiling point to minimize condensation
of the blowing agent in the final foam at
operational temperatures
• Low solubility in the foam polymer to avoid
matrix plasticisation which can cause
dimensional stability problems.
• Low diffusion rate through the polymer
matrix.

When, in 1974, Rowland and Molina made
the first linkage between ozone depletion and
chlorine in the stratosphere, few, if any, from
the polymeric foams industry were watching
developments. However, the discovery of the
Antarctic ozone hole in 1985 added urgency
to the debate and began to implicate the foam
industry, both in flexible and in rigid products.
As the industry began to look for immediate
alternative blowing agents, it was already
known that very few, if any, alternatives
could provide the package of characteristics
displayed by the CFCs.
HCFC-22 was already well established as
a refrigerant in the commercial refrigeration
sector and it was known that the presence of
the hydrogen atom in the molecule reduced
the stability and resulting atmospheric lifetime
of the substance somewhat. However, its
boiling point was inappropriate for a large
section of the industry, and, even where
it wasn’t (e.g. extruded polystyrene), the
molecule was found to permeate the cell walls
too quickly. This situation therefore led to the
search for alternative HCFCs that could fulfil
the same role as CFCs with less likely damage
on the environment.
UNEP DTIE Foam Sourcebook - 2010
Out of that work, three additional HCFCs HCFC-141b and HCFC-142b, the industry
emerged: - HCFC-123, HCFC-141b and learned that variable parameters such as ODP
HCFC-142b. For a long period, HCFC-123 or cost can be compromised to a degree in
looked like the ideal replacement for CFC-11, order to maintain the primary performance
having a very low ozone depletion potential characteristics of the product itself – in this
of 0.012 – i.e. nearly 100 times lower than case thermal insulation performance.
CFC-11 (ODP = 1). However, late in the
Nevertheless, it became increasingly clear,
development phase, it was discovered that
in the early 1990s, as the legislators caught
the toxicity of the substance could be of
up with the pace of technology development
concern. This led to the later introduction
that these were only going to be seen as
of HCFC-141b as the CFC-11 replacement
‘transitional’ solutions, despite the fact that
of choice, even though its ozone depletion
they were seen as part of the solution rather
potential was significantly higher at 0.11
than part of the problem. Therefore the search
(i.e. less than ten times lower than CFC-11).
for further alternatives could not be halted.
HCFC-142b was used alongside HCFC-22 in
the extruded polystyrene and polyolefin foam
sectors, since the HCFC-142b component,
whilst more expensive than HCFC-22,
provided the thermal performance that the
foams required, because it did not diffuse
through the cell walls quickly.
These early experiences of blowing agent
transition taught a number of lessons. Firstly,
the HCFC-123 experience taught that an
alternative, no matter how attractive in other
respects, could not be used if a critical
parameter was unacceptable. In the case of
33
 4.5 Reasons why HFCs are Potential
Replacements for HCFCs
In a list of appropriate criteria for replacement
blowing agents published in 1994, OERTEL
had included ‘zero ODP’ and ‘low GWP’
as desirable parameters. This reflected the
fact that climate factors associated with the
manufacture and use of foams were already
beginning to emerge as important aspects to
be considered.
The regulatory stance on HCFCs had already
been noted and some CFC-users had decided
to make the direct transition to hydrocarbons
(HCs) even though their thermal performance
was poorer than the fluorocarbons and there
were issues surrounding the management
of their flammability. In Europe and Japan,
the most visible sign of this trend was in
the domestic refrigerator sector, where
manufacturers believed that other design
factors could be adjusted to compensate for
the poorer thermal performance of the foam. In
addition, the economies of scale were sufficient
to justify the investment in the management
of safety issues during manufacture. The
consequence of this, and other similar
technology choices, was that the replacement
of CFCs by HCFCs was not a 1:1 replacement.
Indeed, in the polyurethane sector, formulators
had already started to assess how they could
reduce reliance on ODS by increasing the
amount of co-blowing being contributed by the
isocyanate/water reaction and its generation of
in-situ CO2.
Since hydrocarbons were already less
expensive than any of the fluorocarbon
alternatives, there was clearly a commercial
incentive to maximise their use. However,
for small and medium enterprises (SMEs)
in particular, the economies of scale were
insufficient to justify the capital investment.
Even where the incremental cost of the
transitions was funded by the Multilateral
Fund (i.e. for developing countries operating
under Article 5 of the Montreal Protocol) the
investment costs were often prohibitive and
34
understandable threshold limits prevented These issues were probably at their height
investment in hydrocarbon technologies. The in the early years of the decade (i.e. 2002-
default technology choice in this instance 2006) when many technology decisions were
became HCFC-141b. The Cost Paper being made and led to an uptake in the use of
prepared by the Multilateral Fund Secretariat in hydrofluorocarbons (HFCs) as replacements for
2008 (UNEP/OzL.Pro/ ExCom/55/47) provides HCFCs, even though it was known that they
important background on this subject and had relatively high global warming potentials.
highlights the fact that more than 70 per cent The main HFCs that emerged to meet the
of all foam enterprises in Article 5 countries foam blowing need were HFC-134a and HFC-
had an annual CFC consumption below 40 152a for gaseous/frothing applications such
ODP tonnes per year. as extruded polystyrene, polyolefin and one
component PU foams, while HFC-245fa and
Most foam manufacturers in Article 5 countries
HFC-365mfc/227ea emerged for applications
have therefore found themselves in something
reliant on liquid blowing agents, such as the
of a cul-de-sac. They have transitioned to
majority of polyurethane and phenolic foams.
a low-ODP solution in order to respond to
Again, cost and concern about the possibility
the original call of the Parties to the Montreal
of an eventual third transition led the industry
Protocol for CFC phase-out, but have no cost-
to minimise its uptake of HFC technologies
effective way out of HCFCs when it comes
and this was a significantly lower than 1:1
to the implementation of Decision XIX/6 on
replacement against HCFCs as is shown in the
accelerated HCFC phase-out. Although there
following graph:
is more time to make this second transition
than in developed countries (non-Article 5), the
technology choices are not always obvious,
particularly where thermal performance is
an on-going requirement. HFCs remain one
option, but their potential cost and availability
have remained a cause for concern.
Although the thermal efficiency of
hydrocarbon-based foams has improved in
recent years as a result of development focus,
foam manufacturers in developed countries
have still been challenged by three factors in
seeking to make the onward transition from
HCFCs to zero-ODP alternatives. These are:
• Insufficient economies of scale to
accommodate the safety requirements
associated with flammable blowing agents
(and, in the case of PU Spray Foam, an
overall technical constraint)
• Product flammability concerns in sensitive
markets
• Lack of guaranteed thermal performance
in areas where thermal performance is
critical
Global Trends in Blowing Agent Consumption by Type (1990-2014)
300000
Total HCs
Total HFCs
250000 Total HCFCs
Total CFCs
200000
CONSUMPTION (tonnes)
150000
100000
50000
0
1990 1992 1994 1996 1998 2000 2002 2004 2006 2008 2010 2012 2014
YEAR

4.6 Why HFCs can be Sub-optimal
Solutions for Climate
Recent analysis has shown that HFCs are
being used in a variety of foam technologies
globally, these include, but are not limited to:
• PU Steel-faced panels (both continuously
and discontinuously produced)
• PU Spray Foam
• Extruded polystyrene foams (XPS)
• PU Integral Skin foams and Shoe Soles
• PU Appliance Foam (particularly in North
America)
Section 3 of this Guidance has already
provided an overview of the factors to be
considered when evaluating the climate impact
of technologies and making comparisons
between them. One of the lessons to be drawn
from such analyses is that climate impact
is driven by emissions and not technology
choice per se. Therefore, it is important to
ensure that, when considering the use of
HFCs, due account is taken of any measures
that may be implemented across the lifecycle
of the product to limit emissions. For foams,
this could include capture of blowing agents
during the production process or end-of-life
management provisions.
UNEP DTIE Foam Sourcebook - 2010
The use of HFCs could therefore be justified Assessing the applications listed earlier in
on an on-going basis if it could be guaranteed which HFCs are being used currently, it can
that emissions were largely avoided from all be seen that the use in PU integral skin and
phases of the lifecycle. Equally, there would shoe soles might be the hardest to defend on
be a case for the on-going use of HFCs if the climate grounds, since they are totally emissive
incremental energy efficiency advantages could and the use of HFCs does not contribute to
be quantified and would result in the lower any thermal benefit..
level of overall greenhouse gas emissions,
For the thermal insulation products, the case
when corrected for the appropriate global
might be greater, although the relative high
warming potential of the HFCs used. To
emissions associated the extruded polystyrene
make this judgement, it is necessary to have
foam manufacturing process (see the IPCC
access to the comparative impacts of different
table below) makes the case harder to justify,
blowing agent types. Although this is covered
particularly when HFC-134a is the blowing
further in the next Section, the following Table
agent of choice, since this has a GWP of 1410.
extracted from the IPCC/TEAP Special Report
on Ozone and Climate is likely to be helpful at
this juncture:
Apart from the global warming potential of the
blowing agent itself, one of the other factors
that needs to be considered alongside the
energy efficiency assessment is the carbon
intensity of the fuels used to heat and/or
cool. This can be particularly important where
electrical heating/cooling is applied routinely,
since it will be the fuel used to generate the
power that will count in this case.
35
 Environmental Characteristics of various Fluorocarbons

Gas GWP for direct radiative GWP for indirect radiative forcing Lifetime (years) UNFCCC
forcing a
(Emission in 2005 ) b
Reporting GWPc

CFCs
CFC-12 10,720 ± 3750 -1920 ± 1630 100 n.a.d
CFC-114 9880 ± 3460 Not available 300 n.a.d
CFC-115 7250 ± 2540 Not available 1700 n.a.d
CGC-113 6030 ± 2110 -2250 ± 1890 85 n.a.d
CFC-11 4680 ± 1640 -3420 ± 2710 45 n.a.d

HCFCs
HCFC-142b 2270 ± 800 -337 ± 237 17.9 n.a.d
HCFC-22 1780 ± 620 -269 ± 183 12 n.a.d
HCFC-141b 713 ± 250 -631 ± 424 9.3 n.a.d
HCFC-124 599 ± 210 -114 ± 76 2.8 n.a.d
HCFC-225cb 586 ± 205 -148 ± 98 5.8 n.a.d
HCFC=225ca 120 ± 42 -91 ± 60 1.9 n.a.d
HCFC123 76 ± 27 -82 ± 55 1.3 n.a.d

HFCs
HFC-23 14,310 ± 5000 ~0 270 11,700
HFC-143a 4400 ± 1540 ~0 52 3800
HFC-125 3450 ± 1210 ~0 29 2800
HFC-227ea 3140 ± 1100 ~0 34.2 2900
HFC-43-10mee 1610 ± 560 ~0 15.9 1300
HFC-134a 1410 ± 490 ~0 14 1300
HFC-245fa 1020 ± 360 ~0 7.6 _c
HFC-365mfc 782 ± 270 ~0 8.6 _c
HFC-32 670 ± 240 ~0 4.9 650
HFC-152a 122 ± 43 ~0 1.4 140

PFCs
C2F6 12,000 ± 4200 ~0 10,000 9200
C6F14 9140 ± 3200 ~0 3200 7400
CF4 5820 ± 2040 ~0 50,000 6500

Halons
Halon-1301 7030 ± 2460 -32,900 ± 27,100 65 n.a.d
Halon-1211 1860 ± 650 -28,200 ± 19,600 16 n.a.d
Halon-2402 1620 ± 570 -43,100 ± 30,800 20 n.a.d

Other Halocarbons
Carbon tetrachloride (CCl4) 1380 ± 480 -3330 ± 2460 26 n.a.d
Methyl chloroform (CH3CCl3) 144 ± 50 -610 ± 407 5.0 n.a.d
Methyl bromide(CH3Br) 5 ± 2 -1610 ± 1070 0.7 n.a.d

a
Uncertainties in GWPs for direct positive radiative forcing are taken to be +35% (2 standard deviations) (IPCC, 2001).
b
Uncertainties in GWPs for indirect negative radiative forcing consider estimated uncertainty in the time recovery of the ozone layer as well as uncertainty in the negative radiative forcing
due to ozone depletion.
The UNFCCC reporting guidelines use GWP values from the IPCC Seconf Assessment Report (see FCCC/SBSTA/2004/8, http://unfccc.int/resource/docs/2004/sbsta/08.pdf).
c

d
ODSs are not covered under the UNFCCC.
The IPCC Second Assessment Report does not contain GWP values for HFC-245fa and HFC-36mfc. However, the UNFCCC reporting guidelines contain provisions relating to the
e

reporting of emissions from all greenhouse gases for which IPCC-assessed GWP values exist.

36
UNEP DTIE Foam Sourcebook - 2010

37
 DEFAULT EMISSION FACTORS FOR HFC-134A AND HFC-152A USES
(FOAM SUB-APPLICATIONS ) (IPCC, 2005)

Sub-Application Product First Year Loss % Annual Loss % Maximum

Life in years Potential
End-of-Life Loss %

Polyurethane – Integral Skin 12 95 2.5 0

Polyurethane – Continuous Panel 50 10 0.5 65
Polyurethane – Discontinuous Panel 50 12.5 0.5 62.5
Polyurethane – Appliance 15 7 0.5 85.5
Polyurethane – Injected 15 12.5 0.5 80
One Component Foam (OCF) a 50 95 2.5 0
Extruded Polystyrene (XPS)b - HFC-134a 50 25 0.75 37.5
Extruded Polystyrene (XPS) - HFC-152a 50 50 25 0
Extruded Polyethylene (PE) a 50 40 3 0

a
Source: [Ashford and Jeffs, ETF, 2004] assembled from UNEP FTOC Reports 1998, 2002.

b
Vo and Paquet: An Evaluation of Thermal Conductivity over time for Extruded Polystyrene Foams blown with HFC-134a and HCFC-142b

* Emission factors predicted for the products and processes identified.

Source: IPCC 2006 Reporting Guidelines Table 7.6

Even where the emission profile is relatively HCs. This is despite the fact that such panels
controlled, product groups that do not need have the potential for recovery and destruction
to rely on HFCs for process or property and end-of-life and are relatively non-emissive
reasons are continuing to move away from during their other life cycle phases (see the
these blowing agents. A prime example is IPCC table above)
the continuous panel industry in the United
Kingdom, where the fire performance
requirements of the industry have now been
largely met by hydrocarbon technologies,
thereby facilitating a transition from HFCs to

38
 UNEP DTIE Foam Sourcebook - 2010

DEFAULT EMISSION FACTORS FOR HFC-245FA/HFC-365MFC/HFC-227EA USES

(FOAM SUB-APPLICATION)

Sub-Application Product First Year Loss % Annual Loss % Maximum

Life in years Potential
End-of-Life Loss %

Polyurethane – Continuous Panel 50 5 0.5 70

Polyurethane – Discontinuous Panel 50 12 0.5 63
Polyurethane – Appliance 15 4 0.25 92.25
Polyurethane – Injected 15 10 0.5 82.5
Polyurethane – Cont. Block 15 20 1 65
Polyurethane – Disc. Block for pipe sections 15 45 0.75 43.75
Polyurethane – Disc. Block for panels 50 15 0.5 60
Polyurethane – Cont. Laminate / Boardstock 25 6 1 69
Polyurethane – Spray 50 15 1.5 10
Polyurethane – Pipe-in-Pipe 50 6 0.25 81.5

Sources: [Ashford & Jeffs ETF, 2004] assembled from UNEP FTOC Reports 1998, 2002

* Emission factors predicted for the products and processes identified.

Source: IPCC 2006 Reporting Guidelines Table 7.7

In summary, therefore, it can be seen that, GWPs. This highlights the importance of
while HFCs are still a current technology treating each technology option on its merits
selection option, they may be sub-optimal and avoiding generalisations about classes of
for a significant number of applications. Care compounds. The next Section deals in more
therefore needs to be taken in advocating their detail with blowing agents currently available or
selection. In making these comments, it should likely to be available in the near future.
be noted that they apply to the currently
available ‘saturated’ HFCs. There are a further
generation of ‘unsaturated’ HFCs (sometimes
referred to as ‘HFOs’) which may still formally
classify as HFCs but will have much lower

39
Section 5.
General review of alternative
blowing agents

“Alternatives exist for all current HCFC

applications and the majority of these
have low global warming potentials”

40
 UNEP DTIE Foam Sourcebook - 2010

Section 5.
General review of
alternative blowing
agents
The major blowing agents being commercially
used as substitutes for HCFCs in the foam
sector, or being considered for commercial
introduction in the short-term, are shown in
the sub-sections that follow – each of which
contains a table with basic properties and
supply information.
These tables are supplemented by descriptive
paragraphs which provide technical information
on the blowing agents themselves and some
information on usage patterns and commercial
availability. It should be noted that there are
no references to regulatory constraints in this
Section. While the impact of ODS regulations
is probably well known to the reading audience
and does not require further iteration here, it
might be useful to note, for example, that other
environmental factors, such as classification as
volatile organic compounds (VOCs) may have
a bearing on local acceptance. The reader is
therefore encouraged to make a full evaluation
of the national and local circumstances when
choosing blowing agent options.
5.1 Hydrocarbons (both directly The major potential drawback with the
hydrocarbon family is their flammability. This
added and pre-blended with polyol)
can have impact on both the capital costs for
These five major blowing agents (cyclo-
processing (to ensure that safety is properly
pentane, n-pentane, iso-pentane, iso-butane
engineered) and on product properties.
and n-butane) continue to be the primary
For some product types, the impact of
hydrocarbon alternatives offered to the foam
hydrocarbon inclusion on fire performance
sector. The boiling point range is sufficiently
is less than for others. These aspects are
wide to allow for gaseous blowing agent
covered in more depth in Section 7.
processes such as extruded polystyrene and
one-component polyurethane systems to From a processing perspective, the
be served by the ‘butanes’, while the higher flammability of hydrocarbons is at its most
boiling point, liquid applications can be served acute when the blowing agents are used in
by the ‘pentanes’. concentrated form at the foam manufacturing
premises. This can be particularly problematic
A significant further advantage of the
for smaller enterprises. Efforts have been
hydrocarbon family is that they can easily
made to establish whether the pre-blending
be blended to provide a combination of
of hydrocarbons into polyols at systems
properties. For example, it has always
houses can limit this flammability and provide
been known that cyclo-pentane offered
a less hazardous material at the point of
better thermal performance (lower gaseous
foam manufacture. Since early experiences
conductivity) than the other hydrocarbons,
(during the CFC phase-out) produced
but its boiling point is relatively high leading to
mixed results, the matter has been taken
lower blowing efficiency and, in some cases,
up by the Multilateral Fund together with the
poorer processing. This led to the realisation
Implementing Agencies and a pilot project has
that blending cyclo-pentane with iso-pentane
been sponsored. In view of the large number
could retain the overall thermal properties while
of Small Medium Enterprises (SMEs) involved,
lowering the overall boiling point and improving
the further penetration of hydrocarbon-based
the processing characteristics – the latter, in
blowing agents into the PU sector during
turn, leading to lower densities. In addition,
HCFC-phase-out will depend very much on
the cost of iso-pentane is generally lower than
this outcome of this work.
for cyclo-pentane and cost savings could be
achieved. This, therefore, led to the ‘birth’ of
what became known as the “cyclo-iso blends”.

Cyclo-Pentane n-Pentane Iso-Pentane Iso-Butane n-Butane

Chemical Formula (CH2)5 CH3(CH2)3CH3 CH3CH(CH3)CHCH3 CH3CH(CH3)CH3 CH3CH2CH2CH3

Molecular Weight 70.1 72.1 72.1 58.1 58.1
Boiling Point ( 0C ) 49.3 36 28 -11.7 -0.5
Gas Conductivity (mW/mK @ 10 C) 0
11.0 14.0 13.0 15.9 13.6^
Flammable Limits in Air (vol.%) 1.4-8.0 1.4-8.0 1.4-7.6 1.8-8.4 1.8-8.5
TLV or OEL (ppm) (USA) 600 610 1000 800 800
GWP (100 yr time horizon) <25* <25* <25* <25* <25*

Chevron Phillips Exxon Mobil Exxon Mobil Chevron

Key Producers
ExxonMobil Dow Haltermann Dow Haltermann Bayer
Dow Haltermann Chevron Phillips Chevron Phillips Huntsman
Maruzen Shell Shell Phillips
Haldia Petrochem Maruzen Jilin Jinlong Quhua Yonghe
Yixing City Changjili Beijing Yanshan Productos Quimicos Chemical
Productos Quimicos Productos Quimicos Coin Jinling
Coin Coin Petrochemical

^ Measured at 00C * Precise figure varies according to local atmospheric conditions

41
5.2 Liquid Carbon Dioxide
Carbon Dioxide (CO2) is a gas at normal
temperature and pressure (triple point occurs
at 5.11 bar pressure and – 56.60C) and is only
viable as a blowing agent when it is supplied
under pressure (see the Phase Diagram
below).
Liquid CO2 has found widespread use,
particularly in Europe, in the extruded
polystyrene sector, but has also offered
opportunities in other product/process types.
The attraction of using CO2 is its relative
inertness and also its low global warming
potential (GWP=1).
Handling gases at pressure, however, requires
significant engineering resources and one of
the challenges of rolling out such technologies
to a wider processing base has been the ability
to control the foaming reaction in a consistent
way, when ambient conditions may vary
substantially.
The use of liquid CO2 is therefore limited to
those processes which lend themselves to
gaseous blowing agents and have a sufficiently
high degree of in-built engineering to be robust
in the field of operation.
P (atmos)
5.3 In-situ Carbon Dioxide (water
blown foams)
All of the attractive properties of CO2
highlighted in Section 5.2 are, of course,
available to foam manufacturers no matter
what source of carbon dioxide is used. For PU
foam manufacturers, the opportunity exists to
take advantage of the presence of isocyanate
in the formulation to generate carbon dioxide
in-situ. This possibility is created by the
fact that excess isocyanate can be used to
generate CO2 through a reaction with water –
which can be added as required.
This process bypasses all of the processing
complications that arise from the use of liquid
CO2. However, it does bring with it a number of
complications of its own. These include:
• Isocyanate is typically a more expensive
component of the formulation and using
excess of it as a means to generate CO2 is
often not an efficient use of the material
• Formulations that are high in isocyanate
tend to be highly cross-linked and this can lead
to less resilience and poorer cell structure
• The generation of CO2 in-situ means that
its availability is governed by the chemical
reaction itself. In some instances, this can lead
5.4 Oxygenated Hydrocarbons
(Methyl Formate, Methylal and
Dimethyl Ether)
As the industry has searched for cost-effective
solutions to HCFC substitution, the potential
for using oxygenated hydrocarbons has
emerged. These had broadly been ignored in
non-Article 5 countries because the economies
of scale were sufficient to allow the direct use
of hydrocarbons. However, substances such
as methylal had been commercially available
for a considerable time, based on its use in
other areas.
The emergence of methyl formate (typically
marketed as Ecomate®) has brought this
class of compounds to centre-stage, although
there is still considerable debate about how
wide a range of applications it can serve. In
parallel with pre-blended hydrocarbons, methyl
formate has therefore become the subject of
a Multilateral Fund supported pilot project to
explore the capabilities of this material. The
outcomes of this work will be important, since
methyl formate does, on paper at least, meet
the majority of criteria for an environmentally
sound alternative to HCFCs as is shown in the
following table.

100
to less efficient blowing and densities can be
higher than intended.
90
80 PC
70
60

50
• Since CO2 is a small molecule it tends to
40 migrate from the cells of the foam rapidly.
30 Where no other blowing agent is present this
LIQUID
can result in loss of cell pressure and potential
20
shrinkage (or other forms of poor stability).
To compensate for this, higher densities may
SOLID

10 need to be targeted intentionally.

9
8

6
7
GAS Liquid CO2 normally the case that (CO2) water
5 PT blown foam formulations are reserved for some
4
of the less demanding roles.
3

1
0
-60 -50 -40 -30 -20 -10 0 +10 +20 C

42
 UNEP DTIE Foam Sourcebook - 2010

The US Environmental Protection Agency
has evaluated methyl formate and related
substances in its Significant New Alternatives
Program (SNAP) and, in the absence of data
to the contrary, has suggested that their global
warming potential is negligible. Di-methyl ether
is the only one for which a GWP is cited by the
Inter-Governmental Panel on Climate Change
(IPCC) and the Fourth Assessment Report
(AR4) provides a value of 1. However, as with
all short-lived compounds, there is a degree of
uncertainty dependent on local atmospheric
circumstances. For this reason, the authors
have grouped methylal and methyl formate Di-methyl ether is placed to serve the gaseous
with other hydrocarbons at <25. blowing agent market in view of its boiling
point. It has an established market as an
Methylal has been typically used as a co-
aerosol propellant and capacity is growing
blowing agent rather than as a blowing agent
rapidly based on its potential as an alternative
in its own right. It has been marketed primarily
to Liquid Petroleum Gas. The product is
within the thermoplastic foam sector (extruded
already used as a propellant/blowing agent
polystyrene and polyolefin) as a co-blowing
in one component foams and is also being
agent with HFC-134a to date. However,
evaluated for extruded polystyrene
the literature suggests that polyol miscibility
in polyurethane systems may provide a
processing advantage, as well as better skin
forming properties (important for integral skin
foams).

Methylal Methyl Formate Di-methyl Ether

Chemical Formula CH3OCH2OCH3 CH3(HCOO) CH3OCH3

Molecular Weight 76.1 60.0 46.07
Boiling Point ( 0C ) 42 31.5 -24.8
Gas Conductivity (mW/mK @ 15 C) 0
Not available 10.7 (@ 25 C)
0
15.5
Flammable Limits in Air (vol.%) 2.2-19.9 5.0-23.0 3.0-18.6
TLV or OEL (ppm) (USA) 1000 100 1000
GWP (100 yr time horizon) <25* <25* 1

Spectrum Chemicals BOC Multiple Chinese producers

Key Producers
Alcan International Foam Supplies Air Liquide
Kimbester (China)
Caldic
Lambiotte & Cie

* These products are sometimes cited as ‘zero-GWP’ or ‘negligible GWP’ but see narrative below

43
5.5 Chlorinated Hydrocarbons
(Methylene Chloride, Trans-1,2
di-chloroethylene and
2-chloropropane)
Methylene Chloride became a widely used
substitute for CFCs as an auxiliary blowing
agent in flexible and moulded polyurethane
foams throughout the 1990s. However,
there remains some debate about the health
effects of methylene chloride exposure which
has led to significant regional variations in
uptake. The primary area of contention has
been the potential of methylene chloride as
a carcinogen. This has led to slightly differing
treatments in North America and Europe with
the latter tending to be more conservative in
its approach. The need for care in managing
exposure is reflected in the relatively low
threshold limit value (TLV) range of 35-100
ppm.
Although, methylene chloride is well
established as an auxiliary blowing agent,
its use, in general, is on the decline. The full
characteristics of methylene chloride, trans-
1,2-dichloroethylene and 2-chloropropane are
shown in the following table.
In similar fashion to methylal, trans-1,2-
dichloroethylene has not been used
significantly as a blowing agent in its own right,
but has tended to be used as a co-blowing
agent in order to modify the processing
characteristics of other blowing agents. It
has found a particular niche in modifying the
froth foaming behaviour of HFC-134a and
HFC-245fa, as well as enhancing the blowing
efficiency of these materials.
2-chloropropane (also known as iso-propyl
chloride) has been used only to a limited extent
as a blowing agent. Most notably it has found
use in the manufacture of phenolic foams in
Europe for some years. It is understood that
preliminary evaluation has also occurred in
polyurethane foam systems, although the
outcome of tat work is not known.
Despite their chlorine content, all three of these
compounds, and many like them, escape from
consideration under the Montreal Protocol
because of their very short atmospheric
lifetimes which make it that the respective
molecules do not reach the stratosphere
and trigger ozone depletion. However, as
with all short-lived halogenated substances,
care needs to be taken to evaluate the
impact of breakdown products created in the
troposphere

Methylene Chloride Trans-1,2-dichloroethylene 2-chloropropane

Chemical Formula CH2Cl2 ClHC=CHCl CH3CHClCH3

Molecular Weight 84.9 97 78.5
Boiling Point ( 0C ) 40 48 35.7
Gas Conductivity (mW/mK @ 100C) Not available Not available Not available
Flammable Limits in Air (vol.%) None 6.7-18 2.8-10.7
TLV or OEL (ppm) (USA) 35-100 200 50
GWP (100 yr time horizon) Not available <25 Not available

Multiple Sources Arkema Alfa Aesar

Key Producers

* These products are sometimes cited as ‘zero-GWP’ or ‘negligible GWP’ but see narrative below

44
 UNEP DTIE Foam Sourcebook - 2010

5.6 Saturated HFCs
The case for and against the use of saturated
HFCs has already been covered substantially
in Sections 4.5 and 4.6 of this Sourcebook.
Although uptake has been less in developed
countries than had been anticipated by a
number of stakeholders, the potential for their
use in developing countries remains very real
and potentially damaging to efforts to reduce
climate impact through the early phase-out
of HCFCs. The following table illustrates the
specific characteristics of the commonly
available HFCs and indicates that the range
of boiling-points is sufficient to meet most of
the requirements of the foam manufacturing
industry.
HFC-227ea is seldom used on its own for does depend considerably on the price of
foam-blowing purposes, but is usually co- isocyanate prevailing at the time. In addition,
blended with HFC-365mfc at varying levels to the co-blowing strategy does reduce the
modify the flammability characteristics of the potential impact of the direct emissions of
latter. Similarly, HFC-152a is normally used as blowing agent from the foam.
a co-blowing agent with HFC-134a in order to
enhance blowing efficiency. However, despite
its relatively low GWP, its partial flammability
and high cell wall permeability make it less
suitable as a blowing agent on its own. There
is some recorded use of HFC-152a on its
own in XPS, but this is only where long-term
thermal performance is less critical
As noted in Section 4.5, there has been a
strong tendency in polyurethane foam sectors
to co-blow HFC-based foams with CO2 (water)
by taking advantage of the isocyanate/water
reaction. This can offset the increased cost
of HFCs, but the magnitude of the offset

HFC-134a HFC-152a HFC-245fa HFC-365mfc HFC-227ea

Chemical Formula CH2FCF3 CHF2CH3 CF3CH2 CHF2 CF3CH2 CF2 CH3 CF3CHF CF3
Molecular Weight 102 66 134 148 170
Boiling Point ( 0C ) -27 -25 15.3 40.2 -16.5
Gas Conductivity (mW/mK @ 100C) 12.4 14.3* 12.5* 10.6* 11.6
Flammable Limits in Air (vol.%) None 3.9-16.9 None 3.8-13.3 None
TLV or OEL (ppm) (USA) 1000 1000 N/A N/A 1000
GWP (100 yr time horizon)^ 1410 (1300) 122 (140) 1020 782 3140 (2900)

Arkema DuPont Honeywell Solvay Solvay

Key Producers
DuPont Solvay Central Glass
INEOS
Honeywell
Solvay
Chinese Producers

* Measured at 24-250C ^ As in SROC (2005) with Second Assessment Report (SAR) values in Brackets, where appropriate

45
5.7 Unsaturated HFCs (HFOs)
This class of compounds represents an
emerging group of potential blowing agents
which spans the blowing agent range required
for foam manufacture. They exhibit a number
of the characteristics also displayed by
saturated HFCs, but have considerably lower
GWPs. The prime reason for these lower
values relates to the shorter lifetime of the
molecules in the atmosphere, which itself is
caused by the presence of a double bond
between adjacent carbon atoms (the so-called
unsaturation).
Since these compounds are still in the state
of development and early commercialisation,
there is often incomplete information available.
This is sometimes because testing is still in
progress, but, more often, because companies
are seeking to maintain confidentiality
while establishing their respective patent
positions. The most advanced, in terms of
commercialisation and disclosure, is
HFO-1234ze which has already been
introduced into the European market as a
replacement option for HFC-134a in the PU
one-component foam (OCF) market. The
product has a GWP of 6 in this instance.
The following table also illustrates the various
other compounds that are believed to fall in
this class.
Further disclosures are expected on these and
other potential blowing agents over the next
months, but it is clear that, despite some very
promising characteristics, they are unlikely
to be available in sufficient time to meet the
early stages (pre-2015) of the HCFC phase-
out required under Decision XIX/6. This is
particularly frustrating, since compounds such
as FEA-1100, HBA-2 and AFA-L1 seem to
have the potential of replacing HCFC-141b,
which will be amongst the first technologies
to be phased-out under ‘worst-first’ principle
mandated by the Decision.

HFO-1234ze FEA-1100 HBA-2 AFA-L1

Chemical Formula Trans- CF3CH=CHF Cis- CF3-CH=CH-CF3 Undisclosed Undisclosed

Molecular Weight 114 164 Undisclosed Undisclosed
Boiling Point ( 0C ) -19 32 15.3<T<32.1 10.0<T<30.0
Gas Conductivity (mW/mK @ 100C) 13.0 10.7 Not Reported 15.9
Flammable Limits in Air (vol.%) None to 28 C^
0
None None None
TLV or OEL (ppm) (USA) Unpublished 9.7 Undisclosed Undisclosed
GWP (100 yr time horizon) 6 5 <15 <15

Honeywell DuPont Honeywell Arkema

Key Producers

^ Flame limits of 7.0-9.5 at 300C are quoted

46
UNEP DTIE Foam Sourcebook - 2010

47
Section 6.
Decision-making process

“When developing country experience is

limited, a balanced assessment of available
information is critical”

48

Section 6.
Decision-making process
6.1 Establishing Technical Feasibility
and Economic Viability
The technical feasibility of a blowing agent
technology will depend on a number of factors
which will include:
• The chemistry of the foam formulation
being processed
• The existing (or future) foam processing
equipment being proposed
• The quantity of foam being manufactured
and sold each year
• The application of the foam and the local
standards pertaining
• Experience already gained by others both
internationally and locally in similar processes
and applications
Chemistry of the foam formulation
being processed
Foam formulations are selected and optimised
for a variety of differing purposes. For rigid
foams, these can include such aspects as
reaction to fire, mechanical strength and
resilience. For flexible foams these might be
matters such as softness and elastic response.
Inevitably, the relationship between these
properties and density of foam required to
deliver them, becomes a key aspect of the
assessment, making the inter-linkage between
technical and economic components of the
decision-making process almost unavoidable
from the outset. The formulation itself
could also require additional components to
accommodate certain blowing agent solutions
(e.g. flame retardants) and these can affect
the overall economic viability of a potential
solution.
Existing (or future) foam processing
equipment being proposed
Every project will have its constraints with
respect to equipment. These may be
imposed through the existing equipment at
hand, particularly if no capital is available to
support the proposed technology transition.
Alternatively, where capital is availa ble,
it is likely that the budget will be capped.
This may be on an absolute basis or on a
level of investment per unit quantity of foam
manufactured or blowing agent used. Either
way, there may be the potential necessity to
make compromises in order to accommodate
the equipment that can be made available.
Quantity of foam being manufactured
or sold each year
Where capital investments need to be made,
the cost-effectiveness of the investment
will depend on the quantity of foam being
produced on the equipment currently and
will also need to take into account any future
trends that are expected. Although the most
cost-effective investment is not always the
best, it is likely that a threshold will exist (in
US$ per unit of production) above which,
the investment is viewed as non-viable.
Conversely, the same assessment might be
made by establishing the minimum amount
of foam that would need to be manufactured
annually to support the investment.
UNEP DTIE Foam Sourcebook - 2010
Application of the foam and the local
standards pertaining
There is no value in producing foam in the
most cost-effective manner if it is not fit-
for-purpose in its intended application. In
some instances, this may not be established
immediately but could emerge only with time.
In order to combat this risk, attempts are often
made to mimic the long-term requirements on
the foam in an accelerated fashion (e.g. ageing
at elevated temperatures). This approach
serves to provide a view of the likely future
performance of the foam. However, since
the predictive capabilities of such techniques
always have their limitations, the tendency
is naturally to be a little more conservative
in the deployment of new technologies. In
some instances, local standards will also
introduce a level of conservatism in order to
ensure fitness-for-purpose. Enterprises need
to satisfy themselves that risk is mitigated to
the extent possible, but that the final approach
is not so over-cautious as to rule out perfectly
acceptable alternatives. This is usually an issue
of expert judgement and will involve a number
of local factors as well as generic technology
issues.
49
Experience already gained by others
both internationally and locally in
similar processes and applications
One of the primary factors in providing
confidence about technology selection
emerges is knowledge that a technology
has been deployed successfully elsewhere –
particularly if the circumstances are similar to
those pertaining to the proposed technology
transition. Accordingly, an enterprise needs to
be alert to the information available to it from a
number of sources. This can include any of the
following:
• International Foam Conferences
• Assessments contained in the UNEP
Foams Technical Options Committee Reports
• Advice and information from National
Ozone Units
• Local trade associations
• Periodic regional workshops convened by
one or more Implementing Agencies
• Supplier Literature (particularly where this
contains case studies)
• Supplier Literature (particularly where this
contains case studies)
These sources take on increased importance
when technology transitions are contemplated,
particularly if the pace of technology
development is rapid. In this context, there is
no doubt that the implementation of Decision
XIX/6 has brought about challenges that were
previously unforeseen. As technology suppliers
respond to these challenges, the level of
offerings in the market place increases – often
specifically tailored to the needs of developing
country enterprises and markets. In these
circumstances, good market intelligence is a
critical part of the decision-making process.
50
6.2 Evaluating Safety Aspects and However, apart from climate impacts, there
can be a number of other environmental
Environmental Impact
considerations. These include:
There are a number of examples where the
some excellent technological options have • Impact on low level ozone formation
been ruled out or, at least demoted, because (usually associated with VOCs)
of their safety aspects and/or environmental
• Environmental (or human) toxicity of
impacts. For a long period, HCFC-123 was
atmospheric breakdown products
seen as a very promising replacement for
CFC-11 as a foam blowing agent (low ODP Decision XIX/6 is careful in its language to
and GWP) but was eventually ruled out ensure that the evaluation process includes
because of its intrinsic toxicity to man. this wider perspective when it encourages
Parties to the Montreal Protocol to:
Evaluating safety is a complex issue and
involves the assessment of risk, as defined ‘…….promote) the selection of alternatives to
by the intrinsic hazard of a chemical and HCFCs that minimise environmental impacts,
the statistical likelihood of exposure. Even in particular impacts on the climate, as well
hazardous chemicals can be handled safely as meeting other health, safety and economic
where the solution can be engineered to considerations’.
avoid exposure. An example would be the
However, seldom does one technology
regular handling of petroleum on a fuel station
minimise all health, safety and environmental
forecourt. However, for foam, the fact that
impacts at the same time and there is therefore
many blowing agents remain in the foam
a value judgement to be made between
after manufacture and slowly diffuse during
them. For HCFC alternatives, some criteria
the use phase, means that having intrinsically
are absolute (e.g. zero ODP), while others are
hazardous substances as blowing agents is
graduated factors, such as embodied energy
usually not tolerable. For this reason, it is only
and(GWP. When selecting a technology it
in exceptional circumstances that such an
is therefore important to identify the non-
option would be contemplated. Toxicity testing,
negotiable elements and use them for
in particular, is therefore a high priority for
screening purposes before evaluating these
potential blowing agents and enterprises would
graduated factors. This process is shown
be cautioned against choosing a technology
schematically in Section 6.4.
where the toxicity of the blowing agent has not
already been fully characterised.
Section 3 of this Sourcebook has already
addressed the evaluation of environmental
impact of technology transitions as it relates
to the climate criterion. As noted there, three
separate parameters can contribute to the
overall impact. These are:
• Embodied (or embedded) energy
• Direct emissions of greenhouse gases
(particularly of those used as blowing agents)
• Indirect emissions of CO2 related to the
energy consumption of buildings or products
(where the energy saved by a foam can
reduce those emissions)

6.3 Assessing Cost Effectiveness
and Practicality
Cost effectiveness is another graduated factor
and can be assessed either in the context of:
I. Initial capital costs
II. On-going variable costs
III. A combination of the two
The appropriate choice for comparison often
depends on the size of the operation being
managed by the enterprise. Where the plant
throughputs are potentially high, a greater
degree of capital investment can be justified,
since the investment per unit of production
is still relatively low and may be recovered
by operational savings. However, where
plant throughputs are likely to be low, capital
investment might need to be minimised with
possible incremental cost being incurred at
the operational level. Of course, the best
option under any method of evaluation is one
that involves minimal capital cost and results
in operational savings. In practice, the basis
of comparison is a choice for the individual
investor. However, the key aspect to bear in
mind is that competing technologies need to
be assessed using the same approach.
Care needs to be taken to ensure that cost
comparisons take into account all factors.
For example, a blowing agent may be more
expensive per kilogram purchased, but may
result in a foam that can deliver the required
properties at lower density. Such a blowing
agent may therefore be more cost effective
than a less expensive alternative, which does
not have the same capability. The improved
cost-effectiveness arises through the fact
that less of the overall chemical formulation is
needed.
UNEP DTIE Foam Sourcebook - 2010
If cost effectiveness is a graduated factor, then
some aspects of practicality are absolute in
their nature. For example, a key parameter
in making technology selections is the local
availability of the alternative blowing agent.
Although it may generally be viewed that
an alternative blowing agent is available
‘globally’, it is always worth checking the local
distribution network. Long shipment distances
can affect costs but, more importantly, can
jeopardise production continuity if supplies are
subsequently interrupted through lack of local
stocks.
Not only is availability an issue, but packaging
can also be a factor. This may be dictated
by the physical characteristics of the blowing
agent (e.g. boiling point) and also local
legislation. In some instances, local legislation
may limit the amount of the blowing agent that
can be stored in one place.
6.4 Summary Decision Tree
In summary, there are a number of absolute
and relative factors that combine to influence
technology selection. In some instances,
the process of selection can be iterative.
However, the following Decision Tree is an
attempt to provide some guidance on the
logical prioritisation of issues to be considered
if the maximisation of climate benefit is to be
achieved while seeking to be compliant with
the ozone objectives of Decision XIX/6.
51
 Commission further
pilot/demonstration trials to

START establish states of

candidate technologies.

YES

NO Can the project be NO

Is proven technology
delayedpending further
available today to phase-out
development and the country
current ODS usage?
YES
still meet ozone obligation?

YES TECHNICAL

NO
Does this technology
What would be the preferred
reflect the best environmental
choice for climate and
option, particularly
why is it not being chosen?
for climate?

YES COST

YES Is the cost-effectiveness NO

Is there a cost penalty
of additional carbon savings
associated with the choice
attractive when compared with
of this technology?
other climate options?
NO YES

NO YES

YES NO
Is a co-funding source
Confirm technology selection
available which can deliver
and implement, together with
parallel to the
an assessment of climate
Multilateral Fund ?
impact arising.

NO

YES
Should it be done
irrespective of cost?

NO

Revert to sub-
optimal climate technology
with prospect of further transition
later. Assess climate impact of
sub-optimal transitions.

52
UNEP DTIE Foam Sourcebook - 2010

53
Section 7.
Review of specific factors
influencing the selection of
alternative technologies at
application level

“Demands on blowing agents

vary substantially by process and
application, so specific information
is essential”

54
 UNEP DTIE Foam Sourcebook - 2010

Section 7.
Review of specific
factors influencing the
selection of alternative
technologies at
application level

As noted in the previous Section, there
are a number of key factors that influence
technology decision choices.
These are:
• Technical Feasibility
• Economic Viability
• Safety Aspects
• Environmental Impact
• Cost Effectiveness
• Practicality
Each of these factors will have a component
which is relevant to the technology sector as a
whole (e.g. PU Rigid Foams) and a component
which is relevant to the specific application
area (PU Spray) into which the new blowing
agent technology is being applied. In order to
avoid repetition this Section is structured in
such a way as to distinguish between those
factors that are related to the technology
sector as a whole and those that are specific
to an application. This means that the reader
may need to look into both the sub-Section
and the sub-sub-Section in order to gain a full
picture of the alternative technologies available.
7.1 PU RIGID FOAMS
The majority of rigid polyurethane foams are
required for insulating and semi-structural
purposes. The major characteristics required
for these applications are similar, but the
emphasis on each can vary. The following table
illustrates the primary required foam properties
and their relative importance in different
applications

7.1 Application Required Foam Property or Process Characteristic

Ease of Curing Insulating Mechanical Density Ozone Global

Processing Time Capability Strength Depletion Warming

Domestic Refrigerators/Freezers 444 444 444 444 44 444 44

Other Appliances 4 44 44 4 4 444 44 444 44

Transport and Reefers 4 4 44 444 44 4 444 44

Boardstock 444 444 444 444 44 444 444

Continuous Panels 444 444 44 444 44 444 44

Discontinuous Panels 4 4 44 44 444 44 444 44

Spray 44 44 44 444 44 444 444

Blocks 4 4 44 44 44 44 444 444

Pipe-in-Pipe 444 44 44 44 44 444 44

One Component Foams 44 444 4 44 44 444 444

55
Critical Foam Processing and
Product Properties
Each of the required foam properties and
processing characteristics are addressed in
turn below:
1. Ease of processing can be measured in
a variety of ways relating to both handling of
chemicals (polyol and isocyanate components)
and the action of those chemicals once
combined. In practice, often the most
significant factor is the capability of the
polyurethane system when fully mixed to flow
easily. This is particularly important for injection
processes, such as the filling of cabinets, but is
also very relevant when producing boardstock
and other laminate products, since thickness
tolerances and density distribution can all be
affected by flow characteristics. In the case
of cabinet filling, the combination of a well
flowing formulation and a well-designed cavity
should enable the optimum foam densities to
be achieved. This is an important element for
cost, strength and weight, as described under
sub-bullet 5.
56
2. Curing Time. During foaming, expansion
takes place through the vaporization of the
blowing agent and (in most formulations) the
generation of the carbon dioxide from the
water-isocyanate reaction. This expansion
process - accompanied by the progress of
the polymerization and the exotherm of the
reactions - results in the generation of an
increasing internal pressure. This process
exerts force upon the constraining surfaces,
which can be either the walls of the cabinet/
mould or the faces of a press (either static
or conveyor). The curing time is the time at
which the constraint can be removed without
further expansion of the foam beyond pre-
determined specifications. Since the curing
dictates the minimum residence time in either
a mould or laminating press, it is directly linked
to productivity, either through the number of
injections that can be achieved per hour or
the line speed that can be maintained while
achieving adequate cure. Of course, slow
curing time can be overcome by increasing the
number of moulds/jigs in use or by increasing
the length of a continuous laminator, but these
are major capital items and are not addressed
lightly.
3. Insulating Performance. Where polyurethane
foams are used for insulation purposes,
they contribute directly to the overall energy
consumption of the object into which they
are placed. This can range from a domestic
refrigerator or water heater, right through to a
building. The energy consumption is greatly
influenced by the insulating performance of the
foam, but other variables such as compressor
efficiency (in the case of refrigerators) and
boiler efficiency in the case of buildings can
be equally significant. In addition, heat gains
and losses through air movement are critical
contributors to overall energy performance.
Therefore, door gaskets on refrigerators,
draught excluders in buildings and the
behaviour patterns adopted by users are
all critical factors. The thermal conductivity
of the foam, measured on a sample cut
from a cross section of the foam, is a good
indication of the foam insulating performance
and is relatively easy to measure. However,
this also needs to be monitored over time
to identify any trends arising from blowing
agent losses from the cells. Typical thermal
conductivity values range from 0.018 W/mK to
0.04 W/mK when measured at normal ambient
temperatures. For a refrigerator, as a rule of
thumb and maintaining the other parameters
constant, when the foam thermal conductivity
is increased by a given percentage, the energy
consumption of the refrigerator increases in
value by half of that percentage.
 UNEP DTIE Foam Sourcebook - 2010

4. Mechanical Strength. During the lifetime of
a product the foam must remain dimensionally
stable. There is an important correlation
between the dimensional stability of closed
cell foams and the compressive strength. This
is primarily related to the degree of cross-
linking achieved. As the ambient temperature
changes, there are changes in internal
pressure within the foam caused by expansion
or contraction of the cell gas. In some
instances, the blowing agent’s condensation
or diffusion out of the cell leads to significant
pressure differences relative to prevalent
atmospheric conditions. If the foam is to be
dimensionally stable, the compressive strength
must be greater than this pressure difference.
For example, when the foam is cooled, a
pressure difference as large as 1 bar can occur
when the blowing agent gases are completely
condensed (OERTEL, 1994). There is a direct
relationship between the compressive strength
(or, more correctly, the overall mechanical
properties of the foam) and the foam density.
Higher density typically results in greater
compressive strength, but at the same time
higher cost. The foam should also be able to
act as an adhesive to the facing materials with
which it comes in contact (plastic and metal) in
order to form a dimensionally stable composite
structure (adhesion).
5. Foam Density. As mentioned in the above Blowing Agent Selection and how
point, there is a direct relationship between
it contributes to Required Foam
foam density and the strength foam properties,
particularly the compressive strength and Properties
dimensional stability. The foam density is As a consequence of the required foam
usually not uniform throughout the foam properties and the items mentioned earlier in
section, whether injected or laminated. It this Section, the key criteria for blowing agent
generally increases from a minimum value choice in PU rigid foam applications are as
located at the centre of the foam to a follows: (DEDECKER, 2002; OERTEL, 1994)
maximum figure at the skin. For this reason,
when referring to this property, the type of
density should be specified: Core and Skin
densities, as their names indicate, are the
values obtained at the centre and at the
skin of the section respectively. Meanwhile
Moulded or Average density reflects the global
density of the foam (i.e. total weight divided
by volume). In domestic refrigeration,
the moulded density is typically greater by
4 kg/m3 than the core density. When using
HCFC-141b as blowing agent the foam core
density varies from 31 to 33 kg/m3, equivalent
to a moulded density range of 35 – 37 kg/m3. In
other product types, densities can be as high
as 60 kg/m3. However, this reflects the role in
which the foam is placed. In general terms,
all manufacturers will seek for cost reasons
to minimise the density required to achieve a
desired performance objective and the blowing
agent choice will be a critical component in
achieving this objective.

Required Property Relevant Blowing Agent Property

1. Ease of Processing Flammability (the lower the better)

Boiling Point (significance depends on handling equipment)

Solubility in Formulation (the higher the better)

2. De-mould time Gas Thermal Conductivity*

Permeability through Cell Wall (the lower the better)**

3. Insulating Performance Gas Thermal Conductivity*

Permeability through Cell Wall (the lower the better)**

4. Mechanical Strength Solubility in Cured Matrix (the lower the better)

Boiling Point (the lower the better to improve cell pressure & avoid condensation)

5. Foam Density Blowing Efficiency (molecular weight)

6. Environmental GWP

ODP

* In the normal density range (30 – 40 kg/m3) the thermal conductivity of polyurethane rigid foam is primarily determined by the composition of the cell
gas. However, it should be noticed that the cell structure (morphology) also has a strong effect on the thermal conductivity (thermal radiation).
** Permeability is the combination of the gas diffusivity though the cell wall and its solubility in cured matrix

57
Using this analysis of desirable properties as a
guide for the selection of a blowing agent, the
following table provides an assessment of the
various blowing agent groups in the context of
these properties in order to assist technology
selection:
From this table it can be seen that each of the
blowing agent options provides some relevant
qualities in meeting the requirements, some of
them considerably better than the HFC-141b
being replaced. Performance can be further
optimised by blending blowing agents within
and between groups. However, this table
does not reflect some of the economic and
investment challenges faced. This aspect is
address in the next section.

Rating of Blowing Agent Types by Criterion

HCFC-141b Hydrocarbons Saturated Unsaturated Methyl Formate CO2 (water)

Blowing Agent Criterion HFCs HFCs (HFOs)

Flammability ++ + +++ ++/+++ +/++ +++

Boiling Point (Processing) ++ ++/+++ ++/+++ ++/+++ ++ ++
Solubility in Formulation +++ ++ +++ +++ ++ N/A

Gas Thermal Conductivity ++ +/++ ++/+++ ++/+++ ++ +

Permeability through Cell +/++ ++ +++ +++ +/++ +
Insolubility in cured matrix ++ ++/+++ +++ +++ ++ ++
Boiling Point ++ ++/+++ ++/+++ ++/+++ ++ +++
Blowing Efficiency ++ +++ ++ ++ +++ +++
Ozone Depletion Potential + +++ +++ +++ +++ +++
Global Warming Potential +/++ ++/+++ + ++/+++ +++ ++/+++

+++= Good ++= Fair += Poor

Economic Viability and Cost It can be seen that the challenge when
using hydrocarbons is to overcome the
Effectiveness Criteria
investment costs in order to benefit from the
As can be seen from the table above
attractive operating costs. Whether the use
hydrocarbons offer a number of technical
of hydrocarbons is possible or not is critically
advantages and, with the on-going
linked with the likely annual consumption
optimisation of formulations, now offer few
of blowing agent, both currently and in the
significant disadvantages. However, the key
future. In many plants in developed countries,
factor influencing the decision to choose
the decision is easily made because of the
hydrocarbons is the management of the
size and maturity of the markets served. In
flammability issue. Section 5.1 has already
essence, the market supports the investment.
addressed this issue and highlighted the
For emerging markets in developing countries,
fact that pre-blended hydrocarbons (i.e.
the situation is less certain and a high up-front
hydrocarbons pre-blended with polyols
investment carries greater risk. In addition,
are being evaluated as a possible way of
care needs to be taken to ensure that a tight
overcoming the engineering costs associated
operating discipline is established in order to
with the handling of hydrocarbons. However,
minimise the risk of accidents. The following
for the purposes of this Section, it is assumed
table on costs (WORLD BANK- OORG, 2009)
that the only commercial means available
gives an indication of the incremental capital
is to handle neat hydrocarbons at the
cost for a typical foam manufacturing facility
manufacturing facility. The following table
consuming 25-50 tonnes of blowing agent per
illustrates the impact that this has on the
annum:
decision process.
58
 UNEP DTIE Foam Sourcebook - 2010

Economic viability and cost effectiveness criteria

HCFC-141b Hydrocarbons Saturated Unsaturated Methyl Formate CO2 (water)

Blowing Agent Criterion HFCs HFCs (HFOs)

Investment Costs + +++ + + +/++ +

Operating Costs ++ + ++/+++ +++ +/++ ++/+++
Widespread Availability ++ ++ +/++ + +/++ +++
Potential for BA blends ++ ++/++ +++ ++ ++ +++

+++= High ++= Medium += Low

Typical Equipment Costs for PU Rigid Projects

Equipment Costs Costs Comments

One Dispenser Two Dispensers
(US$ ‘000)* (US$ ‘000)*

Storage tank, piping Up to 270 Up to 400

Optional 1 pre-mixer for 2

Pre-blending station 120 240
dispensers

Optional 1 day tank for 2

Day tanks 15 30
dispensers

Assuming high pressure

Metering unit retrofit 15-55 30-110
machines installed

Safety sensors 30-37 37-56

Exhaust 15-40 15-40

Grounding 7-15 7-15

Strongly dependent on factory

Civil work 7-15 15-30
location and layout

Installation & Commissioning 27-80 27-80

Totals (US$ ‘000) 230-640 390-995

*Conversion rate €1 = US$1.34

59
The pentane storage tank is major element
(30 - 40%) of the costs and, in certain
circumstances, could be replaced by the
pentane transport container. The second
largest elements are the pre-blending stations
and all the safety related components. So
far, formulations containing pre-blended
pentane have not been supplied but two
pilot projects have been proposed under the
Multilateral Fund (MLF) scheme to investigate
the feasibility/safety of such an operation.
The above costs assume that the enterprises
already have high pressure metering units.
If this is not the case, then high pressure-
metering units costing up to US$150,000 to
250,000 each would be required.
A point to consider is a potential increment in
the operation costs. Pentanes for the foaming
industry are not locally produced in many
developing countries and transportation costs
may be expensive. In additional to the local
cost difference of the blowing agents, the
following items deserve further consideration:
• The higher blowing efficiency of pentanes
due to their lower molecular weight. In
economic terms the benefit of this feature
depends on the relative local cost of the
other polyurethane raw materials compared
to HCFC-141b. If the PU raw materials are
more expensive, an incremental operating
cost will exist.
Application Area Methyl Formate Methylal
Domestic Refrigerators/Freezers
Other Appliances
Transport and Reefers
Boardstock
Continuous Panels
Discontinuous Panels
Spray
Blocks
Pipe-in-Pipe
One Component Foams
60
• The need to increase the foam density to must be taken about availability. This may
meet the dimensional stability requirements. vary by region, but also by the specific HFC in
question. It may be that the liquid HFCs
• More expensive polyols than those
(HFC-245fa and HFC-365mfc) are harder to
normally used with HCFC-141b may be
obtain locally because they have no parallel
required to match the foam insulating
use in the refrigeration sector, unlike HFC-134a
performance. In some specific cases a 3%
and HFC-227ea and HFC-152a.
increase in the local cost of the formulated
polyol has been anticipated. For reasons of commercialisation and
availability, it is unlikely that unsaturated
There may be additional expenditure to cover
HFCs (HFOs) will play a significant role in the
the provision of nitrogen for the blanketing of
replacement of HCFCs in developing countries
storage tanks and other tanks and pipes. The
in the rigid polyurethane foam sector. However,
cost will depend on the level of facilities already
other emerging technologies such as methyl
installed (WORLD BANK – OORG, 2009).
formate and methylal may have a significant
As indicated by the comparative table earlier in role to play over the same time-scale. The
this sub-Section, other blowing agent options following table illustrates the sectors in which
do not present the same investment cost these technologies have been (or will be)
challenge even though they may be flammable evaluated under the Pilot Project activities
to a lower degree in some instances (as was targeted at this sector:
HCFC-141b). The uptake of each of these
Local costs for these emerging alternatives
therefore hinges on issues of the cost of the
are still being established, although both
blowing agent itself, the impact of this cost
blowing agents are expected to be relatively
on overall formulation cost and, finally, on
competitively priced once available.
availability.
Apart from their high global warming
potentials, saturated HFCs are relatively costly
and would not typically be sustainable if it were
not for the fact that they can be successfully
co-blown with CO2 (water). For this reason
they do represent a genuine option the rigid
polyurethane foam market, although care
Pilot Project Scope for Methyl Formate and Methylal
4 4
4 4
4 4
4 4
4 4
4 4
4 4
 UNEP DTIE Foam Sourcebook - 2010

7.1.1 PU RIGID – Domestic

Refrigerators and Freezers

Refrigerators and refrigerators/freezers are

built by joining an outer case, normally painted
metal, and an inner plastic case which is
typically vacuum drawn from high impact
polystyrene (HIPS) or acrylonitrile-butadiene-
styrene (ABS). The void between the two
cases is then filled with rigid polyurethane
foam to create an integrated cabinet which
delivers the necessary insulation to maintain
the temperature differential at least energy
consumption (DESCHAGT, 2002). The
refrigerator door is built in the same way from
Carrousel type line for cabinets foam injection in domestic refrigeration
an inner thermoplastic sheet and a painted
metal outer sheet, with the space between
the two sheets also filled with rigid
polyurethane foam.

Historical trends in actual Blowing

Agent selection
The diagram below illustrates the historic
CFC11
transitional strategies that have been
undertaken in the domestic refrigeration
sector. It depicts the fact that the technology
transition has taken two separate and parallel
paths depending on the local/regional 50% reduced
attitude towards the use of hydrocarbons. CFC11
As is evidenced from the table in Section
7.1, the flammability of hydrocarbons is
their key weakness. However, some major
HCFC 141b c-pentane
appliance manufacturers identified relatively
early in their research of alternatives that
the flammability issue could be managed HFC134a
with appropriate equipment selection and
Cyclo/iso- c-pentane/
engineering safeguards. For others, particularly HFC245fa
in North America, either the challenge of
pentane Other
investment or local safety regulations meant
that the hydrocarbon option was viewed as
unmanageable, leading to the transitions to
HCFC-141b and onwards into saturated HFCs Source: Huntsman
(particularly HFC-245fa).

61
 0.1442
20.2 Iso-/N-Pentane Gen 1
0.1428
20.6
Iso-/N-Pentane Gen 2 0.1414
20.4
0.1401
Hydrocarbons 20.2 HFC134 0.1337

Thermal Conductivity, mW/mk 00C

For developing countries, where economies
of scale are sufficient and where investment
funding may be available through the
Multilateral Fund, the main route for
polyurethane rigid foams in domestic
refrigeration has been to use hydrocarbons,
specifically cyclo-pentane and cyclo-pentane/
iso-pentane blends. Sometimes cyclo-pentane
blends with isobutene have been applied to
improve foam flow-ability and compressive
strength.
The hydrocarbon technology introduced
in Europe in the early 1990s has been well
established to accommodate the flammability
of hydrocarbons and allow their safe use.
Approximately 50 % of the currently used
formulations are based on a mixture of cyclo
and iso-pentane since it leads to lower foam
densities with acceptable foam properties.
As a result of intensive system reformulation
aiming at the cell structure optimization,
foam thermal conductivity values as low as
18.7 mW/mK have been obtained. These
values are very similar to those achieved
with HCFC-141b blown foam. The following
graph that correlates the foam thermal
conductivity with Brett mold expansion
(inversely proportional to demould time) shows
the progress achieved through the different
generations developed with the hydrocarbon
technology (DOW, 2008).
Hydrofluorocarbons (HFCs)
In the early years of the 21st century, special
HFCs were developed to replace HCFC-141b
in polyurethane rigid insulating foams. The
aim was to develop a non-flammable “liquid”
blowing agent. In domestic and commercial
refrigeration HFC-245fa was the blowing agent
of choice. Mainly used in North America, it
develops foams with thermal conductivity and
other physical properties very similar to those
based on HCFC-141b. Although an additional
capital investment is not needed it results
in significant higher operating costs mainly
because of the higher price of the blowing
agent. There is comparatively little use of
HFC-134a in polyurethane insulating foams.
The major drawbacks of the HFCs are their
high GWP and price per kg of substance.
In the case of HFC-245fa, the significant
higher price combined with the lower blowing
efficiency resulting of the greater molecular
weight can lead to incremental operating costs
higher than 30 % compared to HCFC-141b.
20.0
19.8
19.6
CP Gen
19.4
19.2
19.0
18.8
CP Gen4
18.6
18.4
18.2
1 2
Brett mold expansion (mm), 8 mins
Improvement of Hydrocarbon Thermal Performance with Development Input
Source: Dow
The use of HFC-245fa can require some
measures to counteract its comparatively low
boiling point of 15.30C. A static mixer can
be used to blend the blowing agent into the
polyol formulation. Alternatively, the chemicals,
blowing agent and polyol formulation, can be
cooled to about 100C before blending. The
miscibility of HFC-245fa is very good in the
polyol formulation with stability of several days.
Carbon Dioxide
The technology based on CO2, derived from
the isocyanate-water reaction, has been tried
from time to time with limited success, and is
broadly unsuitable for domestic refrigeration.
As noted in Section 7.1.2, it does find some
limited use on its own in the commercial
refrigeration sector.
More importantly, the use of CO2 (water) as
a co-blowing agent with fluorocarbons and
hydrocarbons is a viable and popular route to
reduce cost and improve processing flow.
Emerging Technologies
As seen in the earlier tables, unsaturated
HFCs (HFOs) offer some significant potential
as alternatives to HCFC-141b and saturated
HFCs in the domestic refrigeration sector.
However, this transition step is still seen as
some way off, even in the developed countries
such as the United States of America and
Canada, where HFC-245fa is still widely used.
Methyl formate is already being used in a
significant number of applications including,
commercial refrigeration, discontinuous panel,
PU spray and integral skin foams. Annual
global consumption was estimated in 2009
0.1373
CP Gen
0.1360
CP Gen
0.1345
CP Gen
0.1331
CP Gen
0.1317
HCFC 0.1303
CFC 11
0.1290
0.1276
HCFC
0.1262
6 BTU .in/ft hr F
2 0
3 4 5
to be around 400 tonnes with expectations
that this will increase to 1,000 tonnes in 2010.
The technology is becoming established
in Australia, Brazil and the USA in integral
skin, specialty flexible and most rigid foam
applications, while some use in China, New
Zealand and South Africa has been noted.
It is therefore on the cusp of moving from
an emerging technology to an established
technology, although its ultimate potential
may still be considerably greater than current
projections suggest.
Concluding remarks
For domestic refrigeration, based on an
analysis of the key selection criteria and
available options, hydrocarbons - along
with the use of CO2 (water) as a co-blowing
agent - offer the best long term alternative
to replace HCFCs. Thanks to the successful
polyol reformulation for foam thermal
conductivity improvement over the recent
years, they offer similar energy efficiencies,
smaller operating costs and lower GWPs
than currently available HFCs. The only
drawback is the required initial capital
investment.
The commercial introduction and further
developments with HFCs of low GWP (~
5) such as FEA-1100, HBA-2 and AFA-L1
should be monitored. The handicap of this
technology is the potentially high operating
cost driven by the price of the blowing
agent.

62

7.1.2 PU RIGID – Other Appliances
This category involves all “appliance”
applications other than domestic refrigerators
and freezers. The list includes water heaters,
commercial refrigerators and freezers (including
vending machines, display units etc.), picnic
boxes (coolers) and flasks and thermo-
ware. The use of rigid polyurethane foams
is described in each of these applications
together with an assessment of the historic
blowing agent selections that have occurred
in each.
Water Heaters
The benefits of applying rigid polyurethane
foam to water heaters (hot water cylinders) are
in energy efficiency and structural strength.
For many years the insulation of choice was
glassfibre, since there was no concern about
moisture ingress to a cold face. However,
because of the energy conservation policies
of the 1980s, glassfibre was replaced by
rigid polyurethane foam. The critical foam
properties to take into account for an optimum
formulation design are (ABISALEH et al.,
2002):
• Good vertical flow
• Compressive strength
• Good dimensional stability
• Low foaming pressure, maximum 0.3 bar
owing to the thin metal of the casing
• Thermal efficiency
• Good metal-foam adhesion
UNEP DTIE Foam Sourcebook - 2010
Historical trends in actual Blowing
Agent selection
The water heater sector was particularly
focused on transitions from CFC-11 to
HCFC-141b (and to a lesser extent HCFC-22
in places like Australia) in the first transition
period, since confidence to move straight to
hydrocarbons was less prevalent than with
domestic refrigerators. However, experiences
in the domestic refrigerator sector over the
last 15-20 years has given the industry more
confidence to experiment with hydrocarbons,
particularly where the markets are large
enough to support the investment. In these
cases, either cyclo-pentane is used on its
own or in combination with lower boiling point
hydrocarbons such as iso-pentane.
Other blowing agent options
include CO2 (water), HFC-245fa,
HFC-365mfc/HFC-227ea blends and
methyl formate. For many enterprises,
HFC-245fa and/or HFC-365mfc/HFC-227ea
blend can be the best option when combined
with the use of relative large amounts of water
for co-blowing (CO2). The purpose of co-
blowing with CO2 is to limit the amount of HFC
required. This has two benefits:
1. It decreases the overall climate impact of the
formulation
and
2. It decreases the overall cost, provided that
densities can be constrained at low levels
In high ambient temperature regions the
relatively low boiling point of HFC-245fa could
be a limitation when supplied blended with
polyol (fully formulated polyol).
Although all water blown foams have been
found to meet the energy standards of this
application their use is limited because of
the higher foam densities needed to assure
dimensional stability. Additionally, if they are not
properly formulated, metal-adhesion problems
can result from the high polyurea content of
the polymer.
Methyl formate continues to be the focus of
attention in this and other sectors, since it
offers many of the characteristics achieved
with the HFC/ CO2 (water) blend at lower
environmental and financial cost. Recent
assessments conducted within a UNDP pilot
project have covered all aspects of the other
appliances sector, with encouraging results
when used in water heaters.
63
Commercial Refrigerators (including
Vending Machines & Display
Cabinets)
These are typically much larger than domestic
units and include open top display units. For
vending machines, included in this category,
there have been requirements for zero ODP
and low GWP blowing agents from large
manufacturers of soft drinks (Coca-Cola,
Pepsi, etc.).
Basic performance requirements are the same
than those for domestic refrigerators, but the
additional space availability often associated
with these units, means that there are more
degrees of freedom in meeting the thermal and
processing requirements. Notwithstanding this,
flow requirements can be more demanding
because of the increased size of the cabinets.
In any event, the delivery of the required
mechanical strength at lowest possible density
remains the challenge for most systems.
Since many of the manufacturers in this
sector are small/medium enterprises, the
foam components are often supplied as fully
formulated polyols ready for further reaction
with the isocyanate.
Historical trends in actual Blowing
Agent selection
As with water heaters, this sector favoured
HCFC-141b as its first technology transition
out of CFCs in the absence of experience with
hydrocarbons. However, as the sector has
approached the second technology transition
in developed countries, hydrocarbons have
64
ranked higher amongst the options, having in For small/ medium manufacturers the other
mind the demand for lower GWP substances. low GWP options are:
Accordingly, cyclo-pentane alone or preferably
blended with iso-pentane is now the blowing
• CO2 (water): Although high foam densities
are required to meet the dimensional stability
agent of choice for large enterprises. Especially
requirements.
in this application, when capital investment is
affordable the cyclo/isopentane blend provides • Methyl Formate: There are some commercial
a good balance between foam properties and refrigerators manufacturers that are using or
density. have used this substance as blowing agent.
They report a 10 % increase in operating costs
When addressing the HCFC conversion,
arising from the need for higher densities to
one of the questions frequently asked is the
combat foam instability.
minimum size (HCFC consumption) that an
enterprise should have to develop a cost Where high GWP compounds are a possibility,
effective hydrocarbon-based project. HFC-245fa or HFC-365mfc/HFC-227ea can
The “rule of thumb” that was used during be blended with high amounts of water for
the CFC-11 phase out to guide decisions in co-blowing present as described for water
project preparation was 50 tonnes per annum. heaters. However, operating costs can be
Current conversion cost for a small higher under such circumstances and, as
manufacturer (consumption of 30 to 50 noted earlier, some major outlets may object to
tonnes of HCFC-141b), including one high the supply of units containing saturated HFCs.
pressure dispenser with two mix heads, is in
the range of US $ 450,000 to 550,000. At
this consumption level a storage underground
tank for pentane is not necessary and the
operation can handle with 200 – 250 kg
drums. However, a pentane storage area
having a polyol/pentane premix station should
be conditioned in agreement with safety
standards. An enterprise should analyze the
balance between the relatively high capital
investment cost required for hydrocarbons
and the long term sustainability (low operating
costs, low GWP) of the option.

Picnic Boxes (Coolers), Flasks and
Thermoware
As in the case of water heaters, the benefits of
using rigid polyurethane foam are in a premium
insulation value and the increased strength-
to-weight ratio achievable with intermediate
density foams. In
general, technology
requirements are
not as demanding
in these sectors as
in other forms of
appliance, although
resilience is a key
component for a
long product life.
Historical
trends in actual Blowing Agent
selection
In view of their size and relatively low-tech
image, these products have not received
the attention from the chemicals suppliers
to which other sectors have been treated. It
was therefore natural, in the first instance that
they defaulted to the easiest of first-stage
transitions – i.e. primarily to HCFC-141b.
As the sector now looks to move out of
HCFC use, the options are the same as
for the other product groups discussed in
Section 7.2. Depending on the operation size,
hydrocarbons, CO2 (water), methyl formate
and HFC-245fa and HFC-365mfc/HFC-227ea
may be the choice, with blends of two or more
blowing agents being favoured to optimise
formulation performance in some cases.
Concluding remarks
When compared with the stringent
requirements of the domestic refrigeration
sector, the demands on polyurethane
systems are less severe for ‘other
appliances’. However, the range of
products and equipment manufactured
mean that the overall chemistry needs to be
both robust and versatile.
Hydrocarbons (particularly cyclo/iso-
pentane blends) are undoubtedly the
blowing agents of choice where the critical
mass is sufficient to justify the investment.
Most other technologies are, to some
degree, compromises, the choice of which
will depend on the ranking of the foam
performance criteria.
UNEP DTIE Foam Sourcebook - 2010
7.1.3 PU RIGID – Transport and Flammability is not a product performance
issue in this instance, but may still present
Reefers
challenges in processing. However, as with
This sector of foam use covers two distinct
most other automated processes, it should
groups of insulated container. The first is
be possible to engineer solutions to manage
typically a road trailer which can be either a
the risk. In this context, hydrocarbons are
tank or of straight-sided construction. The
seen to represent probably the best option,
second is a demountable insulated heavy
particularly in the light of recent formulation
steel box. These containers are often called
improvements which have delivered better
‘reefers’ and are fundamentally designed
thermal performance. N-pentane is understood
for shipping, although with the capability to
to represent the most favoured option at the
be transported inter-modally on roads and
moment, since its boiling point provides better
railways. The international nature of their use
processing than other options.
means that they may often circum-navigate
the world several times during their lifetime, The potential for methyl formate may also
thereby making it important that the structural emerge further in future, but the technology
integrity of the unit is retained while in use and will need to demonstrate advantages. With
the materials of construction are identifiable at dimensional stability being a critical aspect of
end-of-life. It is estimated that the number of this application, the solubility of methyl formate
reefers currently in circulation globally is in the in the matrix may demand higher densities.
order of 1,000,000, carried on over 10,000
Even more unproven, but still of potential
container ships.
interest are the unsaturated HFCs, since
These applications, more than any other, they may be able to deliver significant
place particular emphasis on the durability thermal upsides. However, this assumes that
of the foam used in the construction. In additional energy performance will be relevant.
addition, there is the clear commercial In practice, the benefit will not be in lower
challenge of maximising the storage capacity, retained temperatures but in the ability to
while minimising the overall spatial footprint maintain the desired temperature for longer.
of the container. In many instances, the This is an extremely important factor on board
outside dimensions of both road-based and container ships where multiple containers have
intermodal transport are legally defined so their refrigeration units connected to the ship’s
that consistency can be assured. This puts power supplies.
a particular strain on the requirements of
the foam in order to achieve the minimum
wall thickness whilst maintaining the level of
insulation required to avoid the contents of
containers being spoiled (FTOC, 2006).
The challenge for manufacturers of both types
of insulated container is the need either inject
or laminate foam systems in such a way
as to create durable structures capable of
withstanding the rigours of transportation.
Typical foam densities in these applications
are in the order of 40 to 45 kg/m3. Historically,
CFCs were used to create the foams, often
in-situ. The bulk of manufacturing has now
switched to HCFC-141b in order to retain the
thermal insulation characteristics. However,
where HCFCs have already been phased
out, the main choice has been between
saturated HFCs co-blown with CO2 (water)
to the extent permissible without sacrificing
thermal properties, and hydrocarbons. With
the vast majority of reefer manufacture now
concentrated in China, the significance of the
technology choice when replacing HCFC-141b
is self evident.
65
Historical trends in actual Blowing
Agent selection
Reefers
As noted earlier, the insulated containers
known as ‘reefers’ are primarily designed for
intermodal use, with a particular emphasis on
shipping. These units were typically insulated
with CFC-blown foam and converted naturally
to HCFC-141b across the world when CFC
restrictions came into place. With product
lifetimes in the order of 10-15 years typically,
most of the CFC-containing units are likely to
be out-of-service in the next few years, but
require active management at end of life if the
blowing agents are not to be released. The
opportunity for recovery is significant because
the steel structures retain the blowing agent
throughout the service life of the containers.
HCFC-141b is still the blowing agent of choice
for most reefer manufacture because the bulk
of the global production has moved now to
China, thereby avoiding the need for developed
country producers make a further technology
transition. The previous sub-section outlined
the options available for the Chinese producers
and it is likely that there will be considerable
focus on making hydrocarbons work.
66
Truck Bodies Concluding remarks
For truck bodies, saturated HFCs, The use of insulation foam in transport
co-blown with CO2 (water), have been used applications provides a performance
as HCFC-141b replacements in developed enhancement which is critical to the cold
countries. HFC-365mfc/227ea blends chain in general and the food chain in
generally provide better flow characteristics particular. There are a number of variants
than HFC-245fa, which tends to froth foam in terms of transport design and modality,
and create additional back pressure. Where therefore generalisations across the
safe use can be assured, hydrocarbons are sector are difficult to make. However,
also having an increasing role, based on the hydrocarbons are likely to play a significant
improved formulations mentioned earlier. role in meeting the HCFC phase-out
It seems likely that there will be some interest requirement – particularly where levels of
in unsaturated-HFCs (HFOs) in this sector in automation can be achieved.
future, if they are seen to offer better thermal
performance or other operational advantages.
Tanks
Tanks present a specific processing challenge
because of their shape. Therefore foam
formulations need to be particularly versatile to
process successfully in these circumstances.
CFCs and HCFCs have been able to provide
the level of versatility required, but other
options are less well proven. Hydrocarbons
may be less favoured in these less well-
controlled environments and this may leave an
opening for methyl formate, with its reported
lower flammability. However, capability in
processing will need to be confirmed. The
HFCs (both saturated and unsaturated) remain
the other options and saturated HFCs may
provide the solution in developed countries for
the foreseeable future until unsaturated-HFC
technologies mature.

7.1.4 PU RIGID – Boardstock
Continuous processes for rigid polyurethane
foams have been mostly limited to developed
countries, where the size and maturity of
the markets has supported the investment.
In North America, a high proportion of the
demand for PU Boardstock (often referred to
in the United States as “polyiso”) comes from
the residential sheathing market, where the
product competes with extruded polystyrene
and mineral wool. In Europe, the use is
focused much more on the commercial and
industrial buildings sector, although recent
increases in energy standards in the residential
sector have improved its competitive position
with respect to mineral wool.
In developing countries, continuous laminators
are rare with only Turkey and Mexico known
to have significant investments. However,
this situation is expected to change rapidly
as attention is focused globally on the need
for greater energy efficiency in buildings in
order to combat climate change. The growth
in construction has already stimulated rapid
growth of the extruded polystyrene market in
China and the development of a significant
polyurethane boardstock industry in China is
expected to follow close behind.
Historical trends in actual Blowing
Agent selection
As with most other sectors based on rigid
polyurethane foam, the blowing agent of
choice for the period up to the early 1990s was
CFC-11. Under pressure to make the transition
from CFCs, most of the industry initially went
to HCFC-141b, with the exception of a few
manufacturers in the European Union. German
manufacturers, in particular, were encouraged
by pending regulatory pressures to move
directly to hydrocarbons and managed to
make the transition directly.
The cost-effectiveness of the hydrocarbon
solution spurred others to investigate it, and
where the product’s fire classification was
not impaired, further transitions took place.
UNEP DTIE Foam Sourcebook - 2010
However, the primary shift to hydrocarbons
came in the 2003-2004 period when the
North American “polyiso” industry, facing a
ban on the further use of HCFC-141b in 2005,
decided to move to hydrocarbons rather
than to saturated HFCs, which were its other
choice.
Only very few developed country
manufacturers have made the transition to
saturated HFCs and this has been primarily
where product fire requirements have
necessitated this transition and the cost
burden can be absorbed.
The few developing country activities are either
using HCFC-141b or HCFC-22 currently.
Retrofit to hydrocarbons would require
significant further investment and it may be
easier for new capacity to be installed based
on hydrocarbon from the outset in view of the
likely growth in demand for this product type in
coming years.
Concluding remarks
The PU Boardstock industry is heavily
focused in developed countries at present,
but substantial growth is expected to
occur in developing countries as the focus
increases on the insulation of buildings
globally. The growth of construction in
places such as China means that increased
levels of insulation are essential. In this
context, there will be few, if any, PU
laminators meeting the cut-off date for
transitional investment under Decision
XIX/6, but it will be important for new
investments to be guided to the most
environmentally sound technologies, in
view of their future significance.
67
 7.1.5 PU RIGID – Continuous One exception to this for a number of years
was the UK market where stringent fire codes,
Panels
underwritten by the insurance companies,
The continuous PU panel market has grown
prevented the use of hydrocarbons for such
substantially in Europe over the last 20-30
applications. In the face of the need to transfer
years as demand for pre-fabricated distribution
from HCFCs by the end of 2004, a number
‘sheds’ has increased. Continuous panels
of manufacturers switched to saturated HFCs
provide a particularly effective way of achieving
(typically HFC-365mfc), but have gradually
highly engineered structures with low air
switched towards hydrocarbons as further
leakage rates. Although the recent economic
formulations have been developed and
downturn has slowed the rate of growth
optimised.
significantly, the products continue to take
market share from more conventional forms on There is little current exploitation of PU
construction. continuous panel technology in developing
countries to date and that which exists is
The technology has been successfully
understood to be still using HCFC-141b, with
transferred into the North American and
minor use of hydrocarbons and HCFC-22.
Australasian markets and is expected to
move into Asia. In Japan, steel-faced panels Concluding remarks
already have a market based but this is more
As with PU Boardstock, this sector does
focused on the residential sector where the
not represent a significant challenge under
products are used for sidings. It is clear that
the auspices of Decision XIX/6, since few
volumes need to be sufficient to support
technology transitions will be required.
continuous processes and it is quite common
However, there is a need to ensure that
to see initial market development occur
any new capacity established in Article
with discontinuously produced panels or
5 countries takes due account of the
with panels traded from other regions. This
environmental impacts associated with
shipment is possible because of the relatively
such investments.
high added value of the products.

Historical trends in actual Blowing

Agent selection
The major growth in the steel-faced panel
sector has primarily occurred since the phase-
out of CFCs, although examples of earlier
CFC-containing panels are likely to emerge in
the waste stream over the next 15-20 years.
These were typically much thinner than today’s
products (30-40mm then vs. 80-100mm
today). The initial technology transition in
Europe was to HCFC-141b although, as with
PU Boardstock, national regulatory pressures,
and economies of scale led to an increasing
focus on the use of hydrocarbons.

68
 UNEP DTIE Foam Sourcebook - 2010

7.1.6 PU RIGID – Discontinuous
Panels
In contrast to the continuous processes,
discontinuous panel manufacture is more
endemic in developing countries and, as in the
developed countries, it is concentrated within
small and medium sized enterprises (SMEs).
The markets served are also rather different,
with many of the panels being used for internal
cold storage purposes rather than as external
cladding.
Historical trends in actual Blowing Agent
selection
In similar fashion to other discontinuous
processes, manufacturers of discontinuous
polyurethane panels have been consistently
concerned about the health and safety impacts
of technology transitions in their factories.
CFCs and, in particular, CFC-11 was an ideal
blowing agent under these circumstances
because of its inert nature and versatile
processing characteristics.
the industry, efforts have been made to install
equipment that can handle hydrocarbons.
Accordingly, there has been some shift
towards the use of hydrocarbons in sector
over recent years.
Both methyl formate and unsaturated HFCs
are seen as potential future blowing agents.
The manufacture of discontinuous panels
using methyl formate has been included in the
recent Brazil/Mexico Pilot Project conducted
by UNDP and initial results look encouraging.

PU discontinuous panel is more likely to
compete against steel-faced panels produced
with expanded or extruded polystyrene cores,
where fire codes allow these products to be
used. The market can therefore be highly cost
sensitive and it is often difficult to support
significant investments.
Many discontinuous panel manufacturers
also serve the refrigerated transport sector
and, as noted in Section 7.1.3, this sector
requires products made to precise tolerances
and, often tailored to specific circumstances.
This allows the panel manufacturer to recover
more of the value-added in its product
pricing in order to offset the more competitive
construction market.
At the point at which the first transitions Concluding remarks
out of CFCs had to made, it was clear that
This sector has a significant population of
HCFCs were the only option that could be
enterprises engaged in it throughout the
accommodated with existing equipment.
Article 5 countries. It is therefore likely to be
Hence the transition to HCFC-141b was
a significant focus within HCFC Phase-out
virtually universal, with the exception of some
Management Plans under Decision XIX/6.
manufacturers who had processes that
There is a growing degree of confidence
depended on froth foaming. In these instances,
that solutions avoiding the selection of
blends involving HCFC-22 were also used. In
saturated HFCs can be made based on
at least one instance, HFC-134a was used for
emerging technologies.
the same purpose.
Subsequent transitions out of HCFCs have
primarily been towards saturated HFCs, with
both HFC-245fa and HFC-365mfc/227ea
being adopted in a number of applications. As
foaming equipment has been replaced across

69
 7.1.7 PU RIGID – Spray
Sprayed rigid PU foams are closed-celled, air
tight, resistant to mildew and fungal attack,
provide no food value to rodents and have
good vapour barrier properties (Randall &
Lee, 2002). They find utility as an in situ
applied insulation in applications where
irregular shapes or the need for a monolithic
layer of foam exists. These applications
include building envelope, pipe insulation,
tank insulation, rail cars, residential roofing
and floors (Gum, 1992). Sprayed foam
is now finding increasing applications in
retrofitting/refurbishing roofs, walls, floors
and windows of existing buildings as well as
in new constructions such us commercial
offices, industrial factories and warehouses,
agricultural pig and chicken farms (Randall
& Lee, 2002). In the 2008 Progress Report
the Foams Technical Options Committee
states: “PU Spray Foam is being increasingly
recognized as an efficient means of retrofitting
a number of building types”. The use of spray
rigid foam has significantly increased both in
developed and developing countries since it
combines the PU insulation properties with
ease of application and the unique adhesive
ability to provide in-situ insulation on a variety
of surfaces.
70
In general, the use of PU spray foam is most
prevalent on flat roofs and also between the
studs of walls in timber frame buildings. These
applications require differing densities of foams
based on the fact that roofs generally have
to carry some foot traffic, or at least need to
be able to support crawling boards. Typically,
the roofs also require a UV protection coat, as
shown in the diagram. The spray foam product
to fill the cavities between studs, however, is
much lighter in density (typically 20-25 kg/m3)
and its primary purpose is to deliver thermal
insulation and gap filling. The latter is very
helpful in avoiding air leakage which, in turn,
can improve the overall energy performance
of a building substantially. Typically, such
low density foams do not hold their thermal
performance irrespective of the blowing agent
used. This means that these applications are
less sensitive to blowing agent choice, at least
from a thermal conductivity perspective.
The chemical components are mixed and
sprayed directly onto the substrate using
fixed ratio (normally 1:1 in volume) positive
displacement pump portable machines,
equipped with spray guns. A high ~30 kg/
min output machine is using for roofing
whilst a small ~10 kg/min output equipment
is more suitable for stud wall insulation.

Generally polyurethane technology is used,
but for some specific fire or temperature
requirements polyisocyanurate (PIR) is applied.
Good adhesion between the substrate and
the sprayed foam is extremely important so
all substrates should be clean, dry and free
of grease, oil, loose material or dust. The
foam needs to be highly reactive, especially
for adhering to vertical surfaces. Typical core
densities are in the range of 35 to 40 kg/
m3 for roofs. Additional foam requirements
are: high resilience, low moisture absorption
and transmission; good thermal properties;
sufficient fire performance to meet relevant
building codes; application capability in a
variety of climatic conditions; and ease of use
(FTOC, 2006).
The use of PU Spray Foam is at its most
prevalent in North America, Spain and Japan.
All three regions have therefore already faced
the challenge of HCFC-141b phase-out. Early
experiments with hydrocarbon technologies
in the United States resulted in incidents
which confirmed that the flammability of
hydrocarbons was unmanageable in this
application. Attempts to overcome this set-
back with changes in practice have failed to
deliver and interest in the use of hydrocarbons
has waned.
In Japan, super-critical CO2 technology has
been introduced and made some headway,
although levels of market penetration,
whilst significant, suggest that there maybe
limitations in some applications. Nonetheless,
the technology has now become the focus of a
possible UNDP pilot-project which might shed
more light on the potential.
As noted earlier, CO2 (water) provides an
option for less critical applications, but the
system must be well formulated to prevent
shrinkage and to promote good adhesion.
Apart from the saturated HFCs which are now
well established, there is initial evidence to
suggest that unsaturated-HFCs could have a
significant role to play in the future of PU Spray
Foam worldwide. A recent study (BOGDAN,
2009) that covered the diversity of the polyol
blends found in the industry indicated that
spray foams blown with unsaturated HFCs
of low GWP were equivalent or better quality
compared to current HFC-245fa based foams
and that they can be processed in existing
commercial equipment.
There is also the possibility that methyl formate
could have a role to play, but it is not yet clear
whether the flammability of methyl formate
will be sufficiently low to meet the safety
requirements of the application. Although PU
Spray was included in the recent UNDP pilot
project on methyl formate, results are still
awaited on the foams produced. In addition, it
is not yet clear how the processing boundaries
were evaluated.
For super-critical CO2, the technology relies on
direct CO2 injection to the polyol component.
With a minor modification to conventional
spray machines (Gusmer FF type with a
1:1 mixing ratio by volume) supercritical
CO2 assisted water blown foams with good
dimensional stability and a comparable
density to HCFC-141b blown systems are
produced. Liquid CO2 cooled to 0 °C with a
heat exchanger is supplied to the Gusmer
type auxiliary pump which is remodelled so
that brine can circulate internally and the CO2
injected to the polyol component. The unitary
cost to modify conventional Gusmer type
equipment is estimated to be US $ 14,000.
Foams with either normal rigid polyurethane
(PUR) or polyisocyanurate (PIR) for applications
requiring flame-retardant systems can be
provided. Despite its significant penetration in
the Japan spray foam market it is still not clear
how widely applicable this technology may be
outside of the country.
UNEP DTIE Foam Sourcebook - 2010
Historical trends in actual Blowing
Agent selection
Originally, the technology used throughout
the world was based on CFC-11. At the point
where CFC-11 was phased-out, HCFC-141b
became the obvious replacement and few
others were evaluated. Only at the point of
HCFC-141b phase-out, were hydrocarbons
and saturated HFCs seriously evaluated.
In the United States, there was also some
intermediate evaluation of HCFC-22 in view of
the fact that the phase-out date for HCFC-22
was later and the most appropriate saturated
HFCs (notably HFC-245fa) were only just
becoming available.
A proportion of the PU Spray Foam market in
all three territories (North America, Spain and
Japan) moved to CO2 (water) blown foam, but
this was not seen to be a universal solution.
The choice of saturated HFC depended to an
extent on availability, which itself was driven
by the patent cover in each region. This led to
only HFC-245fa being used in North America
while, in Europe, both HFC-245fa and HFC-
365mfc/227ea have been used successfully.
In Japan, where pressure to avoid saturated
HFCs has been greater, the balance of the
market has been shared between HFC-245fa
and super-critical CO2.
The rapid growth of the PU Spray market in
China over recent years based on HCFC-141b
has created an urgent need to evaluate the
best alternatives for this region – particularly
because of the ‘worst-first’ presumption in
Decision XIX/6.
Concluding remarks
This is another sector where the prevailing
technology in use in developed countries
is unlikely to provide a full solution for
Article 5 country transitions. The emerging
technologies include super-critical CO2,
methyl formate and unsaturated HFCs, but
it is still unclear which of these will best
meet developing country needs.
71
 7.1.8 PU RIGID – Blocks
PU rigid foam blocks (called ‘buns’ in the
United States) can be produced by either
continuous or discontinuous processes. The
purpose of producing foams in this form is to
create the largest level of utility from a single
manufacturing source. This makes PU Block
manufacture particularly popular in small
and emerging markets. Blocks can be cut
into slabs in order to allow the production of
composite panels with metal or plasterboard
surfaces. They can also be cut into foamed
pipe sections using computer-controlled
specialist cutting equipment. This type of
approach becomes even more powerful for the
fabrication of three dimensional shaped for the
insulation of tanks and vessels.
However, the penalty paid for the versatility
offered by block foam technologies is in
the utilisation of the foam itself. Even for
well designed computer-controlled cutting
equipment it is difficult to get above 55%
yields for foam utilisation. This leads to
considerable waste streams and a requirement
for appropriate waste management strategies
– particularly if the blowing agent selection
involves gases that are either ozone depleting
or contribute significantly to climate change.
The situation is slightly less severe for
continuous processes than for discontinuous
processes, but the waste issue remains a
significant one for all fabricated parts.
Historical trends in actual Blowing
Agent selection
The often small-scale nature of PU Block
Foam plants has meant that polyurethane
systems have needed to be both versatile
and tolerant. Most, if not all, PU Block Foam
facilities therefore used CFC-11 until, at least,
the early 1990s when HCFC-141b began to
emerge as a virtual drop-in replacement. For
72
the manufacture of blocks, the rise/cure profile
is critical and this relates directly back to the
boiling point of the blowing agent. If the cure
is too slow it leads to block collapse, but if
the curing on-set is too early it leads to highly
distorted cell structures.
Hydrocarbons (particularly n-pentane) also
meet these requirements but the concern has
always been the management of accumulation
of pockets of blowing agent within the
manufacturing facilities. Flame proofing and
adequate ventilation are both required to
avoid these risks and the level of investment
is typically too great for this type of process
– particularly in the case of discontinuous
production.
Transitions from HCFCs in developed countries
have tended to follow the saturated HFC
option, with HFC-365mfc/227ea blends being
used in Europe (primarily because of their
boiling points) and HFC-245fa tending to be
used in North America, where experience with
froth foaming technology is more advanced
than elsewhere.
Concluding remarks
This type of process has particular use in
Low Volume Consuming (LVC) countries
because of its relatively low investment
cost and its versatility in meeting a number
of foam end-uses. The most likely solution
for the HCFC-141b phase-out could be pre-
blended hydrocarbons (avoiding the need
to mix on site) or methyl formate. However,
in both cases, the flammability risks need
to be fully characterised in order to define
the minimum investments required (if any)
for adequate risk management.

7.1.9 PU RIGID – Pipe-in-Pipe
The deployment of this technology has
grown rapidly in the last 25 years based on
the increased trends towards district heating
systems. These systems were already well
established in former Eastern Bloc countries,
but have been promoted further by recognition
that small-scale, localised combined heat
and power (CHP) facilities are an important
component of future decentralised energy
generation strategies to combat climate
change.
The technology involves the in-situ foaming
of polyurethane insulation foam between a
steel pipe and outer casing which may be
high density polyethylene pipe or other similar
product. There are a number of continuous
and discontinuous processing methods
including casting, injecting with a withdrawing
mixing head (see first illustration) and forming
the external jacket in a continuous process
(see second illustration).
The drawbacks of this method include the
difficulty in manufacturing long pipe sections
and ensuring that the quality of the foam is
consistent throughout. Similar issues exist for
a variant of this process called the paper draw-
through method.
For continuous processes the method is as
shown below:
In this instance the key to the success of the
process is in ensuring that the external pipe
covering provides an integral seal. This is
important since many such pipes are installed
underground and need to be particularly
immune to water ingress.
UNEP DTIE Foam Sourcebook - 2010
Additional challenges for continuous processes
include the fact that changes in pipework and
insulation diameters can involve long set-up
times. There is also a need for sophisticated
process control.
Historical trends in actual Blowing
Agent selection
As with many other complex processes,
the technology was simplified by the original
adoption of the most versatile of blowing
agents, CFC-11. In transitioning from
CFC-11, a significant part of the industry
went to HCFC-141b in order to optimise
thermal performance. However, a number of
European manufacturers also focused on the
further development of hydrocarbon systems
based on n-pentane and/or cyclo-pentane.
These have since been optimised and are
now perceived as broadly state-of-the-art.
Other users of HCFCs in developed countries
have transitioned to saturated HFCs, such as
HCFC-245fa and HFC-365mfc/227ea.
Concluding remarks
The future technology options for
pipe-in-pipe polyurethane foams in
developing countries seem to be based
on the capability to achieve appropriate
transfer of hydrocarbon technologies.
There are very few intrinsic drawbacks
with the hydrocarbon choice since the
manufacturing processes are relatively
sophisticated and engineering solutions
can be managed. For the products
themselves, they are largely underground
and represent little intrinsic hazard. In
addition, there is little penalty in insulation
thicknesses with the most recent,
optimised hydrocarbon technologies.
73
 7.1.10 PU RIGID – One Component
Foams
These are different from a number of other
foam types, since the technology relies on the
moisture-curing (from atmospheric sources)
of low density polyurethane foam that has
been froth foamed. The primary use of such
products is for gap filling in buildings to
prevent excessive air movements. The thermal
insulating properties of these products are
broadly secondary.
The technology has widespread use in Europe
both in support of products for new build and
also for renovation. The foam is delivered in
aerosol cans which can be relatively small
for direct consumer sales, but may be larger
canisters for trade uses.
Historical trends in actual Blowing
Agent selection
Since the blowing agent also acts as a
propellant, they need to be gaseous in nature.
CFC-12 was the blowing agent of choice
in the early phases of market development.
Although there were some moves towards
HCFC-22, in the first transition, a number of
key manufacturers elected to move directly to
solutions based around HFC-134a. In some
instances, this included co-blends with
di-methyl ether and other hydrocarbons.
The emissive nature of the application
caught the attention of the EU regulators
on fluorinated gases as early as the late
1990s and led to a focus on the potential to
phase-out the use of HFCs from the sector.
There was considerable discussion about the
potential for all-hydrocarbon solutions, but
74
this met with resistance from a number of
manufacturers based in countries where either
process or product standards prevented the
use of hydrocarbons in isolation.
In the F-Gas Regulation that finally emerged,
pressure was placed on the substitution of
HFC-134a for blowing agents with lower global
warming potentials (e.g. HFC-152a and, more
latterly, unsaturated HFCs) by the imposition of
a future ban, albeit with potential exceptions on
safety grounds. The use of di-methyl ether has
therefore grown on the back of this technology
driver, but many manufacturers have also seen
the potential for HFO-1234ze, which has been
commercialised by Honeywell in time to meet
the F-Gas phase-out schedules for HFC-134a.
Honeywell have reported significant market
development in this sector as a consequence.
Concluding remarks
From the developing country perspective,
the opportunity exists to move relatively
swiftly from the use of HCFC-22, where
used, provided that access to appropriate
technology can be negotiated. This
technology step should jump over the use
of saturated HFCs and may lead to the
adoption of hydrocarbon technologies
based on di-methyl ether, possibly in
combination with unsaturated HFCs.
 UNEP DTIE Foam Sourcebook - 2010

7.2 PU FLEXIBLE FOAMS Critical Foam Processing and

At the time of the CFC phase-out in the late Product Properties
1980s and early 1990s, this sector represented Both applications require three primary
a substantial element of the ODS consumption characteristics. These are hardness, resilience
in the foam sector, even though the chemicals and skin formation. Moulded polyurethane
were only used as an auxiliary blowing agent. foams with integral skins provide the precise
Their prime purpose was to bring an extra combination of characteristics to deliver these
boost to the CO2 (water) already present and properties and have therefore increasingly
allow lighter and softer foams to be produced. dominated the market for both. Within car
This was (and is) of particular importance in the interiors, the use of integral skin polyurethane
bedding and furniture sectors, which are the foam has extended as far as the steering
largest segments of the flexible polyurethane wheel, where the technical specifications are at
foam market. their highest.
Being close to the consumer interface and The following table illustrates the primary
needing a relatively rapid phase-out strategy, technical requirements of PU integral skin foam
the bulk of the flexible foam industry did systems:
not wait for the development of a technical
replacement for CFCs (i.e. HCFCs) but elected
instead to invest in existing technologies, such
as the use of methylene chloride, despite the
fact that health concerns had been expressed
in some quarters. The two major sectors that
decided not to take such a route were the
flexible integral skin applications (e.g. car dash
boards) and the shoe sole sector, both of
which had (and still have) relatively challenging
specifications. In both of these instances,
HCFC-141b and, to a lesser extent, HCFC-22
became the blowing agents of choice.

Application
Required Foam Property or Process Characteristic

Ease of Skin Resilience Mechanical Hardness Ozone Global

Processing Formation Strength Depletion Warming

PU Integral Skin Foams 444 444 444 44 444 444 44

PU Shoe Soles 44 44 4 4 4 44 44 444 44

75
 In general, the specifications for automotive
applications are more stringent than for other
applications in view of the safety implications
associated with these uses. This is reflected in
the requirements shown in the table.
1. Ease of processing. Virtually all of the
products manufactured in this sector are
moulded. The processing characteristics that
are most significant therefore relate to the flow
of the polyurethane system through the mould,
and its consistency of rise and cure. A further
property of importance is mould-release.
All of these parameters are fundamentally
a combination of the polyurethane system,
the mould design and mould operation. It is
therefore difficult to point to a universal foam
formulation that delivers optimum properties in
all integral skin foam applications.
2. Skin Formation. This is an absolutely
critical characteristic both from the point of
view of aesthetics and longevity of service.
Imperfections in the surface finish can lead to
further accidental damage, since the integrity
of the surface can be breached more easily. As
is shown later in this sub-Section, the choice of
blowing agent can have a substantial influence
on the quality of skin formation.
3. Resilience. In softer foams, the
characteristic would be known as visco-
elasticity. It is fundamentally, the ability to
regain its original shape following impact.
In most integral skin applications, where
densities are higher, the process is virtually
instantaneous and the foam is described
as resilient. This property is dependent on
76
a balance between polyurethane system Blowing Agent Selection and how
formulation and foam density. These can
it contributes to Required Foam
be varied to a degree, but automotive
manufacturers understandably seek the Properties
required resilience at minimum density in order The following table provides an overview of
to save weight in their vehicles. the interaction of blowing agent selection with
desired foam properties:
4. Mechanical Strength. Again, mechanical
strength in the foams is broadly a function of
density. It is important that the foams are able
to provide sufficient structural integrity to meet
their requirements. For automotive fascias, for
example, the foam can be used to encompass
glove compartments and other such features.
It is therefore important that factors such as
tear strength, elongation, tensile strength and
compression are all sufficient to meet the
application requirements.
5. Hardness. This is a characteristic that is
measured across many plastics and rubbers
and is effectively assessing the resistance to
indentation. There are a number of routine test
regimes, amongst which Shore and Rockwell
are the most well known. The avoidance of
skin penetration is critical for both automotive
and shoe sole applications in order that the
products concerned can have a level of
longevity.
Although significantly inter-related, these
properties collectively represent an expression
of what needs to be achieved by a successful
polyurethane foam system. The impact that
blowing agent selection can have on these
characteristics is the subject of the next sub-
Section.
 UNEP DTIE Foam Sourcebook - 2010

Required Property
Relevant Blowing Agent Property

1. Ease of Processing Flammability (the lower the better)

Boiling Point (significance depends on handling equipment)

Solubility in Formulation (the higher the better)

2. Skin Formation Boiling Point (blowing agent to condense at surface under temp./pressure)

Solubility in Formulation

3. Resilience Broadly independent of blowing agent choice, if processing OK

4. Mechanical Strength Broadly independent of blowing agent choice, if processing OK

5. Hardness Broadly independent of blowing agent choice, if processing OK

6. Environmental GWP

ODP

It can be seen that the primary interaction
between blowing agent choice and foam
properties occurs on the issue of skin
formation and, indeed this has been the
experience in practice – particularly in the more
demanding applications of the automotive
sector. The following table illustrates the HCFC
alternatives available and their strengths and
weaknesses.

Rating of Blowing Agent Types by Criterion

HCFC-141b Hydrocarbons Saturated Unsaturated Methyl Formate CO2 (water)

Blowing Agent Criterion HFCs HFCs (HFOs)

Flammability ++ + +++ ++/+++ +/++ +++

Boiling Point (Processing) ++ ++/+++ ++/+++ ++/+++ ++ ++
Solubility in Formulation +++ ++ +++ +++ ++ N/A

Boiling Point (Skin Form) ++ ++/++ ++/+++ ++/+++ ++ +

Solubility in Formulation +++ ++ +++ +++ ++ +
Ozone Depletion Potential + +++ +++ +++ +++ +++
Global Warming Potential +/++ ++/+++ + ++/+++ +++ ++/+++

+++= Good ++= Fair += Poor

77
 The table demonstrates that hydrocarbons
perform at least as well, if not better than
HCFC-141b for this application. The only
aspect that creates a serious challenge is the
flammability of the blowing agents themselves.
This is more of an issue for integral skin
applications than, for example, domestic
refrigeration applications where the injected
systems are largely enclosed, both during
processing and in the final product. The
variety of shapes also being processed in a
typical moulding environment also adds to the
potential for blowing agent release. For this
reason, there has been an understandable
reluctance to adopt hydrocarbons widely in
the sector, although some product lines have
sufficient consistency to accommodate the
approach using n-pentane. Even in these
cases, investment levels can be similar to
those experienced in the rigid polyurethane
foam sector and outlined previously in
Section 7.1.
CO2 (water) has obvious attractions of
simplicity and minimisation of cost, but the
technology has been dogged by the low
boiling point of CO2 and its lack of solubility,
both of which conspire to create difficulties
in skin formation. Some manufacturers have
Economic viability and cost effectiveness criteria
HCFC-141b
Blowing Agent Criterion
Investment Costs + +++
Operating Costs ++
Widespread Availability ++
Potential to blend for BA blends ++
+++= High ++= Medium
78
sought to over-come this by using in-mould Economic Viability and Cost
coatings, but the cost of the additional
Effectiveness Criteria
materials and the time and labour involved
Since the blowing agent technologies
in this extra process step have made the
are similar to those being considered for
technology relatively unattractive. Nevertheless,
the majority of rigid polyurethane foam
there are a few automotive suppliers applying
applications, the economic viability and cost
this type of technology.
effectiveness criteria are also very similar, as
Both saturated and unsaturated HFCs offer shown in the table below:
a significant technical solution. However, for
As noted in the previous sub-Section, the
saturated HFCs, the fact that the blowing
degree to which the safety of hydrocarbon use
agent is fully emitted shortly after manufacture
can be engineered will vary as a consequence
only serves to emphasise the environmental
of the types of products being manufactured
drawbacks of the approach. Unsaturated
and their variability. Accordingly, a full
HFCs would not have this particular challenge,
assessment of the range of costs is beyond
but are, as yet, unproven in the application and
the scope of this Sourcebook and will need
there would also be some concern about cost
to be evaluated on a case-by-case basis.
and availability, particularly in the short-term.
However, if methyl formate continues to fulfil its
Methyl formate has been trialled successfully initial promise, there is a likelihood that this will
for integral skin applications and results replace hydrocarbons as the primary option
assessed in the Pilot Project in Mexico and for affordable integral skin foam manufacture
Brazil have shown comparable properties to in future.
those currently achieved with HCFC-141b.
There is an expectation that this may be one
of the areas where methyl formate might
penetrate the market preferentially, particularly
if cost and availability permit.
Hydrocarbons Saturated Unsaturated Methyl Formate CO2 (water)
HFCs HFCs (HFOs)
+ + +/++ +
+ ++/+++ +++ +/++ ++/+++
++ +/++ + +/++ +++
++/++ +++ ++ ++ +++
+++= Low

7.2.1 PU FLEXIBLE – Integral Skin
(Automotive)
Historical trends in actual Blowing Agent
selection
As with many other polyurethane foam
processes, this application was based almost
exclusively on CFC-11 until the onset of
the ozone depletion. Perhaps more than
others, however, it is a set of applications
that has grown in stature and become part of
mainstream product design during a period
when it has been managing technology
transitions. This has been particularly the case
for the automotive sector, where the use of
PU foams in automotive interiors has grown
significantly through the period.
In order to create minimum disturbance to
the achievement of challenging specifications,
the industry initially moved to HCFC-141b.
However, in view of the global nature of
the automotive industry and the advanced
schedule for HCFC phase-out in developed
countries, there was a need for a further
response by the industry as early as the
year 2000. This was coupled with consumer
pressure for ODS-free products.
UNEP DTIE Foam Sourcebook - 2010
The choices for the substitution of HCFCs Concluding remarks
in this sector have already been described
With the exception of skin formation, the
and it is clear that solutions based on
impact of blowing agent selection on final
HFCs (e.g. HFC-134a, HFC-245fa and
foam properties is limited. However, there
HFC-365mfc), which have been used in a
is a minimum set of requirements that the
number of developed countries might now
blowing agent needs to meet in order to
be less favoured because of pressure from
assist in the satisfactory processing of
regional climate policy. This may play into the
integral skin foams. The processing and
hands of alternatives such as methyl formate,
product demands are at their highest in the
provided that any flammability characteristics
automotive sector, where the specifications
can be contained more cost-effectively than
are very exacting. Alternative blowing
traditional hydrocarbons. The Pilot Project in
agents are available for HCFCs and a
Brazil/Mexico has already gained recognition in
number of these could deliver appropriate
the fact that products manufactured appear to
climate benefits.
meet the specifications set by Volkswagen.
79
7.2.2 PU FLEXIBLE – Integral Skin
(Shoe Soles)
This application is similar to other integral skin
moulding applications, although the size and
consistency of the products manufactured is
much clearer. This allows for a higher degree
of automation and engineering than in other
sectors of the integral skin foam sector.
Although shoe soles are a very well-defined
application, the rate of change is driven by
fashion considerations and, therefore, the
manufacturing environment can be very
dynamic. This has to be reflected in the
versatility of equipment to changes in mould
design and operation.
Historical trends in actual Blowing
Agent selection
Again, CFC-11 was the bedrock of this
application in its early years, since it provided
inert characteristics and met the processing
demands without modification. When pressure
emerged to phase-out the use of CFCs, there
was some active consideration of HCFCs
and some take-up of HCFC-141b. However,
a significant proportion of the market realised
that CO2 (water) would be a genuine option for
this sector, since the processing hurdles were
less challenging than those experienced with
automotive products.
80
The industry is currently divided into these
two camps and it is clear that those already
using CO2 (water) have no particular incentive
to move to other solutions. For those using
HCFCs, however, the options include saturated
HFCs (particularly HFC-134a), unsaturated
HFCs and methyl formate. In developed
countries, a number of manufacturers have
already converted to HFC-134a despite its
environmental profile and total instantaneous
emission. Unsaturated HFCs would seem
like an unlikely candidate in this application
because of cost, but the way would remain
open for methyl formate, based on recent test
assessments within the Pilot Project.
Concluding remarks
This sector is already less reliant on HCFCs
than most of the others covered in this
Sourcebook and the remaining transition
would not seem to represent a significant
international challenge. With CO2 (water)
technology already well established in large
parts of the sector, the other technology
options need to offer significant additional
competitive advantages to gain market
share. The use of saturated HFCs in the
sector would appear avoidable and may
be increasingly discouraged under future
climate-policy frameworks.
7.3 PHENOLIC FOAMS
Phenolic foams have been in existence since
the middle part of the 20th century, but have
only been used substantially in the insulation
foam sector since the development of closed
cell foam technology in the late 1970s and
through the 1980s. Significant markets have
developed in both Europe and Japan since
then based on a combination of Boardstock
and Block/Pipe products. The development of
similar markets in North America was thwarted
by poor experience with a specific roofing
board technology (Koppers) that created
corrosion problems on steel-decks. The
primary benefits conveyed by phenolic foams
are excellent thermal performance (see below)
and intrinsic resistance to fire, with very low
smoke generation.
A further application of phenolic foam has been
as floral foam. When modified with appropriate
surfactants, phenolic foams provide hydrophilic
blocks that can be used to retain water in
flowe r arrangements. The primary brand
globally is known as ‘Oasis’. However, this
material has never significantly been blown
with ozone depleting substances, except in the
case of small ‘me too’ producers. It is therefore
not the prime focus of attention in this section.
Critical Foam Processing and
Product Properties
Phenolic chemistry differs from much of the
polyurethane sector in that blowing agents
are typically insoluble in the base resin. This
means that the overall system is an emulsion
and requires excellent mixing to create a
uniform blend. The emulsion chemistry makes
processing more sensitive, since the mix
viscosity is higher than typical polyurethane
systems. However, the benefit of emulsion
chemistry is that small and very evenly
distributed cell sizes can be achieved. In fact,
this has led to some of the best performing
foams from a thermal insulation perspective,
since this is a net result of small, uniform cells.
The dis-benefit of that same cell structure is
that acoustic insulating properties are poor.
Notwithstanding this, some polyisocyanutate
foam producers have followed the phenolic
lead and moved to emulsion systems.
Critical foam processing and product
properties are very similar to those for rigid
polyurethane foams and are depicted in the
table below for the applications served by
phenolics:
 UNEP DTIE Foam Sourcebook - 2010

Application Required Foam Property or Process Characteristic

Ease of Curing Insulating Mechanical Density Ozone Global

Processing Time Capability Strength Depletion Warming

Boardstock 444 444 444 444 44 444 444

Blocks 44 44 4 4 4 444 44 444 444

Blowing Agent Selection and how it
contributes to Required Foam Properties
Phenolic chemistry is relatively sensitive to
temperature and therefore requires elevated
temperatures to achieve appropriate curing
times. It is therefore important that blowing
agents are selected that boil at appropriate
temperatures and do not have substantial
latent heat effects. The elements of blowing
agent selection impacting foam properties and
processing characteristics are summarised in
the table below:

Required Property Relevant Blowing Agent Property

1. Ease of Processing Flammability (the lower the better)

Boiling Point (needs to be tailored to avoid significant latent heat effects)

Capable of forming well mixed emulsions

2. Curing time Can be impacted by latent heat effects of the blowing agent

3. Insulating Performance Gas Thermal Conductivity*

Solubility in Formulation (the lower the better)

Permeability through Cell Wall (the lower the better)**

4. Mechanical Strength Permeability through Cell Wall (the lower the better)**

Boiling Point (the lower the better to improve cell pressure & avoid condensation)

5. Foam Density Foam Density

6. Environmental GWP

ODP

* In the normal density range (35 – 45 kg/m3) the thermal conductivity of phenolic foam is primarily determined by the composition of the cell gas.
However, it should be noticed that the cell structure (morphology) also has a strong effect on the thermal conductivity (thermal radiation).
** Permeability is the combination of the gas diffusivity though the cell wall and its solubility in cured matrix

81
Against these criteria, the eligible blowing
agents for phenolic foams can be assessed as
follows

Rating of Blowing Agent Types by Criterion

HCFC-141b 2-chloropropane Hydrocarbons Saturated Unsaturated HFCs

Blowing Agent Criterion Hydrocarbons HFCs (HFOs)

Flammability ++ ++ + +++ ++/+++

Boiling Point (Processing) ++ +++ ++/+++ ++/+++ ++/+++
Emulsion Formation ++ ++ ++ +++ ++/+++
Gas Thermal Conductivity ++ ++ +/++ ++/+++ ++/+++
Permeability through Cell +/++ ++ ++ +++ +++
Boiling Point ++ ++/+++ ++/+++ ++/+++ ++/+++
Blowing Efficiency ++ ++ +++ + ++/+++
Ozone Depletion Potential + ++ +++ +++ +++
Global Warming Potential +/++ ++/+++ ++/+++ + ++/+++

+++= Good ++= Fair += Poor

As can be seen, the blowing agent choices
for phenolic foam are similar, but not identical,
to those available for polyurethane foams.
Notable absentees are CO2 (water), since
the isocyanate reaction is not an option, and
methyl formate – which remains untried with
this chemistry.
In the early stages of transition, it was
believed that the selection of hydrocarbons
as alternative blowing agents would be
substantially detrimental to the fire properties
of phenolic foam. However, in practice, as is
described in the following sub-sections, the
phenolic matrix has been demonstrated to be
sufficiently robust to counter any significant
impact from the presence of hydrocarbons. As with other foam types, the capital
This has meant that hydrocarbons have investment for hydrocarbons is the main
emerged as a major alternative for the sector in barrier, while benefits are gained in on-going
recent years. operating costs. However, the reverse is the
case for saturated HFCs and this is likely to
Economic Viability and Cost extend to unsaturated HFCs as well.
Effectiveness Criteria
Picking up on this trend towards
hydrocarbons, the investment to manage the
flammability issue is similar to that for rigid
polyurethane foams. Accordingly, the following
table provides an assessment of the economic
viability and cost effectiveness of alternatives:

Economic viability and cost effectiveness criteria

HCFC-141b 2-chloropropane Hydrocarbons Saturated Unsaturated HFCs

Blowing Agent Criterion Hydrocarbons HFCs (HFOs)

Investment Costs + ++ +++ + +

Operating Costs ++ ++ + ++/+++ +++
Widespread Availability ++ ++ ++ +/++ +
Potential to blend ++ ++ ++/+++ +++ ++

+++= High ++= Medium += Low

82

7.3.1 PHENOLIC – Boardstock
As noted in the introductory paragraphs
of Section 7.3, the growth of the phenolic
boardstock sector has been thwarted to
an extent by technology issues in the North
American market. However, the European
market, and most notably the markets in the
United Kingdom and Benelux have been able
to press ahead with the commercialisation
of technologies into this sector. The intrinsic
fire, smoke and toxicity performance of the
products coupled with their high degree of
thermal performance has made them highly
competitive with other forms of boardstock
product in the marketplace. Market penetration
has been assisted by the fluctuations in cost of
various polyurethane raw materials and, more
latterly, by the rapid growth in demand for
boardstock products in general, as the thermal
requirements in fixed-dimension cavity walls
have increased.
This said, the geographic spread of phenolic
boardstock production and use remains
limited – partly because of the availability of
technology and partly because of the precise
processing parameters associated with these
technologies. There are some less onerous
technology options available, but these have
not tended to meet the product performance
required to make significant market in-roads.
UNEP DTIE Foam Sourcebook - 2010
Historical trends in actual Blowing Concluding remarks
Agent selection Although it is not yet clear how the
The traditional blowing agent for phenolic emergence of unsaturated HFCs might
boardstock was CFC-11, although this was affect the blowing agent choices for
rapidly superseded by HCFC-141b. The use of future phenolic boardstock formulations,
HCFC-141b presented a particular challenge the overall performance of the various
for the phenolic emulsion chemistry because of hydrocarbon-based technologies make it
its solubility and the major technology holders unlikely that there will be further technology
found it necessary to modify the blowing agent transitions in the short term.
with additives to make it less soluble in the
There has been little, if any, implementation
foam mix.
of phenolic foam boardstock facilities in
In the transition that took place from HCFC- developing countries to date, so any future
141b in Europe, it became self-evident that investment is likely to be based completely
the phenolic product itself was sufficiently on technology transfer from Europe or
robust in its fire performance to accommodate elsewhere.
hydrocarbon blowing agents for the bulk of
end-uses. Therefore, the bulk of continuous
processes are now based on n-pentane,
either on its own or in blends with other
hydrocarbons. One technology in Europe
had moved directly from CFC-11 to 2-chloro-
propane and continues to use this blowing
agent as the basis for its product range.
There is limited use for saturated HFCs in
these continuous processes, since thermal
performance based on optimised hydrocarbon
formulations is seen as sufficient for most
end-uses.
83
 7.3.2 PHENOLIC – Blocks
The initial production of phenolic blocks pre-
dated that of phenolic boardstock by at least
15 years. This was generally in the form of
discontinuous blocks and was largely driven
by the interest in floral foam. However, the use
of block-based phenolic foams for a number
of utilitarian uses in the panel sector began to
emerge in the 1980s as the fire performance of
the product began to be recognised.
The development of reliable closed-cell (low
thermal conductivity) technologies in the
early 1980s made the product much more
competitive with other foam types as well
as with mineral fibre. The particular market
that opened up for phenolic block foam
was the pipe section market in the UK,
where fire performance precluded the use
of polyurethane foams. The product was
particularly successful and continues to hold a
dominant market position in the non-domestic
buildings market.
The comments on wastage highlighted in
Section 7.1.8 also apply to the phenolic foam
sector and this was of particular concern to the
pipe section manufacturers. This has led to the
more recent development of a continuous pipe
section manufacturing process which avoids
the high wastage levels for the most popular
pipe sizes and thermal requirements.
84
Historical trends in actual Blowing Concluding remarks
Agent selection Phenolic foam continues to be something
As with other phenolic foam product/process of a niche product in most global markets
types, CFC-11 was the basic blowing agent and has seen little success to date in
of choice, except for the floral foam industry developing countries. However, its innate
where the market leader developed a specific potential continues to be recognised in a
block foam technology based on hydrocarbon number of important and growing markets.
(n-pentane). This necessitated investment in In general terms, it is believed that any
risk reduction measures, which the company further development of a manufacturing
successfully implemented. In same cases, base in developing countries will be
the boiling point of the blowing agent was supported by comprehensive technology
modified by using CFC-11/CFC-113 blends transfer from one of the current technology
in order to ensure the appropriate rise/ holders.
cure profile. This was particularly important
As a consequence, there seems to be little
for phenolic chemistry where the sensitivity
requirement for support for the transition
between temperature and cure rate is high.
of existing phenolic foam facilities in
The reduction in the latent heat of evaporation
developing countries.
in the early stages of the reaction helped to
ensure appropriate processing times.
In similar fashion to the phenolic boardstock
sector, the first transition was to HCFC-141b,
with the same use of additives to reduce
solubility of the blowing agent. In moving from
HCFC-141b under the regulatory pressures in
both Europe and North America, the industry
initially moved to saturated HFCs. The choice
was typically HFC-365mfc/227ea for boiling
point reasons (as for CFC-11/CFC-113
blends). There is still a lack of widespread use
of hydrocarbons in phenolic block processes
for insulation purposes, although its use
continues for floral foams.
As noted in the previous sub-section, the
introduction of a continuous pipe section
process has enabled reduction in foam losses,
but has also enabled a switch in blowing
agent to hydrocarbons, based on the more
controllable environment. The bulk of phenolic
pipe section supply in the UK is now based on
this technology.
 UNEP DTIE Foam Sourcebook - 2010

7.4 THERMOPLASTIC FOAMS In Europe, the requirements are more

As noted in Section 4.1, extruded
thermoplastic foams are the only ones
that have historically used ozone depleting
substances. In the case of extruded
polystyrene, products fall into two categories:
‘board’ and ‘sheet’, with ‘board’ being
used for a variety of insulation, buoyancy
and recreational activities, while ‘sheet’
has been focused on food and other
packaging. Polyolefin (both polyethylene and
polypropylene) foams have also found uses
in these sectors, but the use of polyolefin
foams in insulating applications has been more
limited.
Equipment for the manufacture of extruded
thermoplastic products varies substantially
by region and application. In North America,
where the primary requirement for extruded
polystyrene is insulating sheathing boards
for the residential construction market,
the manufacturing lines tend to be long,
for optimum speed and also capable of
producing wide boards (typically 1.2 metres) at
thicknesses down to 25mm. This requirement
necessitates a substantial engineering solution
and makes the transfer from one blowing
agent to another very challenging.
modest, with many lines generating product
at a maximum of 0.6 metres in width and
at greater thicknesses – often driven by the
higher thermal insulation requirements of the
commercial building sector. In South East
Asia (most notably China), where the demand
for extruded polystyrene foam is growing
at its fastest, the technical and processing
requirements are still more limited. In many
cases, the polystyrene being used for extrusion
has a high recycled content, making it less
easy to process. Products generated in
this scenario tend to be lower grade than in
North America and Europe and are typically
processed on 0.6 metre lines.
Critical Foam Processing and
Product Properties
Extruded thermoplastic foams provide some
significant properties not available with rigid
polyurethane foams. These include an extra
measure of resilience and excellent moisture
resistance. This makes them particularly suited
for floor insulation in construction applications.
The table below highlights these foam
properties and reflects also the demanding
nature of manufacture for the construction
industry in some regions.

Application
Required Foam Property or Process Characteristic

Ease of Moisture Insulating Mechanical Density Ozone Global

Processing Resistance Capability Strength Depletion Warming

XPS – Board (Construction) 444 444 444 444 44 444 44

XPS – Board (Other) 44 44 4 4 444 44 444 44

Polyolefin - Board (Other) 44 44 44 444 44 444 44

85
1. Ease of processing. Since the industry is
working with thermoplastic raw materials,
processing characteristics such as polymer
melt temperature and melt viscosity become
critically important. These characteristics
depend significantly on the quality and
consistency of the raw materials, making the
use of post-consumer recycled materials, as
practiced in China, particularly challenging. The
blowing agent can have in impact of properties
such as melt viscosity, since they can often
plasticise the mix. The compatibility of the
blowing agent can also influence its solubility
and, in particular the pressure at which the
matrix degasses and the foam expands.
2. Moisture Resistance. This is typically a
characteristic of the polymer itself and can be
maintained in foam products provided that the
cell structure is of a high quality. This usually
means that the density cannot be driven too
low or inferior sources of raw materials used.
The process needs to remain consistent
throughout.
3. Insulating Capability. Again, high quality
cell structure is a pre-requisite to deliver
closed cells which can retain the blowing
agents. However, thermoplastic materials are
also more susceptible to diffusion through
the cell walls. Considerable study has been
conducted on the relative diffusion rates of
popular blowing agents and these have been
reported in a number of publications (e.g. Vo
and Pacquet, 2004).
4. Mechanical Strength. Extruded
thermoplastic foams are generally renowned
for their strength-to-weight ratio and their
resilience, since the action of the extruder
is to provide a ‘skinned’ product which
provides a degree of extra protection. For
flooring applications in the construction sector,
particular care needs to be taken in ensuring
that foam quality is high enough to provide the
desired strength at minimum density.
5. Foam Density. Typical foam densities for
thermoplastic foams range from 25-35 kg/m3.
The previously listed properties tend to improve
with density within this range. Therefore,
the skill of the manufacturer is to tailor the
manufactured density to the minimum required
to meet the requirements of the application.
The more consistent the raw materials and
process conditions are, the more confident the
manufacturer can be and the less margin for
variability needs to be applied.
Blowing Agent Selection and how
it contributes to Required Foam
Properties
Most thermoplastic foams still depending
on HCFCs have used a combination of
HCFC-142b and HCFC-22. The proportions
of each have varied considerably depending
on the application and, in some instances,
each blowing agent has been used in isolation.
This will be discussed further in Section 7.4.1.
The inter-relationship between foam property/
processing characteristic and blowing agent is
shown in the following table:

Required Property Relevant Blowing Agent Property

1. Ease of Processing Flammability (the lower the better)

Boiling Point (significance depends on handling equipment)

Solubility in Formulation (the higher the better)

2. Moisture Resistance Broadly independent of blowing agent choice, if processing OK

3. Insulating Performance Gas Thermal Conductivity*

Permeability through Cell Wall (the lower the better)**

4. Mechanical Strength Broadly independent of blowing agent choice, if processing OK

5. Foam Density Blowing Efficiency (molecular weight)

6. Environmental GWP

ODP

* In the normal density range (25 – 35 kg/m3) the thermal conductivity of thermoplastic foams is primarily determined by the composition of the cell
gas. However, it should be noticed that the cell structure (morphology) also has a strong effect on the thermal conductivity (thermal radiation).
** Permeability is the combination of the gas diffusivity though the cell wall and its solubility in cured matrix

86
 UNEP DTIE Foam Sourcebook - 2010

Alternatives to HCFC-142b/22 include, saturated and unsaturated HFCs, hydrocarbons, CO2 and CO2/ethanol. CO2, in isolation, has
been found to be particularly difficult to process, which is one of the reasons why combinations with oxygenated hydrocarbons have
been explored. Even then, there have been some short-comings in the technology that have limited processing speeds and product
ranges. The following table provides an indication of some of the perceived strengths and weaknesses:

Rating of Blowing Agent Types by Criterion

HCFC-141b Hydrocarbons Saturated Unsaturated CO2 CO2 /ethanol

Blowing Agent Criterion HFCs HFCs (HFOs)

Flammability ++ + +++ ++/+++ +++ ++

Boiling Point (Processing) ++/+++ +++/+++ ++/+++ ++/+++ + +/++
Solubility in Formulation +++ +++ ++ ++ + ++
Gas Thermal Conductivity ++ +/++ ++/+++ ++/+++ +/++ +/++
Permeability through Cell ++ ++ +++ +++ +/++ +
Blowing Efficiency ++ ++ ++ ++ +++ +++
Ozone Depletion Potential + +++ +++ +++ +++ +++
Global Warming Potential +/++ +++ +++ +++ +++ +++

+++= Good ++= Fair += Poor

87
 It can be seen here that unsaturated HFCs
have the potential to provide the best all-
round solution from a purely technical and
environmental perspective. Hydrocarbons also
offer a significant solution provided that the
flammability issues can be managed at both
product and process level. The extruded foam
industry has had significant experience of
managing hydrocarbons in the ‘sheet’ sector
which tended to bypass HCFCs and move
straight to hydrocarbons when phasing out of
CFCs. However, the experience of fires was
common-place and led some to conclude
that this was not really a sustainable solution.
Nevertheless, few ‘sheet’ manufacturers have
stepped back from their choice and have
presumably found coping strategies.
HCFC-142b/22
Blowing Agent Criterion
Investment Costs + ++/+++
Operating Costs ++
Widespread Availability ++
Potential to blend ++
+++= High ++= Medium
88
There is an additional challenge for ‘board’ Economic Viability and Cost Effectiveness
products, however. ‘Sheet’ products tend Criteria
to be relatively thin and lose their blowing
Some of the major challenges for the
agent rapidly, whereas board products can be
thermoplastic foams sector lay in dealing
substantially thicker for both construction and
with investment costs and/or blowing agent
packaging applications. In developed countries
availability. The following table illustrates
where hydrocarbons have been adopted
the fact that penalties are likely to be faced
(particularly in polyolefin foams), this led to a
either in the context of investment cost (e.g.
particular problem with boards in storage and
hydrocarbons or CO2) or in operating costs
transport. In essence, the rate of diffusion
and availability (saturated and unsaturated
of hydrocarbon out of the products was not
HFCs). However, it should be noted that
sufficiently fast after production to avoid the
HFC-134a is relatively widespread because of
build-up of flammable gases in the post-
its use as a refrigerant.
production areas. This led to some incidents.
The matter was finally addressed by most
manufacturers through the use of perforating
equipment to release the hydrocarbon blowing
agent physically.
Hydrocarbons Saturated Unsaturated CO2 CO2 /ethanol
HFCs HFCs (HFOs)
+ + +++ ++/+++
+ ++/+++ +++ +/++ +/++
++ +/++ + +/++ +/++
++/+++ +++ ++ ++/+++ ++/+++
+= Low

7.4.1 EXTRUDED POLYSTYRENE
– Board
As noted in previous sections, the use of
extruded polystyrene is primarily in the
construction sector where it is used for a
variety of insulation purposes, both in walls and
roofs, but most notably in floors, where the
product has specific competitive advantages.
The product has competed successfully
against both rigid polyurethane foams and
mineral fibre in all the major regions of the
world, although its mode of success has varied
depending on the regional demand patterns.
This point speaks to the versatility of extruded
polystyrene in its application.
Historical trends in actual Blowing
Agent selection
The whole extruded thermoplastic foam
sector was established on the ease of use
of CFC-12 as a blowing agent. The blowing
agent provided the inert character and thermal
performance to deliver high quality products
at affordable prices. It was only when the
phase-out of CFCs was required that the
split between choices for ‘board’ and ‘sheet’
materials occurred. As noted in Section 7.4,
sheet products moved predominantly to
hydrocarbons, while board products chose
to use HCFC-142b/22 blends for the most
part, in order to retain the requisite thermal
performance.
When the blend was chosen, it was known
that the cell wall permeability of HCFC-142b
was significantly lower than that of HCFC-22.
Therefore, the long-term thermal performance
of products would largely be determined
by the proportion of HCFC-142b in the
blend and its subsequent retention. Since
UNEP DTIE Foam Sourcebook - 2010
HCFC-22 is a major refrigerant, its availability
has been greater, and its price lower,
throughout its period of use. This has been
particularly important in some developing
country regions where access to HCFC-
142b has been more difficult and the cost
significantly higher. Since some product and
building codes will have been written around
the sole use of HCFC-22, it may make the
transitional hurdle a little easier when phase-
out of HCFCs is finally embraced.
Concluding remarks
The extruded polystyrene sector is
continuing to grow rapidly in China and
elsewhere in Asia and practical transitional
solutions will be essential. It seems unlikely
that either saturated or unsaturated HFCs
will make major in-roads in the markets for
reasons of cost and availability. Therefore,
the most likely solution will be based on
hydrocarbons, on their own or in blends.
The level of investment needed to support
this is unclear, but, since the plants are
relatively small, and there is parallel
experience with extruded polystyrene
sheet, it may be that the transition will be
less challenging than currently envisaged.
CO2 seems unlikely as a solution in
isolation. The extrusion process remains
highly emissive, and this puts a particular
burden on the avoidance of high GWP
solutions, such as saturated HFCs. The
only time when such an approach might be
justified is in applications and jurisdictions
where thermal performance is absolutely
paramount. In these cases, it may be
possible to maker further transitions from
saturated to unsaturated HFCs in due
course.
89
 7.4.2 POLYOLEFIN FOAMS
Polyolefin foams have made less penetration
into the construction markets that have been
the bedrock of the extruded polystyrene
industry. The one exception to this has
been in the pipe insulation sector, where
the added resilience offered by the product
has proved of substantial value. The primary
use for polyolefin foams has been as a high
performance packaging material – particularly
when used for the packaging of delicate, high
value equipment.
Historical trends in actual Blowing
Agent selection
The choice of blowing in the polyolefin foam
sector has followed a very similar pattern to
that of extruded polystyrene foam. However,
because of the lack of a large demand for
insulating properties, the industry switched
more fully to hydrocarbons when transitioning
from CFCs. It therefore had to address some
of the issues discussed in sub-Section 7.4
regarding the storage and transport of these
products.
90
The remaining use of HCFCs in this product
sector is much more limited than in the
extruded polystyrene sector. Nevertheless,
where use does exist – possibly in goods
related to recreational applications – technical
assistance may be necessary to ensure that
appropriate precautions are taken in any final
switch to hydrocarbons
Concluding remarks
The polyolefin foam sector is only seen to
present a limited challenge in the efforts to
phase of HCFCs under Decision XIX/6. It
would appear that relevant climate-positive
solutions are available and that widespread
experience exists concerning their use.
There maybe some, as yet, unidentified
niche applications that could present more
of a challenge, but no evident has yet
emerged to this effect.
UNEP DTIE Foam Sourcebook - 2010

91
Section 8.
Funding Strategies

“The provisions for the funding of HCFC

phase-out investments are becoming
clearer, although some aspects related
to climate benefits remain uncertain”

92

Section 8.
Funding Strategies
8.1 Funding the Ozone Component
The Multilateral Fund was established at
the London Meeting of the Parties to the
Montreal Protocol in 1990. The London
Amendment signalled the intent of the non-
Article 5 Countries to assist financially the
Article 5 Countries in meeting their phase-
down (and ultimately phase-out) obligations
for CFCs. The principle was extended to
what were then known as Countries with
Economies in Transition (CEIT) through the
Global Environment Fund (GEF). Both the
Multilateral Fund and the GEF therefore had
early exposure to the challenges of technology
transition for ODS.
As noted in Section 1, the Beijing Amendment
introduced a time-certain phase-out for HCFCs
for Article 5 Countries based on a production/
consumption freeze in 2016 followed by a final
phase-out in 2040. No phased reductions
were scheduled at that time. These came
later in Decision XIX/6 when the phase-out
was effectively brought forward to 2030 by
restricting the tail of use between 2030 and
2040 to 2.5% of the initial capped level of
consumption in 2013. Additional steps were
inserted for 2015 (10%), 2020 (35%) and
2025 (65%) as already described in Section
1. Within the same negotiation it was agreed
that a similar funding provision would be made
for HCFC phase-out under the Multilateral
Fund, even though there had been an earlier
rule preventing the funding of ‘second
conversions’.
Since the negotiation of Decision XIX/6,
the Parties in general, and the Executive
Committee of the MLF in particular, have
sought to define the funding rules for
transitions away from HCFCs. These have
proved to be more challenging than originally
envisaged for a number of reasons:
UNEP DTIE Foam Sourcebook - 2010
• Threshold limits for investment had for the period 2009-2011, but growing to US$
previously been calculated in terms of cost 238.3-357.5 million in the triennium 2012-2014
per ODP- tonne. However, the lower ozone as the project activities in advance of the 2013
depletion potentials of HCFCs result in much freeze were undertaken.
higher costs for each ODP-tonne phased out
These figures were believed to be a pragmatic
and provide a significant discontinuity with
estimate of the likely technology transitions
previous practice.
foreseen at the time, but did not specifically
• There has been an increase in multi- exclude some implicit climate impacts. Other
national ownership of companies in scenarios that were considered were:
developing countries and this makes a higher
1. Lowest cost technology options only,
proportion of the installed capacity ineligible
irrespective of climate benefit or dis-benefit
for funding.
(the Baseline Scenario)
• Where overarching HPMPs provide a
2. A cost estimate based on an available
phase-out schedule, often on a sector-
threshold investment for climate (e.g. US
by-sector basis, there is no obligation for
$20 per additional tonne of CO2 saved) (the
individual enterprises to comply with the
Functional Unit Scenario)
schedule unless the HPMP is enforced
through national regulation 3. The cost of achieving the total technically
feasible climate benefits.
• There has been a need to re-establish cut-
off dates for funding and the inter-relationship In most instances, it was viewed as
with rules for second conversions premature to make these assessments since
a high level of project analysis would be
• The ‘worst-first’ principle may place focus
required to produce meaningful estimates.
on sectors that are not the most cost-
In addition, there was concern that, with
effective to convert and take flexibility from
further developments in technology options
the HCFC Phase-out Management Plans
likely, the estimates would become rapidly
themselves.
outdated. Nevertheless, these arguments did
• As noted in Section 3, there is still not diminish interest in this type of analysis
some uncertainty about how to factor the and one of the most interesting conceptual
climate component into decision-making assessments was deemed to be the evaluation
and prioritisation under the MLF. This is a of the cost of the ozone-related transition
separate issue from climate co-funding itself, element only – i.e. the investment that would
but is closely inter-related. lead to climate neutrality. The value of such
an analysis arises from the possibility of
These factors have made it extremely difficult
distinguishing between ozone-related finance
for the Montreal Protocol bodies to assess
and climate-related finance. The following
the likely funding requirements for HCFC
graphic illustrates the principle:
phase-out. An initial assessment in 2008 by
the Technology and Economic Assessment
Panel (TEAP) through its Replenishment Task
Force estimated project costs (excluding
refrigeration servicing) of US$ 66.5-115 million
HCFC replacement
technology
Climate Component
(various funding options)
Existing HCFC Use
Ozone Component (Usually MLF funded)
93
In taking this approach, there is an implicit
assumption that climate co-funding can be
made available to meet any additional cost
related to further climate benefit. This can
come in one of two forms: - (i) cost-coverage
and (ii) market valuation. These are covered
further in Section 8.2.
At the 60th Meeting of the Executive
Committee in April 2010, the members were
finally able to reach consensus on the basic
rules relating to HCFC Projects. The primary
items are as follows:
• The cut-off date agreed for eligibility of
equipment for conversion is 21st September
2007. Equipment installed after that date will
not qualify
• Second stage conversions will be
accepted in the period to 2013, where
projects can demonstrate that:
• They are essential for compliance with
the 35% cut by 2020 and/or
• They represent the most cost-effective
options for compliance
• Where neither of these criteria applies,
funding will be limited to installation, trials
and training
• In order to avoid dis-incentivising early
action, countries can identify starting points
prior to the baseline assessment in 2009-
2010. These can relate to the point of HPMP
submission or the date of project submission
– whichever is the earliest. The starting points
can be based on the last reported HCFC
consumption under Article 7 on the Montreal
Protocol or on the average of consumption
forecast for 2009 and 2010.
With respect to incremental costs in achieving
2013 and 2015 targets, the following rules
were established:
• The technical information in UNEP/
OzL.Pro/ExCom/55/47 shall be used as a
reference point for project preparation
• To overcome the impact of the lower
ozone depleting potentials of HCFCs, the
94
previously established threshold limits for
CFCs would be applied on a ‘per metric kg.
basis’ for HCFCs, thereby taking the ODP
issue out of the assessment.
• Up to 20% of the funding allocated
for incremental operating costs can be
transferred to cover incremental capital costs
as long as this flexibility does not change the
intent of the project.
• For the foam sector, the following
thresholds were set:
• Incremental operating cost of US$1.60
per metric kg. of HCFC-141b
• Incremental operating cost of US$1.40
per metric kg. of HCFC-142b
• ExCom can award higher IOC levels for
CO2 (water) projects
• Systems houses are able to calculate their
allowances based on the total downstream
uses of HCFCs.
All of these measures are seen to provide
additional clarity to the funding scenarios for
Article 5 countries as they seek to implement
their HPMPs. However, perhaps the most
striking of all of the measures agreed at the
60th Executive Committee meeting was a
decision to allow additional funding amounting
to 25% of the normal cost-effectiveness
threshold for projects adopting low-GWP
alternatives.
This development, whilst welcome in its
intention to prioritise climate issues in the
technology transitions occurring under
Decision XIX/6, creates a number of additional
questions based on the contents of this Foam
Sourcebook. These include:
1. How will the term Low-GWP be defined in
practice? The Report from TEAP responding
to Decision XXI/9 provides some thinking in
this area, including a cut-off point for ‘Low-
GWP’ of 300, but it is not clear whether such
an analysis will have any place in this type of
funding regime.
2. How will the measure be aligned with
the wider requirement of Decision XIX/6 to
assess both energy and GWP aspects in its
prioritisation of measures?
3. How will the provision of extra funding
for apparent climate-beneficial technologies
influence the ability of projects to seek climate
co-funding from other sources (this matter is
also touched on in Section 8.2)
4. How will the life cycle emissions
characterisations included in the MCII be
factored in to the climate funding mechanism,
if at all?
These matters will be points of discussion for
a number of months to come, but the initiative
to promote projects with perceived climate
benefits is clearly a significant one at this
juncture.

8.2 Climate Co-Funding
Opportunities within the Montreal
Protocol Framework
The Multilateral Fund of the Montreal Protocol
provides financial assistance to Article 5
countries for the incremental costs of phasing
out ozone depleting substances. The total
incremental costs can include both agreed
capital investment costs and incremental
operating costs (IOCs). IOCs will generally only
be met for a limited period after the technology
transition is made.
In cases where the enterprise proposing the
project would get additional benefits from a
technology upgrade, the Multilateral Fund
does not pay for such costs as they are not
considered “incremental.” In such cases,
the enterprise has to bring its own funding to
cover the technology upgrade. However, this
principle does not apply to climate benefits,
which are viewed as in line with the objectives
of the objectives of the accelerated HCFC
phase-out.
Decision XIX/6 of the Meeting of the Parties
encourages countries to select alternatives
to HCFCs that minimize the climate impact.
Decision XXI/9 taken at the 21st Meeting
directs the Executive Committee of the
Multilateral Fund “to consider providing
additional funding and/or incentives for
the additional climate benefits where
appropriate….” This key decision, along with
Decision XIX/6, gives quite clear guidance to
include additional funding for projects that
benefit both ozone layer and global climate.
The provision of up to 25% additional funding
for the introduction of low-GWP alternatives
can be viewed as first step to obtain climate
benefit from ozone layer protection projects.
UNEP DTIE Foam Sourcebook - 2010
The Multilateral Fund is considering the
establishment of a Special Funding Facility
for HCFC phase out projects which produce
climate gains. The reader is advised to keep in
contact with his/her country’s National Ozone
Unit and the relevant Implementing Agency to
understand the additional funding mechanism
through the Special Funding Facility, as and
when it is established.
Additional avenues for financing
HCFC phase out projects that have
climate benefits
A number of parallel, grant-financed and
market-financed opportunities also exist for
co-funding of climate benefits. These include:
• Voluntary Carbon Market (VCM)
-supported by frameworks such as those
provided through the Voluntary Carbon
Standard;
• Pre-compliance Market - supported by
frameworks such as those provided through
the Climate Action Reserve ;
• Clean Development Mechanism (CDM) - in
cases where the project results in improved
energy efficiency;
• Global Environment Facility (GEF);
• Other donor-led funds - such as those that
may emerge via the Copenhagen Accord
Since the options are evolving quickly, it
is important that the reader discusses the
applicability of these financing schemes with
the National Ozone Unit and the relevant
Implementing Agency. Some of these financing
options are dependent on the existence of
international regulatory frameworks, and
attention must be paid to the rules and
regulations of the respective mechanism.
1
The Climate Action Reserve activities also extend to the voluntary
carbon market
95
Section 9.
Conclusions

“The schedule established

for HCFC phase-out creates
pressure for the foam sector to
act urgently”

96
 UNEP DTIE Foam Sourcebook - 2010

Section 9.
Conclusions

This Sourcebook has hopefully provided

relevant guidance on available technology
options and the major factors that need to be
considered in making technology selections. In
doing so, it has illustrated the following:

• There are a number of emerging

technologies that may provide optimal
alternatives to HCFCs and may bypass the
need for high GWP solutions

• In some sectors these alternatives may be

well established, although they may require
certain economies of scale to be justified
under likely funding scenarios

• It seems likely that additional funding could

be available to support the achievement
of incremental climate benefits. However,
the route by which these might be
made available is still largely unclear and
considerable further work may be required
before these provisions can be finalised. The
one exception to this is the 25% increase
in incremental cost thresholds for low-GWP
solutions under the Multilateral Fund

• Although there may be arguments to

delay final technology decisions until the
situation is clearer. However, the reality of
the 2013 freeze in compliance terms and
the impact of the ‘worst-first’ imperative on
HCFC-141b projects may make such a delay
a luxury that cannot be afforded within many
HPMPs. In practice, there are a number of
low GWP solutions already available.

97
 The following tables summarise the
characteristics of some of the main alternative
technologies available:

Sector Option Maturity Energy GWP Emissions Cost

Impacts Production Use Phase E-o-L Investment Operating

- Domestic Appliance HCs High Medium Low Low Low Variable High Low

s-HFCs Medium Medium High Low Low Variable Low MedHigh

u-HFCs Low Medium Low Low Low Variable Low High

- Other Appliance HCs Medium Medium Low Low Low Variable High Low

MF Medium Medium Low Low Low Variable Low/Med Low/Med

CO2/H2O High High Low Low Low Variable Low MedHigh

- Transport & Reefers HCs Low Medium Low Medium Low MedHigh Medium Low

s-HFCs Medium Low High Medium Low MedHigh Low MedHigh

- PU Boardstock HCs High Medium Low Low/Med Low/Med MedHigh High Low

u-HFCs Low Low Low Low/Med Low/Med MedHigh Low High

- PU Continuous panel HCs High Low/Med Low Low/Med Low Variable High Low

s-HFCs High Low High Low/Med Low Variable Low MedHigh

u-HFCs Low Low Low Low/Med Low Variable Low High

- PU Discontinuous panel MF Low/Med Medium Low Medium Low Variable Low/Med Low/Med

s-HFCs MedHigh Low High Medium Low Variable Low MedHigh

u-HFCs Low Low Low Medium Low Variable Low High

- PU Block Foam HCs Medium Medium Low MedHigh Medium MedHigh High Low

s-HFCs MedHigh Low High MedHigh Medium MedHigh Low MedHigh

MF Low Medium Low MedHigh Medium MedHigh Low/Med Low/Med

- PU Spray Foam s-HFCs High Low High High Medium High Low MedHigh

MF Low/Med Medium Low High Medium High Low/Med Low/Med

u-HFCs Low Low Low High Medium High Low High

- PU Pipe-In-Pipe HCs High Low/Med Low Low Low Low MedHigh Low

- PU Rigid Integral Skin HCs Low Low Low MedHigh MedHigh High MedHigh Low

MF Low Low Low MedHigh MedHigh High Low/Med Low/Med

98
 UNEP DTIE Foam Sourcebook - 2010

Tables of this nature need to be approached choices in such a summarised format. of the relative technologies and to focus
with caution, since it is impossible to cover Nevertheless, the intention, as with the on the areas that may need more in-depth
all of the possible technology and application Sourcebook overall, is to provide some initial investigation and project and/or programme
nuances that can influence the validity of guidance in the strengths and weaknesses level.

Sector Option Maturity Energy GWP Emissions Cost

Impacts Production Use Phase E-o-L Investment Operating

- PU One Component s-HFCs High Low High Low High N/A Low MedHigh

u-HFCs Low/Med Low Low Low High N/A Low MedHigh

DME Medium Low Low Low High N/A Low High

- PU Flexible Integral Skin MF Low/Med Low Low Low High N/A Low/Med Low/Med

CO2/H2O MedHigh Low Low MedHigh High N/A Low/Med MedHigh

- Phenolic – Boardstock HCs MedHigh Medium Low Low/Med Low/Med MedHigh High Low

u-HFCs Low Low Low MedHigh Low/Med MedHigh Low High

- Phenolic – Block HCs Medium Medium Low MedHigh Medium MedHigh High Low

s-HFCs MedHigh Low High MedHigh Medium MedHigh Low MedHigh

u-HFCs Low Low Low MedHigh Medium MedHigh Low High

- XPS – Board CO2 Medium MedHigh Low High Low/Med MedHigh High Low

s-HFCs High Low High High Low/Med MedHigh Low/Med MedHigh

DME Low Low Low Low/Med Low/Med MedHigh Low High

u-HFCs Low/Med Medium Low Medium Low/Med MedHigh Low/Med Low/Med

- Polyolefin HCs MedHigh Low High Medium MedHigh MedHigh Low MedHigh

s-HFCs Low Low Low Medium MedHigh MedHigh Low/Med MedHigh

u-HFCs Low Low Low MedHigh MedHigh MedHigh Low/Med High

Fully Sustainable

Partially Sustainable

Largely Unsustainable

* Options listed are coded as follows: s-HFCs = Saturated HFCs

u-HFCs = Unsaturated HFCs

HCs = Hydrocarbons

MF = Methyl Formate

DME = Dimethyl Ether

Other abbreviations; N/A = Not applicable

E-o-L = End-of-life

99
Section 10.
Annexes

100
 UNEP DTIE Foam Sourcebook - 2010

Section 10.
Annexes
10.1 Sources of Information
This Annex provides a Section-by-Section Guide to relevant references cited in the text. Where a reference is repeated in more than one Section,
the reference itself is cited in full on its first occurrence, and is cross-referenced thereafter.

Summary

UNEP 2009. Handbook for the Montreal Protocol on Substances that Deplete the Ozone Layer, Eighth edition, ISBN: 9966-7319-0-3,
United Nations Environment Programme, Nairobi, Kenya, 2009

Introduction

UNEP 2009. Handbook for the Montreal Protocol on Substances that Deplete the Ozone Layer, Eighth edition, ISBN: 9966-7319-0-3,
United Nations Environment Programme, Nairobi, Kenya, 2009

Interface between Ozone Depletion and Climate Change

IPCC/TEAP. 2005. Special Report: Safeguarding the Ozone Layer and the Global Climate System, SROC 2005.
Available at <http://www.autots.com/hcfc/technology%20option/Refrigeration/transport%20refrigeration.pdf>

IPCC, 2007. Fourth Assessment Report: Climate Change 2007 (AR4).

Available at <http://www.ipcc.ch/pdf/assessment-report/ar4/wg1/ar4-wg1-chapter2.pdf>.

Methods for Quantifying Climate Impact

TEAP, 1999. The Implications to the Montreal Protocol of the inclusion of HFCs and PFCs in the Kyoto Protocol. Mar 2000.

Annex V of UNEP/OzL.Pro/ExCom/55/47. Revised analysis of relevant cost considerations surrounding the financing of HCFC phase-out
(Decision 53/37(I) and 54/40).

Foam Manufacture and Existing Fluorocarbon Technologies

Lee Shau Tarng, C.B. Park and N.S. Ramesh, 2006. Polymeric Foams, CRC Press, New York.

IPCC/TEAP. 2005. Special Report: Safeguarding the Ozone Layer and the Global Climate System.
Available at: <http://www.autots.com/hcfc/technology%20option/Refrigeration/transport%20refrigeration.pdf>

UNEP FTOC, 2002. Report of the Flexible and Rigid Foam Technical Options Committee, 2002 Assessment, ISBN 92-807-2285-9, UNEP/ Ozone
Secretariat, Nairobi, Kenya, March 2003.

Khun E. and Schindler, P, 1993. Advances in the Understanding of the Effects of Various Blowing Agents on Rigid Polyurethane Appliance Foam
Properties, SPI Polyurethanes World Congress 1993, Vancouver, BC, October 10-13.

Molina M.J. & Rowland F.S.,1974. Stratospheric sink for Chlorofluoromethanes – Chlorine atomic catalyzed destruction of ozone,
Nature 249:810-812.

Oertel, Günter (editor), 1994. Polyurethane Handbook, 2nd. Edition, Carl Hanser Verlag, Munich.

UNEP/OzL.Pro/ExCom/55/47. Revised analysis of relevant cost considerations surrounding the financing of HCFC phase-out (Decision 53/37(I)
and 54/40).

IPCC/TEAP. 2005. “Chapter 7: – Table 7.6” Special Report: Safeguarding the Ozone Layer and the Global Climate System, SROC 2005.
Available at <http://www.autots. com/hcfc/technology%20option/Refrigeration/transport%20refrigeration.pdf>

Vo and Paquet, 2004. An Evaluation of Thermal Conductivity over time for Extruded Polystyrene Foams blown with HFC-134a and HCFC-142b

General Review of Alternative Blowing Agents

IPCC, 2007. Fourth Assessment Report: Climate Change 2007 (AR4).

Available at <http://www.ipcc.ch/pdf/assessment-report/ar4/wg1/ar4-wg1-chapter2.pdf>.

Significant New Alternatives Program (SNAP), US Environmental Protection Agency http://www.epa.gov/ozone/snap/

IPCC/TEAP. 2005. Special Report: Safeguarding the Ozone Layer and the Global Climate System, SROC 2005.
Available at <http://www.autots.com/hcfc/technology%20option/Refrigeration/transport%20refrigeration.pdf>

101
10.1 Sources of Information continued

Decision-making Process

TEAP Progress Report, 2008 UNEP Ozone Secretariat, Nairobi, Kenya, Available at: http://ozone.unep.org/Assessment_Panels/TEAP/Reports/
TEAP_Reports/Teap_progress_report_May2008.pdf

Review of Specific Factors Influencing the Selection of Alternative Technologies at Application Level

Oertel, Günter (editor), 1994. Polyurethane Handbook, 2nd. Edition, Carl Hanser Verlag, Munich.

Dedecker, Kristof, 2002. Introduction to rigid foams, in Randall D. and Lee S., The Polyurethanes Handbook, Huntsman International,
John Wiley & Sons, United Kingdom.

WORLD BANK- OORG, 2009. HCFC Replacement in Foams, Ozone Operations Resource Group (OORG), World Bank, Report 8/2009.

Deschaght, Joris, 2002. Appliances, in Randall D. and Lee S., The Polyurethanes Handbook, Huntsman International,
John Wiley & Sons, United Kingdom.

DOW, 2008. Challenges to Replace ODS in PU Appliance Foams in Developing Countries, Presentation given by Dow Brazil in the European
Seminar on HCFC alternatives for Foams, Montreal, April 5-6, 2008

AbiSaleh, T, Hernández, N and Hamilton, A, 2002. Other Construction Applications, in Randall D. and Lee S., The Polyurethanes Handbook,
Huntsman International, John Wiley & Sons, United Kingdom.

UNEP FTOC, 2006. Report of the Flexible and Rigid Foam Technical Options Committee, 2006 Assessment, ISBN 978-92-807-2826-2, UNEP/
Ozone Secretariat, Nairobi, Kenya, March 2007.

Randall David and Steve Lee (editors), 2002.The Polyurethanes Handbook, Huntsman International, John Wiley & Sons, United Kingdom.

Gum, W, Wolfram, R and Henri Ulrich (editors), 1992. Reaction Polymers, Carl Hanser Verlag, Munich.

TEAP Progress Report, 2008 UNEP Ozone Secretariat, Nairobi, Kenya,

Available at: http://ozone.unep.org/Assessment_Panels/TEAP/Reports/TEAP_Reports/Teap_progress_report_May2008.pdf

UNEP FTOC, 2006. Report of the Flexible and Rigid Foam Technical Options Committee, 2006 Assessment, ISBN 978-92-807-2826-2, UNEP/
Ozone Secretariat, Nairobi, Kenya, March 2007.

Bogdan, Mary C. and J.Y.K. Ling and D.J. Williams, 2009. Next Generation (LGWP) of Blowing Agents for Spray Foam Applications,
Polyurethanes 2009, Technical Conference, October 5-7, 2009, Gaylord National, National Harbor, Maryland (Washington D.C.).

Funding Strategies

TEAP, 2008. The TEAP Replenishment Task Force - An initial assessment: Volume 2 Assessment of the funding requirement for the replenishment
of the Multilateral Fund for the period 2009-2011. May 2008.

UNEP/OzL.Pro/ExCom/55/47. Revised analysis of relevant cost considerations surrounding the financing of HCFC phase-out (Decision 53/37(I)
and 54/40).

102
 UNEP DTIE Foam Sourcebook - 2010

10.2 Contact Details of Blowing Agent and related Technology Providers

Air Products and Chemicals Inc.
Dabco and Polycat amine 7201 Hamilton Blvd., Catalyst, Surfactants, info@airproducts.com,
catalysts, Dabco metal Alentown, PA 18195-1501 Crosslinkers, www.airproducts.com
based catalysts, Dabco USA Chain Extenders
silicone surfactants, LK ®
non silicone surfactants

Arkema Forane 420 rue Estienne d’Orves 92705 HCFCs, HFCs, 134a, www.arkema.com
Colombes 141b, 142b,
Cedex 22, 365mfc, 227ea
France

Asahi Glass Asahilklin Japan HFC-245fa, HFC-134a, www.agc.co.jp

HCFC-22,
HFC-152a

BASF Lupranol, Lupranate Carl-Bosch-Strasse 38 Polyols, isocyanates www.basf.com

67056 Ludwigshafen
Germany

Bayer MaterialScience AG Baytherm, Baymer, 51368 Leverkusen Polyols, Isocyanates www.bayermaterialscience.

Desmodur Germany com

Cannon SpA Via Colombo Polyurethane Plants and www.cannon.com

49 20090 Trezzano sul Naviglio (MI) Machineries
Italy

Chevron Phillips 10001 Six Pines Drive isopentane, n-Pentane, www.cpchem.com

The Woodlands, TX 77380 cyclopentane
USA

Desmatec Desmastrasse 3/5 Polyurethane machines www.desma-tec.de

28832 Schim - Low
Germany Pressure

Dow Chemical Co. Voranol, Voranate, Papi, Abbott Road Polyols, Isocyanates www.dow.com
Isonate, Isonol Midland, Michigan
USA

Dow Haltermann Freon, Suva 2030 Dow Center n-Pentane, cyclopentane, www.dow.com/haltermann/
Midland, Michigan 48674. isopentane and blend index.htm
USA

E. I. DuPont De Nemours and 1007 Market Street HFC-134a, HCFC-22 www2.dupont.com

Company Wilmington, DE 19898
USA

Evonik Goldschmidt Gmbh Tegostab, Tegoamin, Goldschmidtrasse 100 Silicon surfactants, amine www.goldschmidt-pu.com
Kosmos 45127 Essen, Germany activators, metal
catalysts

ExxonMobil Chemical Exxsol 5959 Las Colinas Boulevard Irving isopentane, n-Pentane, www.exxonmobilchemical.com
Texas 75039-2298 cyclopentane
USA

Foam Supplies Inc. Ecomate 4387 North Rider Tr Methyl Formate www.foamsupplies.com,
Earth City, Missouri 63103 www.ecomatesystems.com
USA

GAMA Camí Pla. 31 Spray equipment www.gamapur.com

Pol. Ind. Mas Alba
08870 Sitges
Barcelona

Graco Inc. 88 - 11th Avenue NE Spray equipment www.graco.com

Minneapolis, MN 55413-1894
USA

Hangzhou Fist Chemical Co. Ltd. LinPu,XiaoShan HCFC-141b, HCFC-142b, www.fistchem.com

Hangzhou, P.R.China HFC-152a

Hennecke Gmbh Birlinghovener Straße 30 Polyurethane Plants and www.hennecke.com

D-53754 Sankt Augustin Machineries
Germany

103
Hindustan Fluorocarbon Ltd 1402, Babukhan Estate HCFC-22 www.alibaba.com/product
Bashirbagh, Hyderabad, 500001
India

Honeywell Enovate 101 Columbia Road Fluorocarbon blowing www.honeywell.com

Morristown, NJ 07962-2497. agents, HFC-245fa
USA

Huntsman Daltolac, Suprasec Everslaan 45 Polyols, Isocyanates www.huntsman.com/pu

B-3078 Everberg
Belgium

Impianti OMS Via Sabbionetta 4 Machine manufacturer www.omsgroup.it

20050 Verano Brianza (Mi)
Italy

ISOPA, The European Av. E. Van Nieuwenhuyse Laan 4, Industry association www.isopa.org
Diisocyanates and Box 9
Polyol Producers Association B-1160
Brussels

Jiangsu Kangtai Fluorine 99 North Danyang-Men Road HCFC-141b, HCFC-142b, http://jskangtai.en.china.cn

Chemical Co.,Ltd Jintan City, Jiangsu Province HFC-134a
R.P.China

Jinan Haohua Industry Co., Ltd. No.40 Huayuan RD n-Pentane, cyclopentane, www.jnhaohua.com
Jinan City , Shandong isopentane
R.P.China

Klöckner polyPUR Gmbh Vinckeweg 15 Raw materials suppliers: www.polypur.de

D-47119 Duisburg isocyanates, polyols
Germany

Krauss Maffei Gmbh Krauss-Maffei-Strasse 2 Polyurethane Plants and www.kraussmaffei.com

80997 Munich Machineries
Germany

Lambiotte & Cie Avenue des Aubépines, 18 Blowing agents: Methylal www.lambiotte.com
B-1180
Brussels

Lanxess AG Disflamoll, Levagard Kaiser-Wilhelm-Allee 1 Phosphorous based www.lanxess.com

51373 Leverkusen, Germany flame retardants

Maruzen Petrochemical Co. Marukasol FH 25-10, Hatchobori 2-chome Cyclopentane www.chemiway.co.jp

Chuo-ku, Tokyo 104-8502
Japan

Momentive Performance Niax, Fomrez 187 Danbury Road Catalysts, Silicone www.momentive.com
Materials Wilton, CT 06897 Surfactants
USA

Perstorp Scuranate SE-284 80 Perstorp Polyols, isocyanates www.perstorp.com

Sweden

Puma Viale Germania, 5 Manufacturing of www.pumasrl.com

35020 Tribano (PD) polyurethane
ITALY sandwich lines,
continuous and
discontinuous processes

Repi S.p.A. Via B. Franklin 2 Liquid colourants for www.repi.it

21050 Lonate Ceppino VA polyurethane
Italy

Rim Polymers Industries Pte 209 Henderson Road Polyurethane Plants and www.rimpolymers.com
Ltda 03-08 Henderson Industrial Park Machineries
Singapore 159551

SAIP SRL 20090 Opera (Milan) Polyurethane Plants and www.saip.it

Italy Machineries

Shepperd Chemical Co. BICAT 4900 Beech Street

Norwood, Ohio 45212 Bismuth based catalysts www.shepherdchemical.com
USA

104
 UNEP DTIE Foam Sourcebook - 2010

Solvay Solkane Rue du Prince Albert 33 HCFCs, HFCs, 134a, www.solvayfluor.com

B-1050 141b, 142b,
Brussels 22, 365mfc, 227ea

Stepan Stepanpol 22 West Frontage Rd. Polyester polyols www.stepan.com

Northfield, IL 60093
USA

Supresta Fyrol 420 Saw Mill River Road Phosphorous based www.supresta.com
Ardsley, New York 10502 flame retardants for rigid
USA and flexible foams

Tosoh Corporation Toyocoat 3-8-2, Shiba, Minato-ku Amine Catalysts www.tosoh.com

Tokyo 105-8623
Japan

Yantai Wanhua Polyurethanes Wannate, Wanol, Waneflex No. 7 South Xingfu Road MDI based Isocyanates, www.ytpu.com
Co. Yantai,Shangdong Province polyols,
P.R.China Thermoplastic Urethanes

Zhejiang Lantian Enviromental Frog Hangzhou gulf fine chemical zone HCFC-141b, HCFC-142b, www.fltchem.com
Protection shangyu, zhejiang HFC-245fa
Chemical Co.,Ltd. R.P.China

Zhejiang Sanhuan Chemicals YongKang, HCFC-141b, HCFC-142b, www.sanhuanchemicals.com

Co. Ltd. Zhejiang Province HCFC-22, HFC-152a,
P.R.China HFC-134a

Zhejiang Sanmei Chemical Ind. Huchu Industry Area HCFC-141b, HCFC-142b, www.sanmeichem.com
Co. Ltd. Wuyi County HCFC-22, HFC-152a,
Zhejiang Province HFC227ea
P.R.China.

105
10.3 Full text of Decision
XIX/6
F. Decision XIX/6: Adjustments to
the Montreal Protocol with regard
to Annex C, Group I, substances
(hydrochlorofluorocarbons)
The Parties agree to accelerate the phase-
out of production and consumption of
hydrochlorofluorocarbons (HCFCs), by way of
an adjustment in accordance with paragraph
9 of Article 2 of the Montreal Protocol and
as contained in the annex to the present
decision, on the basis of the following:
1. For Parties operating under paragraph 1
of Article 5 of the Protocol (Article 5 Parties),
to choose as the baseline the average of
the 2009 and 2010 levels of, respectively,
consumption and production; and
2. To freeze, at that baseline level,
consumption and production in 2013;
3. For Parties operating under Article 2 of the
Protocol (Article 2 Parties) to have completed
the accelerated phase-out of production and
consumption in 2020, on the basis of the
following reduction steps:
(a) By 2010 of 75 per cent;
(b) By 2015 of 90 per cent;
(c) While allowing 0.5 per cent for servicing the
period 2020–2030;
4. For Article 5 Parties to have completed
the accelerated phase-out of production and
consumption in 2030, on the basis of the
following reduction steps:
(a) By 2015 of 10 per cent;
(b) By 2020 of 35 per cent;
(c) By 2025 of 67.5 per cent;
(d) While allowing for servicing an annual
average of 2.5per cent during the period
2030–2040;
5. To agree that the funding available through
the Multilateral Fund for the Implementation
of the Montreal Protocol in the upcoming
replenishments shall be stable and sufficient
to meet all agreed incremental costs to
enable Article 5 Parties to comply with the
accelerated phase-out schedule both for
production and consumption sectors as set
out above, and based on that understanding,
to also direct the Executive Committee of
the Multilateral Fund to make the necessary
changes to the eligibility criteria related to the
post-1995 facilities and second conversions;
106
6. To direct the Executive Committee, in
providing technical and financial assistance, to
pay particular attention to Article 5 Parties with
low volume and very low volume consumption
of HCFCs;
7. To direct the Executive Committee to
assist Parties in preparing their phase-out
management plans for an accelerated HCFC
phase-out;
8. To direct the Executive Committee, as a
matter of priority, to assist Article 5 Parties in
conducting surveys to improve reliability in
establishing their baseline data on HCFCs;
9. To encourage Parties to promote the
selection of alternatives to HCFCs that
minimize environmental impacts, in particular
impacts on climate, as well as meeting other
health, safety and economic considerations;
10. To request Parties to report regularly on
their implementation of paragraph 7 of Article
2F of the Protocol;
11. To agree that the Executive Committee,
when developing and applying funding criteria
for projects and programmes, and taking
into account paragraph 6, give priority to
cost-effective projects and programmes which
focus on, inter alia:
(a) Phasing-out first those HCFCs with higher
ozone-depleting potential, taking into account
national circumstances;
(b) Substitutes and alternatives that minimize
other impacts on the environment, including
on the climate, taking into account global-
warming potential, energy use and other
relevant factors;
(c) Small and medium-size enterprises;
12. To agree to address the possibilities or
need for essential use exemptions, no later
than 2015 where this relates to Article 2
Parties, and no later than 2020 where this
relates to Article 5 Parties;
13. To agree to review in 2015 the need for
the 0.5 per cent for servicing provided for in
paragraph 3, and to review in 2025 the need
for the annual average of 2.5 per cent for
servicing provided for in paragraph 4 (d);
14. In order to satisfy basic domestic needs,
to agree to allow for up to 10% of baseline
levels until 2020, and, for the period after
that, to consider no later than 2015 further
reductions of production for basic domestic
needs;
15. In accelerating the HCFC phase-out,
to agree that Parties are to take every
practicable step consistent with Multilateral
Fund programmes, to ensure that the best
available and environmentally-safe substitutes
and related technologies are transferred from
Article 2 Parties to Article 5 Parties under fair
and most favourable conditions;
Annex to the decision on Adjustments
to the Montreal Protocol with regard
to Annex C, Group I, substances
(hydrochlorofluorocarbons)
Adjustments agreed by the Nineteenth
Meeting of the Parties relating to the controlled
substances in group I of Annex C of the
Montreal Protocol
The Nineteenth Meeting of the Parties to
the Montreal Protocol on Substances that
Deplete the Ozone Layer decides to adopt,
in accordance with the procedure laid down
in paragraph 9 of Article 2 of the Montreal
Protocol, and on the basis of assessments
made pursuant to Article 6 of the Protocol, the
adjustments and reductions of production and
consumption of the controlled substances in
Group I of Annex C to the Protocol, as follows:
Article 2F: Hydrochlorofluorocarbons
1. The current paragraph 8 of Article 2F of the
Protocol shall become paragraph 2, and the
current paragraph 2 shall become paragraph
3.
2. The current paragraphs 3 to 6 shall be
replaced by the following paragraphs, which
shall be numbered paragraphs 4 to 6:
“4. Each Party shall ensure that for the
twelve-month period commencing on 1
January 2010, and in each twelve-month
period thereafter, its calculated level of
consumption of the controlled substances in
Group I of Annex C does not exceed, annually,
twenty-five per cent of the sum referred to
in paragraph 1 of this Article. Each Party
producing one or more of these substances
shall, for the same periods, ensure that its
calculated level of production of the controlled
substances in Group I of Annex C does not
exceed, annually, twenty-five per cent of the
calculated level referred to in paragraph 2 of
this Article. However, in order to satisfy the
basic domestic needs of the Parties operating
under paragraph 1 of Article 5, its calculated
level of production may exceed that limit by
up to ten per cent of its calculated level of
production of the controlled substances in
Group I of Annex C as referred to in paragraph
2.

5. Each Party shall ensure that for the twelve-
month period commencing on 1 January
2015, and in each twelve-month period
thereafter, its calculated level of consumption
of the controlled substances in Group I of
Annex C does not exceed, annually, ten per
cent of the sum referred to in paragraph 1
of this Article. Each Party producing one or
more of these substances shall, for the same
periods, ensure that its calculated level of
production of the controlled substances in
Group I of Annex C does not exceed, annually,
ten per cent of the calculated level referred
to in paragraph 2 of this Article. However, in
order to satisfy the basic domestic needs of
the Parties operating under paragraph 1 of
Article 5, its calculated level of production may
exceed that limit by up to ten per cent of its
calculated level of production of the controlled
substances in Group I of Annex C as referred
to in paragraph 2.
6. Each Party shall ensure that for the twelve-
month period commencing on 1 January
2020, and in each twelve-month period
thereafter, its calculated level of consumption
of the controlled substances in Group I of
Annex C does not exceed zero. Each Party
producing one or more of these substances
shall, for the same periods, ensure that its
calculated level of production of the controlled
substances in Group I of Annex C does not
exceed zero. However:
i. each Party may exceed that limit on
consumption by up to zero point five per
cent of the sum referred to in paragraph 1 of
this Article in any such twelve-month period
ending before 1 January 2030, provided that
such consumption shall be restricted to the
servicing of refrigeration and air conditioning
equipment existing on 1 January 2020;
ii. each Party may exceed that limit on
production by up to zero point five per cent
of the average referred to in paragraph 2 of
this Article in any such twelve-month period
ending before 1 January 2030, provided that
such production shall be restricted to the
servicing of refrigeration and air conditioning
equipment existing on 1 January 2020.”
Article 5: Special situation of developing
countries
3. The current sub-paragraphs (a) and (b) of
paragraph 8 ter of Article 5 shall be replaced
by the following sub-paragraphs, which shall
become sub-paragraphs (a) to (e):
“(a) Each Party operating under paragraph 1
of this Article shall ensure that for the twelve-
month period commencing on 1 January
2013, and in each twelve-month period
thereafter, its calculated level of consumption
of the controlled substances in Group I of
UNEP DTIE Foam Sourcebook - 2010
Annex C does not exceed, annually, the (e) Each Party operating under paragraph 1 of
average of its calculated levels of consumption this Article shall ensure that for the twelve-
in 2009 and 2010. Each Party operating month period commencing on 1 January
under paragraph 1 of this Article shall ensure 2030, and in each twelve-month period
that for the twelvemonth period commencing thereafter, its calculated level of consumption
on 1 January 2013 and in each twelve- of the controlled substances in Group I
month period thereafter, its calculated level of Annex C does not exceed zero . Each
of production of the controlled substances such Party producing one or more of these
in Group I of Annex C does not exceed, substances shall, for the same periods, ensure
annually, the average of its calculated levels of that its calculated level of production of the
production in 2009 and 2010; controlled substances in Group I of Annex C
does not exceed zero. However:
(b) Each Party operating under paragraph 1 of
this Article shall ensure that for the twelve- i. each such Party may exceed that limit on
month period commencing on 1 January consumption in any such twelve-month period
2015, and in each twelve-month period so long as the sum of its calculated levels of
thereafter, its calculated level of consumption consumption over the ten-year period from
of the controlled substances in Group I of 1 January 2030 to 1 January 2040, divided
Annex C does not exceed, annually, ninety by ten, does not exceed two point five per
per cent of the average of its calculated cent of the average of its calculated levels of
levels of consumption in 2009 and 2010. consumption in 2009 and 2010, and provided
Each such Party producing one or more of that such consumption shall be restricted
these substances shall, for the same periods, to the servicing of refrigeration and air
ensure that its calculated level of production conditioning equipment existing on 1 January
of the controlled substances in Group I of 2030;
Annex C does not exceed, annually, ninety per
ii. each such Party may exceed that limit on
cent of the average of its calculated levels of
production in any such twelve-month period
production in 2009 and 2010.
so long as the sum of its calculated levels
(c) Each Party operating under paragraph 1 of of production over the ten-year period from
this Article shall ensure that for the twelve- 1 January 2030 to 1 January 2040, divided
month period commencing on 1 January by ten, does not exceed two point five per
2020, and in each twelve-month period cent of the average of its calculated levels of
thereafter, its calculated level of consumption production
of the controlled substances in Group I of
in 2009 and 2010, and provided that such
Annex C does not exceed, annually, sixty-five
production shall be restricted to the servicing
per cent of the average of its calculated levels
of refrigeration and air conditioning equipment
of consumption in 2009 and 2010. Each
existing on 1 January 2030.”
such Party producing one or more of these
substances shall, for the same periods, ensure 4. The current sub-paragraphs (c) and (d)
that its calculated level of production of the of paragraph 8 ter of Article 5 shall become
controlled substances in Group I of Annex subparagraphs (f) and (g).
C does not exceed, annually, sixty-five per
cent of the average of its calculated levels of
production in 2009 and 2010.
(d) Each Party operating under paragraph 1 of
this Article shall ensure that for the twelve-
month period commencing on 1 January
2025, and in each twelve-month period
thereafter, its calculated level of consumption
of the controlled substances in Group I of
Annex C does not exceed, annually, thirty-
two point five per cent of the average of its
calculated levels of consumption in 2009
and 2010. Each such Party producing one
or more of these substances shall, for the
same periods, ensure that its calculated level
of production of the controlled substances in
Group I of Annex C does not exceed, annually,
thirty-two point five per cent of the average of
its calculated levels of production in 2009 and
2010.
107
 About the UNEP Division of Technology,
Industry and Economics

The UNEP Division of Technology, Industry and Economics (DTIE) helps

governments, local authorities and decision-makers in business and
industry to develop and implement policies and practices focusing on
sustainable development.
The Division works to promote:

> sustainable consumption and production,

> the efficient use of renewable energy,

> adequate management of chemicals,

> the integration of environmental costs in development policies.

The Office of the Director, located in Paris, coordinates activities

through:

> The International Environmental Technology Centre - IETC (Osaka, Shiga),

which implements integrated waste, water and disaster management programmes,

focusing in particular on Asia.

> Sustainable Consumption and Production (Paris), which promotes sustainable

consumption and production patterns as a contribution to human development through
global markets.

> Chemicals (Geneva), which catalyzes global actions to bring about the sound
management of chemicals and the improvement of chemical safety worldwide.

> Energy (Paris), which fosters energy and transport policies for sustainable development
and encourages investment in renewable energy and energy efficiency.

> OzonAction (Paris), which supports the phase-out of ozone depleting substances in developing
countries and countries with economies in transition to ensure implementation of the Montreal
Protocol.

> Economics and Trade (Geneva), which helps countries to integrate environmental
considerations into economic and trade policies, and works with the finance sector to incorporate
sustainable development policies.

UNEP DTIE activities focus on raising awareness, improving

the transfer of knowledge and information, fostering
technological cooperation and partnerships, and implementing
international conventions and agreements.

For more information,

see www.unep.fr
 Address
For more information, contact:
UNEP DTIE
OzonAction Branch
15, rue de Milan
75441 Paris Cedex 09
France
Tel: +33 1 4437 1450
Fax: +33 1 4437 1474
E-mail: ozonaction@unep.org
www.unep.fr/ozonaction

In September 2007, the 19th Meeting of the Parties to the Montreal

Protocol agreed to Decision XIX/6, which advances the phase-out
dates for HCFC production and consumption in developing countries.
That Decision gives priority to adopting substitutes and alternatives
that minimize other impacts on the environment, including on
the climate, taking into account global-warming potential (GWP),
energy use and other relevant factors. The UNEP DTIE OzonAction
Programme has developed this publication to provide National
Ozone Units and industry managers/owners guidance in selecting
the appropriate alternative technology in the flexible and rigid foam

phase-out of hcfs in the flexible and rigid foam sector

sector. The document gives a brief introduction and description of
the concerned sub-sectors and available technology options, as
per the findings and recommendations based on the findings of the
Foam Technical Options Committee and covering all of the uses of
HCFCs in the manufacture of flexible and rigid foams. Guidance is
also provided on how an enterprise in a developing country should
select alternatives to HCFCs, with particular emphasis on minimizing
the climate impact, including a practical and simplified methodology
for assessing the climate impact of alternatives as compared to
HCFCs as well as sourcing information for commercially-available
technology. This publication is part of a larger set of enabling tools
targeted to assist decision makers and industry players in meeting
the accelerated phase out of HCFCs, and assisting key stakeholders
in developing countries to make informed technology choices in
accordance with Decision XIX/6.