(P Dufton) Flame Retardants For Plastics

Market Report
by
Peter Dufton
Flame Retardants for Plastics

Market Report
by
Dr. Peter W. Dufton
July 2003
Rapra Technology Limited

Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
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accordance with Sections 77 and 78 of the Copyright, Designs and Patents Act 1988.
2003, Rapra Technology Limited

ISBN: 1-85957-385-1
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Contents
1 Introduction.................................................................................................................................... 1
1.1 Background .............................................................................................................................. 1

1.2 The Report................................................................................................................................ 1
1.3 Methodology ............................................................................................................................ 2
2 Summary and Conclusions .......................................................................................................... 3
2.1 Materials................................................................................................................................... 3
2.2 End User Sectors ...................................................................................................................... 5
2.2.1 Automotive........................................................................................................................ 6
2.2.2 Electrical Appliances......................................................................................................... 6
2.2.3 Business Machines and Consumer Electronics ................................................................. 6
2.2.4 Building and Construction................................................................................................. 7
2.2.5 Furniture ............................................................................................................................ 7
2.2.6 Trends................................................................................................................................ 7
2.3 General ..................................................................................................................................... 7
2.3.1 Testing and Environmental Factors................................................................................... 7
2.3.2 Overview ........................................................................................................................... 8
3 Flame Retardants ........................................................................................................................ 11
3.1 General ................................................................................................................................... 11

3.2 Organic Halogen Compounds ................................................................................................ 12
3.3 Phosphorus Compounds......................................................................................................... 12
3.4 Antimony Trioxide................................................................................................................. 13
3.5 Alumina Trihydrate ................................................................................................................ 14
3.6 Magnesium Hydroxide........................................................................................................... 14
3.7 Zinc Borate............................................................................................................................. 15
3.8 Intumescent Materials ............................................................................................................ 15
4 Products and their Markets ........................................................................................................ 17
4.1 Organic Halogen Containing Materials.................................................................................. 17

4.1.1 Bromine Compounds....................................................................................................... 17
4.1.1.1 Dead Sea Bromine Group......................................................................................... 17
4.1.1.2 Great Lakes .............................................................................................................. 21
4.1.1.3 Albermarle................................................................................................................ 22
4.1.1.4 Ferro Corporation..................................................................................................... 24
4.1.1.5 Unitex Chemical Corporation .................................................................................. 24
4.1.2 Chlorine Compounds....................................................................................................... 24
4.2 Phosphorus Containing Compounds ...................................................................................... 25
4.2.1 Introduction ..................................................................................................................... 25
4.2.2 Polymer Modification...................................................................................................... 25
4.2.3 Red Phosphorus............................................................................................................... 25
4.2.4 Ammonium Polyphosphate ............................................................................................. 27
4.2.5 Phosphorus Oxynitride .................................................................................................... 27
4.2.6 Albermarle Corporation .................................................................................................. 27
4.2.7 Polymer Tailoring ........................................................................................................... 28
4.2.8 Akzo Nobel Chemicals.................................................................................................... 28
4.2.9 Great Lakes Chemical Corporation................................................................................. 28
4.2.10 Clariant .......................................................................................................................... 29
4.2.11 Other New Developments ............................................................................................. 30
4.3 Inorganic Minerals and Compounds ...................................................................................... 30
4.3.1 Antimony Trioxide.......................................................................................................... 30
4.3.2 Alumina Trihydrate (ATH) ............................................................................................. 31
4.3.3 Boron Compounds........................................................................................................... 32
4.3.4 Magnesium Hydroxide .................................................................................................... 35
4.3.4.1 Technology............................................................................................................... 35
4.3.4.2 Commercial Products ............................................................................................... 38

4.3.5 Other Inorganic Compounds ........................................................................................... 38
4.3.5.1 Iron Compounds ....................................................................................................... 38
4.3.5.2 Molybdenum Compounds ........................................................................................ 39
4.3.5.3 Tin Compounds ........................................................................................................ 40
4.3.5.4 Talc........................................................................................................................... 41
4.4 Other Materials....................................................................................................................... 41
4.4.1 Coatings........................................................................................................................... 41
4.4.2 Char Forming Polymers .................................................................................................. 42
4.4.3 Potassium Compounds .................................................................................................... 43
4.4.4 Melamine Compounds..................................................................................................... 43
4.4.4.1 Melamine Polyphosphate ......................................................................................... 43
4.4.4.2 Melamine Cyanurate (MC)....................................................................................... 44
4.4.5 Silicon Compounds ......................................................................................................... 45
4.4.6 Graphite ........................................................................................................................... 45
4.4.7 Glass Flake ...................................................................................................................... 47
4.4.8 Low Melting Glasses....................................................................................................... 47
4.4.9 Polymer Blends ............................................................................................................... 47
4.4.10 PTFE.............................................................................................................................. 48
4.4.11 Aluminium Flake........................................................................................................... 48
4.4.12 Hindered Amine Light Stabilisers ................................................................................. 48
4.4.13 Nanocomposites ............................................................................................................ 49
4.4.14 TSWB............................................................................................................................ 51
4.4.15 Noflan............................................................................................................................ 51
5 Polymer Families and Their Flame Retardancy........................................................................ 53
5.1 Polyolefins.............................................................................................................................. 53
5.1.1 Polyethylene .................................................................................................................... 53
5.1.2 EVA................................................................................................................................. 54
5.1.3 Polypropylene.................................................................................................................. 56
5.2 PVC ........................................................................................................................................ 57
5.3 Styrenics ................................................................................................................................. 59
5.4 Polyamides ............................................................................................................................. 60
5.5 Modified PPO (m-PPO) ......................................................................................................... 62
5.6 Polyurethanes ......................................................................................................................... 63
5.7 Thermosets ............................................................................................................................. 66
5.7.1 Unsaturated Polyesters .................................................................................................... 67
5.7.2 Epoxy Resins................................................................................................................... 69
5.7.3 Phenolics ......................................................................................................................... 71
5.7.4 PU Casting Systems ........................................................................................................ 71
5.7.5 Acrylic Resins ................................................................................................................. 71
5.7.6 Dicyclopentadiene ........................................................................................................... 72
5.8 Thermoplastic Polyesters ....................................................................................................... 72
5.9 Polycarbonates........................................................................................................................ 74
5.10 Other Thermoplastics ........................................................................................................... 75
6 Suppliers and the Consumption of FR Additives and Compounds....................................... 77
6.1 General Comments ................................................................................................................. 77

6.2 Suppliers................................................................................................................................. 78
6.2.1 Brominated Flame Retardants ......................................................................................... 79
6.2.2 Melamine......................................................................................................................... 80
6.2.3 Phosphorus Flame Retardants ......................................................................................... 80
6.2.4 Mineral Filler Flame Retardants...................................................................................... 81
6.2.5 Borate Flame Retardants ................................................................................................. 82
6.2.6 General ............................................................................................................................ 82
6.3 Consumption and Market Data............................................................................................... 82
6.4 Compounding for Flame Retardancy ..................................................................................... 87
7 End-User Market Sectors............................................................................................................ 89
7.1 Automotive............................................................................................................................. 89
7.2 Other Transport ...................................................................................................................... 90
7.3 Electrical Components ........................................................................................................... 91
7.4 Electronics Products............................................................................................................... 93
7.4.1 Telecommunications ....................................................................................................... 96
7.4.2 Consumer, Brown Goods ................................................................................................ 97
7.5 Electrical Cables..................................................................................................................... 98
7.6 Building and Construction ................................................................................................... 101
7.7 Upholstered Furniture and Textiles...................................................................................... 103
8 Fire Testing ................................................................................................................................ 105
8.1 Introduction .......................................................................................................................... 105

8.2 Specific Tests ....................................................................................................................... 105
8.3 Comparing Test Results ....................................................................................................... 107
8.4 Tests for Building Materials................................................................................................. 109
8.5 Cable Testing........................................................................................................................ 111
8.6 Mattress Tests....................................................................................................................... 111
8.7 Clothing Tests ...................................................................................................................... 112
9 Environmental and Regulatory Matters .................................................................................. 113
9.1 Fire Safety ............................................................................................................................ 113

9.1.1 European Standards for Television Sets........................................................................ 114
9.1.2 Brominated Flame Retardants ....................................................................................... 116
9.2 Brominated Flame Retardants .............................................................................................. 118
9.3 EU Directives ....................................................................................................................... 122
9.4 Recycling Matters ................................................................................................................ 124
9.5 Postscript .............................................................................................................................. 128
European Suppliers of Flame Retardants Company Names and Addresses ..................... 133
Abbreviations and Acronyms..................................................................................................... 145
Flame Retardants for Plastics Market Report
1 Introduction
1.1 Background
Flame retardant plastics play an important role in our society. They are used in cases where there is
a requirement to protect people and property from a possible fire hazard. Together with other
decisive fire prevention measures, such as structural design and the use of smoke detectors, the
choice of materials is one of the basic decisions to be taken by developers and manufacturers of
plastic parts.
Attempts have been made over the years to harmonise the standards for flame retardant systems
and to produce environmentally friendly products.
These days all products must satisfy application-specific demands on preventative fire protection.
Such demands are best fulfilled technically and economically by the use of flame retardants. These
help to limit flame spread and heat release in incipient fires and frequently to prevent fires from
starting in the first place. The appropriate type of flame retardant material is determined not only
by the required flame resistance standard and the physical dimensions for the particular application
but also by the family of polymers used.
Countless applications require that the polymers used must exhibit ever higher levels of fire safety.
The construction industry is a key one whereby all industrialised countries have their own complex
system of fire tests and fire classifications. This is the main reason that building products still have
to be tested and approved in each and every one.
Since the early nineties, Green parties in Germany and in several Scandinavian countries have
invested considerable effort to try to ban halogenated flame-retardants, claiming that they may be a
source of toxic halogenated dibenzodioxins and dibenzofurans. The spreading of many rumours
and actions to introduce restrictions on brominated flame retardants have resulted in a major
decrease in the use of flame retarded TV housings in the European market. As a consequence of
several years of such practice, TVs have become the primary cause of domestic fires in Germany
while in Sweden, the number of TV fires per million sets more than doubled during the period
1990-1995.
This report provides information and comment on recent events in the environmental and
legislative spheres, and covers some of the product developments in the various families of flame
retardant chemicals available commercially for use with plastics resin formulations. Some longerterm ideas and potential areas of chemical development are also described.
1.2 The Report
The report starts with an executive summary in Chapter 2 and is followed by a brief description of
the different families of flame retardant materials and their uses in Chapter 3.
The trends in materials developments and the products available in the marketplace are examined
in Chapter 4.
Chapter 5 covers most of the main plastics families and some of the methods used to make them
flame retardant. Some producer-specific information is provided as well as more generic comments
on plastics in commercial use.
Chapter 6 reviews the supply chain and discusses the source of materials used by the resin suppliers
and compounders. The market for flame retardant additives is discussed and some statistical data
presented.
Chapter 7 briefly examines some major end uses. These cover
Automotive; Other Transportation

Electrical & Electronic Equipment, and Cables
Building & Construction
Fire testing is discussed in Chapter 8 with fire safety, environmental issues and legislation covered
in Chapter 9.
1.3 Methodology
The study has been compiled from substantial desk research carried out on the subject of fire and
polymeric materials. Opinions expressed are those of the author, unless otherwise indicated.
2 Summary and Conclusions

2.1 Materials
No fundamentally new fire retardant (FR) systems have been developed in recent years. However,
many improvements have been made to existing ones as a drive to halogen-free systems has stirred
R&D teams. Such developments can prove very difficult in many cases on technical and cost
grounds.
New offerings from the bromine companies are all formulated to achieve acceptance under the
German Chemical Banning Ordinance. That is, their potential emissions fall below the threshold
limiting values for dioxins and furans set out therein.
Although the mechanisms are not wholly understood, synergistic reactions are increasingly being
used in the formulation of FR additives and multi-functional systems. This is quite likely to be a
key area for developments in the future. In FR technology, synergistic effects do not simply
produce more efficient systems. They also make it possible to reduce the amounts of other FR
agents employed, and may often make a positive contribution towards delivering efficient flame
retardancy within increasingly stringent FR regulations.
A number of minerals have synergistic action with organic halogenated and phosphorated flameretardants and synergistic processes have also been observed in thermosets, between borates and
other hydrated minerals. Incorporation of minerals in intumescent formulations makes it possible to
manage better the morphology of the expanded structure that develops on exposure to flame.
Growing experience is showing that, despite an apparent increase in material price, FRs used in
judicious combinations can, in fact, reduce the cost of the compound, either by making large
reductions in the active additive, or by offering multi-functional performance.
The most important synergistic FR components currently are antimony oxide and halogen-donor
compounds. Metal oxides and other metal compounds are also very promising, particularly in
engineering thermoplastics compounds.
Formulations with brominated FRs (BFRs) normally contain antimony trioxide as a synergist.
However, because of the filament-like structure of antimony trioxide its dust is classified as a
carcinogenic material and special measures for the protection of workers must be adopted. For this
reason, dust-free systems are on offer that do not cause any problems when processed. Even so,
formulations containing antimony trioxide often still have to be labelled.
Another major trend in development is seen by the pelletisation of new antimony oxides blends.
They extend the benefits of a one-pack system to flame retardants plus the non-dusting and feed
benefits of a masterbatch.
Antimony is relatively inexpensive and has been used in the past in large quantities as a flame
retardant. It is a hazardous material and its use in most countries is controlled by relevant
workplace regulations, and there is a trend towards replacing it, or reducing its use. It has an
effective synergistic action with most types of halogenated FRs, especially in plasticised PVC
compounds. In other polymers (not containing a halogen) a suitably chlorinated or brominated
compounds needs to be present to achieve the required properties.
A potentially good replacement in many systems is zinc sulfide, which until now has been
considered for use as a pigment. New FR grades have been produced for use either alone or in
synergistic compounds.
Pure talcs of fine particle size and high lamellar structure, in combination with a new generation
bromine compound, make it possible to obtain optimum mechanical properties and fire resistance
as well as a limitation on the emission of corrosive by-products. Good results have been recorded
with polyolefins in synergy with bromine compounds, for applications such as connectors and
appliances.
The characteristics of the talc/polymer interface influence both the mechanical and ignition
resistance properties of the compound. Increasing the nucleating effect produced by the mineral
gives better adhesion of the polymer to the filler and a stronger reinforcing effect.
Addition of melamine to mineral filler FRs in polypropylene (PP) generally improves their UL94
test behaviour, eliminating at the same time the after-glow phenomenon that is typical of mineral
fillers used alone. Melamine also reduces the specific weight of FR PP, which results in an
economic advantage and allows the use of relatively cheap inert fillers such as kaolin and talc
which, used alone, do not show any flame retardant properties.
With brominated FRs, a partial substitution with minerals makes it possible to improve certain of
the mechanical properties and reduce opacity and corrosivity of the fumes generated, so reducing
potential environmental hazards.
Specially coated magnesium and aluminium hydroxides confer significantly increased combustion
resistance and lower levels of smoke evolution, permitting large reductions in additive loading,
without sacrificing flame retardant or smoke suppressant performance.
Another change is anticipated, whereby foam and coverings for furniture may be drawn further into
the legislative net in both Europe and North America. This would accelerate the usage of melamine
and phosphorus compounds in foams.
Brominated compounds will continue to hold much of the engineering plastics sector and thereby
some dominance in the electrical and electronics (E&E) sector. They will continue to be the most
significant products because they are the most cost effective (and efficient) solution to many
plastics flame retardancy applications. The EU Waste Electrical and Electronic Equipment (WEEE)
directive and its effect on recycling plus the debate about fire safety versus environmental issues
(especially in domestic appliances) will continue to attract much attention.
Borates represent a novel opportunity for synergism with both brominated and non-halogenated
flame retardant products. Although known for many years, their time has now, perhaps, arrived as
antimony trioxide has come under a cloud. For instance, to capitalise on this opportunity
Albemarle, the leading BFR company, is collaborating with US Borax to develop new boraterelated technologies.
Brominated FRs generate hydrogen bromide in the vapour phase, which then mops up free radicals
generated in a fire, and so suppresses that fire. Borates form a glassy char that cost-effectively
retards the dripping tendency of some FR treated thermoplastics. This is essential because such
materials by themselves may fail certain flammability tests when they generate molten, flaming
drops. Together, the borates and BFRs are a force to be reckoned with.
R&D efforts in halogen-free FRs are often aimed at designing a protective closed barrier on the
burning polymer surface to reduce heat and mass transfer to the combustion zone. In some polymer
applications this can be achieved by the use of intumescent systems. However, these are not always
suitable in other applications for reasons of water uptake, thermal stability or actual FR
performance. Therefore, it is of interest to the material developer to have options available to
control the structure of the burning polymer surface layer. In this layer no cracks should appear
which could allow for the escape of volatile, ignitable gases and so sustain the combustion process.
Aluminium trihydrate (ATH) should continue to experience strong growth but there is much
competition from mineral suppliers all anxious to launch special precipitated grades and those with
new surface treatments to make them more effective. The drive is the requirement for lower
loadings to preserve the balance of mechanical and physical properties for which the particular
plastic system has been chosen. The treatment of hydrophilic ATH particles with hydrophobic
coatings, such as fatty acids or silanes, provides for more uniform dispersion in the hydrophobic
plastic resins.
Refinements in magnesium hydroxide chemistry have been accomplished to enable that material to
sensibly replace ATH in some higher temperature applications.
The hydrated fillers only have an effect at high loadings with the well-known potential impairment
of mechanical properties. By employing special surface treatments in conjunction with
compatibility agents, manufacturers have in recent times managed to largely offset the negative
effects.
The current discussions across the plastics sector show a steady upwards trend in demand for
reduced flammability, minimum smoke generation and low toxicity, yet with optical, mechanical or
electrical properties still being retained. This can be quite difficult to master in technical terms,
since these demands are contradictory in some measure and also because the matrix polymers
display greatly dissimilar behaviour in the event of a fire, with PVC and polyethylene being good
examples.
Another trend in many applications is towards halogen-free products or at least to combinations
which will permit a reduction in the percentage of halogen. Japanese patents have opened up the
market for melamine compounds that can also be used in combination with other FRs such as
magnesium hydroxide or even a filler like talc.
All new innovations such as the increasing use of zinc compounds or borates contribute towards a
safer and cleaner environment. Such developments show that, with a plethora of materials for use
either alone or in combination, and an ever greater understanding of the scientific basis of fire and
combustion, the industry offers meaningful solutions to the problems of health and the
environment, and the cost/performance needs of processors and end-users.
2.2 End User Sectors
Plastics compounded with FR additives may be used in a wide range of applications:
electrical engineering
transportation
construction
domestic appliances
wider general industrial conditions
Each one of these sectors has established its own FR standards and specifications over the past
decades, often with reference to local government regulations. As a result, every market segment
has a large number of regulations and test procedures forcing materials developers to adapt their
formulations to match customer requirements in order to meet the safety legislation of each
relevant authority. In Germany, for example, these can differ from one Land to another.
Currently, attempts are being made to harmonise standards, with the construction industry farthest
along the route to finalise such procedures. Examples of standards are shown in Table 2.1.
Table 2.1 Examples of flame resistance standards

Sector
Test
Evaluation
Construction
DIN 4102 (Germany)
B1, B2 (vertical chimney)
Electrical and appliance UL94 (USA)
V-0, V-1, V-2, HB (vertical test),
IEC 65 (Europe)
(horizontal test), pass or fail
Others
e.g., Mining tests
e.g., tunnel test
Fire protection requirements exist in the fields of E&E engineering, the construction industry,
transportation, textiles and upholstery for furniture. More than 40% of FRs are utilised by the E&E
sector and cables, especially for consumer electronics, business machines, household appliances
and industrial applications.
In the wake of European harmonisation, national fire requirements in the construction industry and
rail-transport sector are gradually being replaced. By 2007, a new classification system and new
test procedures for the fire behaviour of construction products will replace existing national
systems within the EU. This means there will be more stringent requirements overall, calling for a
reassessment of the plastics currently utilised. All the construction products introduced on a
national basis will have to be tested according to the new test procedures, particularly the Single
Burning Item (SBI) Test, involving a higher outlay on material and higher expenditure, since there
are not generally any correlations with the existing national tests. The same applies for railway
rolling stock, whose test procedures are currently harmonised on a national level and will become
so at European level in future.
In the case of international test procedures already introduced, changes are pointing towards an
increasing level of fire protection.
2.2.1 Automotive
Plans are afoot to have the low-level requirements of MVSS 302, which is a Bunsen burner test on
horizontal specimens, upgraded, since, in the latest car models with their compact designs and
electronic door locks, the outbreak of a fire needs to be delayed for longer than has been the case.
In addition to this, the new 42V electrical systems will also place increased requirements on fire
safety; perhaps up to UL94 V-0.
The US National Highway Transportation Safety Administration plans to change its rear-impact
test for cars from 30 to 50 mph. The implications for fire safety are huge, as they would affect fuel
systems, interior as well as certain exterior components.
2.2.2 Electrical Appliances

The Underwriters Laboratory adopted in 2001 new fire safety standards that are resulting in a
major increase in the utilisation of FR chemicals. More than 40 other UL standards, governing
thousands of goods, are directly affected, including hair dryers, toasters, power drills, and electric
can openers. Manufacturers have two choices; to re-design their products or use fire-resistant outer
casings. FR additives are seen by most as the more cost-effective solution.
2.2.3 Business Machines and Consumer Electronics

Business machines and consumer electronics are likely to merge into a single sector in the future,
meaning that the low-level fire safety requirements currently in force in certain regional
applications (TVs in Europe) will be superseded by much more stringent, and uniform,
requirements.
2.2.4 Building and Construction

The European Commission has been preparing for harmonisation of building regulations including
the fire testing side of such controls. This has been proceeding for many years as preliminary work
to the recently introduced Building Products Directive, which has been incorporated into the
national legislation of all Member States. This has covered the harmonisation of fire tests and the
classification systems resulting from them for combustible building products.
Uniform fire test methods that are valid for the whole of the EU will be introduced in the near
future.
2.2.5 Furniture
The US Consumer Product Safety Commission (CPSC) agreed in 2001 to move to tougher, new
safety standards for mattresses. California introduced its own laws for improved sleeping products.
Equally, a consortium of companies and associations drafted federal legislation for higher safety
levels in upholstered furniture.
2.2.6 Trends
What are the current trends and innovations? First of all, demand for flame retardants will rise
worldwide on account of stricter fire-safety levels. It will be spurred on inter alia by the
harmonisation of fire protection requirements for products in the construction industry and for
railway rolling stock within Europe, as well as through the introduction and implementation of fire
regulations in newly industrialised countries, especially in Asia, with particular focus on China.
The 42V power supply in cars and UL94 V-0 television sets in Europe will similarly contribute
towards this trend. Over the medium term, US fire safety requirements could be imposed on
upholstered furniture in the private sphere throughout the entire country, which would ensure a
boom in the demand for flame retardants.
Tried-and-tested flame retardant systems based on bromine compounds will continue to be used,
with just a few exceptions, on account of their outstanding price-to-performance ratio. This is clear
from printed circuits, where halogen-free reactive and additive FR systems are not able to displace
the FR4 laminates based on tetrabromobisphenol-A (TBBA). Such is the case in Europe, at least.
The situation could prove to be different in Asia, since the giants in the sector, such as Sony, have
committed themselves to halogen-free printed circuits. In Europe and Asia, innovations in flame
retardant plastics continue to be in the field of halogen-free systems.
This is borne out by new developments such as nanocomposites in the cable field and in
nanotechnology for PC/ABS blends. Over the medium term, all plastics will be available with
halogen-free systems. It will then be possible to cover all the different requirements with the
established and the new FR plastics and thus serve the market in an optimum fashion.
2.3 General
2.3.1 Testing and Environmental Factors

Of particular importance is the SBI test, which will be used to test building products in future. In
many cases, the fire safety requirements imposed on combustible materials will be more stringent
than those of existing national tests, a fact that should well lead to greater demand for flame
retardants of one sort or another.
Similar considerations have been applied to other sectors. Railway rolling stock is an area for
which harmonised fire tests are planned at European level. Another is electrical and electronic
engineering where international standards already apply to a great extent, but local variations may
be required, considered or tolerated. An example is that of TV housings; provisions in the US and
Asia are strict enough to necessitate the utilisation of flame retardants, whereas in Europe they are
so lax that often flame retardants are no longer used.
As far as environmental questions are concerned, FR systems tend to be assessed much more
pragmatically and less emotionally and ideologically than before. Instead of whole groups of flame
retardants being written off as possessing general polluting potential, each FR is evaluated
nowadays with regard to its environmental properties and a decision is taken as to its suitability for
the intended application. This also applies to mechanical or material recycling, energy recovery and
disposal. It ensures that the technically, economically and ecologically optimum FR system can be
used in the application under review.
The introduction of new fire safety standards and environmental regulations will mean a period of
growth for the FR chemicals market and affect industries such as construction, electronics and
transport.
More stringent flammability standards are already being introduced, such as performance-based
codes in the building industry, and voluntary actions that improve fire safety in consumer products.
This has resulted in greater demand and changing requirements for flame retardants, favouring low
smoke and fume products. The environmental impact of flame retardants has been under discussion
by regulators and has resulted in increasing demand for more environmentally acceptable materials,
which represents one of the biggest challenges for FR producers.
The key driver for future growth will be fire safety and environmental regulations, which will
demand the use of these chemicals in many more industries than before. This new legislation will
also result in end-users changing the type of FR they buy to meet the latest specifications. This in
turn will have a knock-on effect for the producers who will be forced to develop new products to
keep pace and to serve the new markets and applications that will then be covered.
2.3.2 Overview
Public safety issues, especially in the United States, have revealed a very poor record-keeping
tendency with regard to fires in public places. The CPSC, the US Fire Administration, and the
National Fire Protection Association issue annual estimates on fire losses. Around 400,000
domestic fires require fire-fighter response, which kill about 4,000 persons, with another 20,000
suffering severe injury. Some 70,000 fires involve electrical distribution and appliances, another
40,000 stem from furniture and mattress fires. The available statistics grossly underestimate the
problem. For example, the federal government, which employs two million civilians in 8,300
buildings, has no data on even the largest fires on its own property. Also, and incredibly, there have
been years in which large States such as Pennsylvania and California have not reported a single
fire. Clearly this shows that the nationwide fire reporting systems are extremely inadequate.
European countries are not much better, but even with partial data there are reportedly about
80,000 people severely injured in European fires each year. Of these, some 60,000 are hurt in their
own homes. Many injuries result from TV fires.
For all the criticism of FRs, not by scientists or even the environmentalists, but mainly by
politicians, the European Commission acknowledges that there would be 20% more fire deaths in
Europe if FRs were not being used. In the same vein, the UK reports that 1,860 lives have been
saved in the last 10 years or so because of its safety standards for upholstered furniture, due to the
use of FRs.
The marketplace is reflecting this need for action. Companies are responding with products that use
FR additives for extra safety in a wide array of goods, including plastic outer casings and housings,
candles, power cords, and so on.
In the US, as mentioned before, TV housings are made flame-resistant. In Japan some of the major
manufacturers are following suit. This has not been driven by any regulation. They want to do the
right thing. This phenomenon is occurring across a range of goods, although seen, obviously as a
marketing tool, it also covers an ethical reason as well.
It would now appear that Green or Eco labelling that was weighted in favour of the environment,
almost to the exclusion of all else, has now taken on board the need to consider fire safety in some
measure. In various countries, there is an implicit acceptance that fire safety concerns must merit
equal consideration with those for the environment, at the very least.
10
3 Flame Retardants
This chapter gives the briefest of outlines of the different flame retardant families and their
capabilities in protecting plastics compounds. A more comprehensive review of fire chemistry and
the actions of the different types of flame retardant materials is to be found in the previous edition
of this Rapra report, Fire Additives and Materials, Rapra Technology Ltd., 1995.
3.1 General
Protection against fire by the employment of flame retardants in plastics formulations must achieve
at least one of several tasks during the course of a fire. These can briefly be stated as:
raising of the ignition temperature,

reduction of the rate of burning,
reduction of flame spread, and
reduction, if not elimination, of smoke generation.
The most important flame retardant families are based on both organic and inorganic compounds.
In principle, flame retardants act by interrupting the process of combustion in the solid and liquid
phases of the substrate or in the gas phase. Their effect can be of a physical or chemical nature.
Chemically acting flame retardants work best (bromo- and chloro-organic systems in the gas phase,
phosphorus and nitrogen-containing systems in the condensed phase). Physically acting inorganic
flame retardants based on metal hydroxides and salts have a weaker effect.
The active species in fire retarding are the halogens, chlorine and bromine, phosphorus, and water.
The performance of these primary flame retardants is enhanced by synergists: antimony, zinc and
other metal salts. Some help to develop a protective char (e.g., phosphorus-based systems),
separating the unburned polymer from the flame and heat source.
Others change the flame chemistry by inhibiting free radical formation in the vapour phase
(halogen-based systems). Still others release water upon heating (hydrated systems), quenching and
cooling the combustion reactions.
Proper choice of a flame retardant for optimum performance in a plastic depends on the thermal
stability of the flame retardant and the decomposition temperature of the polymer. Ideally, the
flame retardant should be activated at a temperature slightly below the decomposition temperature
of the polymer. In this way, the flame retardant can promote char formation to reduce the amount
of flammable fuel the polymer can generate, or it can mix with potentially flammable vapours to
inhibit ignition or burning.
In the case of a fire, the development of smoke is of equal importance to the flammability of the
plastic. The important factors are density, toxicity and the corrosive effect of the smoke gases.
Carbon black increases the density of the smoke gases, the main toxic elements of which are
incompletely oxidised carbon, usually in the form of carbon monoxide gas. Crosslinked thermosets
generally produce less smoke than most thermoplastics, rather, they tend to carbonise. The
polymers that are highly resistant to heat will keep their aromatic or heterocyclic ring structure in
the case of fire and carbonise into networks similar to graphite.
11
3.2 Organic Halogen Compounds

The halogenated flame retardants may be bromine- or chlorine-based and can be classified as:
(1)
(2)
(3)
halogenated paraffins
chlorinated alicyclic compounds
chlorinated and brominated aromatic compounds
Flame retardants containing bromine are twice as effective as those containing chlorine. However
the price is higher and the UV resistance is lower. The products containing bromine are of
aliphatic, cycloaliphatic, aromatic and aromatic-aliphatic type. Tetra-bromobisphenol A (TBBA) is
condensed as a flame retardant in PC and expanded polystyrene (EPS). In phenolic and unsaturated
polyester (UP) resins di- and tri-brominated phenols and tetra-bromophthalic anhydride serve as
reactive components in the resin backbone.
These materials, when used alone in plastics, provide a limited degree of flammability
performance. The addition of antimony compounds greatly enhances their efficiency, allowing for
lower loadings of the halogenated materials needed for equivalent performance. Several antimony
derivatives are commercially available, with antimony trioxide being the most widely used.
The polybrominated diphenyl ethers (decabromodiphenyl ether, octabromodiphenyl ether) have
been the most widely used of the brominated materials. These additives are cost efficient and are
the conventional choice for high-impact polystyrene, ABS, and other styrenics. However, their use
has been under challenge for environmental reasons. Other brominated species that cannot generate
dioxin species under any conditions are now more in favour than PBDEs.
Halogens function by the formation of halides which inhibit the branching radical reactions that
propagate a flame. In effect, they make the combustion process less efficient. A consequence of
this mechanism is that polymers formulated with halogenated additives burn with a smoky flame.
Moreover, the combustion products are acidic. This means that they are not normally the first
choice for wire and cable applications.
In addition, these materials have been under scrutiny in recent years regarding their toxicity;
however, threatened legislation against these types of product does not appear to have had a great
effect on the extent of their use.
The advantages and disadvantages of this class of materials can be summarised as follows:
Advantages
Effective at low concentration
Relatively little detrimental effect on
physical properties
Easy incorporation and processing
Moderately priced materials
Disadvantages
Generally require a synergist
May be a skin and eye irritant during
handling and processing
Release of toxic combustion products
3.3 Phosphorus Compounds

Phosphorus-containing flame retardants include inorganic phosphates, insoluble ammonium
phosphate, organophosphates and phosphonates, halophosphates and chlorophosphonates,
phosphine oxides, and red phosphorus. The mechanism for flame retardancy varies with the
phosphorus compound and the polymer type. A phosphorus containing flame retardant can function
in the condensed phase, the gas phase, or concurrently in both phases.
12
Important categories are the phosphate esters, extensively used in flexible PVC, modified
polyphenylene oxide and some cellulosic polymers; and chlorinated phosphates, commonly used in
polyurethane formulations.
Some phosphorus compounds decompose in the condensed phase to form phosphoric or
polyphosphoric acids. These can act as dehydration catalysts, reacting with cellulosics for example,
to form a good char. Char yield is also increased with rigid polyurethanes. The polyphosphoric acid
can also form a viscous molten surface layer or surface glass. This layer can shield the polymeric
substrate from the flame (heat) and oxygen. Intumescence, which requires an acid such as
phosphoric acid, results in a dense carbon char on the polymer surface protecting the substrate from
heat and oxygen.
Red phosphorus is also used as a flame retardant disadvantages include high flammability and in
the presence of heat and/or friction it can explode. In the presence of moisture it releases
phosphine. However, red phosphorus has a number of advantages as a flame retardant the
material need only be added in fairly low concentrations of around 6-10%. At this addition level,
the phosphorus has a negligible effect on physical properties.
An overview of the advantages and disadvantages of the phosphorus-containing flame retardants is
given below, but allowances must be made for the differences between the various classes within
this group.
Advantages
Effective at low concentration - organic
types
Easy incorporation and processing
Relatively little detrimental effect on
physical properties
Good UV stability
Low-moderate price materials
Disadvantages
Lack of permanency and hygroscopicity of
inorganics
Potential health hazard during processing
organics
Release of toxic combustion products from
organics
3.4 Antimony Trioxide

Certain antimony compounds function as synergistic flame retardants when used in conjunction
with suitable halogenated organic compounds. When used alone the antimony compounds are
essentially ineffective as flame retardants. Antimony trioxide is the most widely utilised.
In its function as a flame retardant, antimony trioxide, in combination with an organic halogen
compound, forms antimony trihalide and oxyhalide at flame temperatures.
The antimony trihalide is the principal active agent and acts in both the flame phase and the solid
phase to suppress flame propagation. The volatile antimony halide acts as a source of halogen
radicals that react with flame free radicals through a reaction that is less exothermic than the
uninhibited propagation reaction of oxygenated free radicals, thereby reducing the heat generated
and as a consequence reducing the rate of thermal degradation of the plastic matrix. In the solid
phase the antimony oxide promotes the formation of highly crosslinked carbonaceous char, which
serves to insulate the substrate and to restrict the diffusion of volatiles in the flame.
A broad range of halogenated flame retarding compounds can be used in conjunction with
antimony trioxide, typically chlorinated paraffins and chlorinated cycloaliphatic compounds,
brominated aromatic compounds and brominated phosphates. However, the major application for
antimony trioxide in terms of consumption is in flexible PVC, where the chlorine available from
the polymer is sufficient to provide the desired level of flame retardancy.
13
The advantages and disadvantages of antimony trioxide are summarised below.

Advantages
Effective at relatively low concentration,
typically 3-6 wt%
Disadvantages
Requires halogenated compounds
Affects pigmentation and physical
properties
Potential health hazard from dust
Increases smoke and afterglow
High cost
3.5 Alumina Trihydrate

One of the most common approaches to fire-retarding a halogen-free polymer system has been the
addition of high loadings of alumina trihydrate, which can undergo an endothermic dehydration by
releasing 34.6 wt% water in the temperature range 220 to 250 C. Low in cost and environmentally
acceptable, it is used in applications where high filler content is technically possible and processing
temperatures do not exceed 180 C. To be fully effective as a flame retardant/smoke suppressant
ATH has to be used at high loadings (typically 40 to 60% by weight) and it is therefore essential
that consideration be given to the effect on polymer processing and physical properties.
First used as a flame retardant in carpet backing, the largest tonnage of ATH now goes into glassreinforced unsaturated polyester and other thermosets. In wire and cable applications, ATH is used
in PVC, low density polyethylene (LDPE), ethylene-propylene-diene terpolymer (EPDM) and
ethylene-vinyl acetate copolymer (EVA). A range of grades is commercially available, varying
from coarse ground materials to ultrafine precipitated materials.
Recent studies have demonstrated that there are major advantages in using a combination of ATH
and zinc borate in a variety of halogen-free polymer systems.
The advantages and disadvantages of this class of materials can be summarised as follows:
Advantages
Combined filler and flame retardant
functions
Does not require halogens
Does not produce toxic gases
Suppresses smoke formation
Non-volatile and unaffected by water
Low cost
Non-toxic
Disadvantages
Requires high loadings
Affects physical properties and processing
behaviour
Relatively low decomposition temperature
3.6 Magnesium Hydroxide

Magnesium hydroxide, like alumina trihydrate, acts as a flame retardant and smoke suppressant.
Like ATH, it functions by the release of water vapour at elevated temperature, which absorbs heat
and dilutes the combustible gases. However, the major advantage of magnesium hydroxide over
ATH is the higher decomposition temperature, 330-340 C compared with 210-220 C for ATH,
meaning that compounds containing magnesium hydroxide can be processed at higher temperatures
than those using ATH. Again high loadings, typically in the range 50-60%, are required to achieve
desired levels of flame retardancy.
14
The main opportunities for magnesium hydroxide are in PP applications, but it is also used in
elastomeric cable compounds. One of the main limitations is its tendency to agglomerate in
polymers, affecting processibility and performance. This is being overcome by the development of
modified materials using surface coatings etc.
3.7 Zinc Borate
Growing awareness of the smoke hazard posed when using antimony trioxide as a flame retardant
has led to the development of products using zinc borates. The multifunctional zinc borate
(2ZnO.3B2O3.3.5H2O) is an effective and economical fire retardant synergist of organic halogens in
polymers. It has been used extensively as a flame retardant, smoke suppressant and afterglow
suppressant. Zinc borate retains its water of hydration up to a temperature of 290 C and releases
14 wt% water in the temperature range of 290 to 450 C. In contrast to ATH, zinc borate promotes
the formation of a strong residue in a burning polymer. This residue is fire resistant and can protect
the unburned polymer from being exposed to high temperatures and further combustion.
It has been demonstrated that the combination of zinc borate and ATH can be used as an effective
flame retardant and smoke suppressant in halogen-free polymers such as EVA, polyethylene,
EPDM, ethylene-ethyl acrylate copolymer (EEA), epoxy, and acrylics. In some polymers such as
silicone rubbers, zinc borate used alone is very effective as a fire retardant.
Zinc borates have also found uses in PVC formulations. They have been shown to be effective
flame/smoke suppressants when used as partial replacements for the antimony oxide that is
normally used in a typical flexible PVC cable jacket, for example. For flexible vinyl and PVC
plastisol formulations, a half to two-thirds of the antimony trioxide can be replaced by zinc borate
without loss of flame retardancy. If a small decrease in flame retardancy can be tolerated, all of the
antimony trioxide can be replaced with zinc borate, leading to smoke reductions of up to 65%. The
flame retardancy can be increased and smoke formation decreased by adding ammonium
octamolybdate to the borate-containing formulations.
3.8 Intumescent Materials
Intumescents function because, under fire conditions, they foam to produce an insulating carbon
char which both protects the substrate from high temperatures and allows only a small proportion
of polymer to be involved in the fire. Heat release can be controlled because the surface of the char
nearest the flame will ablate, so absorbing energy. This contrasts with conventional flame
retardants that absorb energy by endothermic chemical decomposition or liberation of water, or by
altering the polymers surface chemistry to slow down oxygen access.
Intumescents are said to have a key advantage over filler-type non-halogenated flame retardants in
that they are effective at lower addition levels than traditional materials. For example, an
intumescent based on ammonium polyphosphate will achieve the same level of protection at
addition levels of 25 to 35 parts by weight (pbw) as a typical non-halogenated flame retardant, such
as alumina trihydrate or magnesium hydroxide, at between 60 and 70 parts by polymer weight.
Nitrogen-containing compounds based on melamine are used in a more restricted field (polyamide
and polypropylene).
15
16
4 Products and their Markets

This chapter gives information about some of the flame retardant products on the market and
discusses their applications in various plastics. Comments are made with regard to the eventual
destinations and fitness-for-purpose of the materials.
4.1 Organic Halogen Containing Materials
4.1.1 Bromine Compounds

Materials, like ABS and HIPS are widely used as housings for brown goods, IT and business
machines. Unfortunately they burn easily but can be protected by the correct use of flame retardant
science and technology. The starting point has always been to use brominated FRs plus antimony
oxide as a synergist. However, these long-standing products do not often meet all of the
requirements.
Decabromodiphenyl ether is cost efficient in HIPS but has poor UV stability and is not melt
blendable during injection moulding. TBBA is cost efficient and melt blendable in ABS but has
low thermal stability, poor impact properties and may not meet UV stability standards. It also
lowers heat distortion temperature.
Many companies are developing new, more environmentally friendly brominated flame retardants.
4.1.1.1 Dead Sea Bromine Group

Newer brominated materials from Dead Sea Bromine have been developed to allow the company
non-polybrominated diphenyl ether (PBDE) options for a range of polymers, especially styrenic
copolymers.
Brominated epoxy oligomers (BEO) and modifications of this FR (MBEO) are diphenyl ether-free
products used in high-impact polystyrene. The MBEO has more bromine. Their use allows for a
significant improvement of the impact properties of HIPS. The BEO is designated F-2016 and has a
bromine content of 50% with a softening range of 105-115 C. The MBEO is called F-3014 with
the higher bromine content of 56% and a slightly higher softening range of 113-127 C. Both are
formulated at around 14-16% loadings plus an antimony oxide synergist. They combine good to
excellent UV stability with good melt flow properties during injection moulding but suffer from
rather poor impact properties. F-2016 is used for UV stable ABS applications.
F-2016 is a brominated epoxy oligomer with around 50% bromine and a molecular weight of 1600
designed to ensure optimal properties in styrenic copolymers. Brominated epoxy oligomers offer a
combination of high flame retardant efficiency, UV stability, good mechanical properties and
thermal stability. They are non-blooming due to their physicochemical properties and polymeric
structure.
The epoxy groups provide a good compatibility with the matrix of the plastic; and the oligomeric
structure and its softening range are the main factors that limit the mobility of this particular flame
retardant in styrenic copolymers. The low molecular weight of F-2016 has been chosen to provide
better flow during injection moulding as well as good surface appearance.
F-3020 is an end-capped brominated epoxy oligomer with 56% of bromine and a molecular weight
of 2000. It has been developed to give a better compromise of UV stability and impact properties in
styrenic copolymers than other brominated epoxy oligomers.
17
Improvements have been made to FR-1806, a hexabromocyclododecane (HBCD), to provide better

colour thermal stability for EPS while FR-1206HT can cope with higher temperatures for extruded
polystyrene (XPS) and is also a cost efficient FR for HIPS and PP at V-2 rating under UL94
testing.
FR-720, TBBA bis(2,3-dibromo)propyl ether, offers an efficient combination of aliphatic and
aromatic bromine to meet UL94 V-2 with very low bromine content in HIPS and PP. It contains
68% of bromine. It is widely used for water discharge pipe to pass B1 class in DIN4102, and as
lamp sockets to V-2 and V-0 under UL94. This melt blendable FR has optimal thermal stability but
has a tendency to bloom in PP. 3-5 phr are required for V-2 with 1-1.5 phr of antimony trioxide and
14-18 phr for V-0 with 5-7 phr of antimony trioxide.
Tris(tribromoneopentyl) phosphate with 70% of bromine is offered as FR-370. This combination of
bromine content and phosphorus on occasions obviates the need for any antimony trioxide.
Moreover, the position of the bromine in the molecule contributes to good thermal and light
stability. It also reduces the problem of blooming and plateout. It is recommended for the
production of seats and furniture for use under UV exposure. The melting point of 181 C is
advantageous compared with those of other FRs, and so allows a reduction of 10 to 20 C in the
processing temperature. 2-3 phr of FR-370 is the loading range for V-2 with 1-1.5 phr of antimony
trioxide. Moreover V-2 can also be achieved in an antimony-free formulation containing 6% of FR370. The company believes FR-370 should open up new opportunities for PP in exposed sections.
A special grade, FR-372 has been designed for PP fibre and textiles. The usual method of
application is via a masterbatch containing 30-40% of flame retardant. This concentrate is then
diluted in the PP to reach around 3-5% of FR-372 in the final composition.
FR-1206HT contains 66.2% of bromine and can be processed at up to 240 C at 2-3.5 phr loading
in PP with around 1 part of antimony trioxide.
Flame retardant systems based on decabromodiphenyl ether or its substitutes are often regarded as
the safest ones to provide high standards of retardancy up to UL94 V-0 rating. FR-1210 contains
83% of bromine and these aromatic additives are recommended for situations when polypropylene
is to be processed at over 230 C. However, as PPs ignition temperature is comparatively low,
high loadings of such additives are necessary to reach V-1 or V-0 standard. Typical formulations
contain 35 phr of FR additive plus around 12 phr of antimony trioxide. The total weight of
functional additives present can be reduced by the use of 20% talc in the formulation.
FR-1808, brominated trimethylphenyl indane, contains 73% of bromine. It has good thermal
stability due to the aromatic linkage of the bromine.It is suggested for use in filled polypropylene
compounds at levels of around 20-25 phr with magnesium hydroxide at loadings of 20 to 35% to
give a UL94 V-0 rating. FR-1808 has a melting range of 240-255 C, which has important
beneficial effects on flow properties of the subsequent plastic compound. When processed above its
melting range, FR-1808 behaves as a melt blendable flame retardant and has important benefits on
properties such as impact strength and flow.
It is recommended to carry out injection moulding at a temperature of at least 250 C so that the
FR-1808 is fully melted and to improve impact properties. The additives high melt flow and
impact strength can give thinner wall parts and shorter cycle times.
FR-1808 has undergone extensive toxicological and environmental testing. The tests have shown
very low acute and repeated dose toxicity. In addition, the Fresenius Institute performed analyses
on both the neat product and on gases evolved when simulating conditions in a municipal
incinerator. The results indicate that FR-1808 poses no risk through any release of brominated
dioxin or furan species.
18
The main advantages offered by FR-1808 include a significant improvement in flame retardancy,
with values of limiting oxygen index (LOI) up to more than 50 being achieved quite easily. In
addition, good processing aid properties offer long spiral flow, all of which are especially useful for
the production of thin-wall parts with glass-reinforced thermoplastics. Thermomechanical
properties such as tensile, flex, impact and heat deflection temperature (HDT) are either maintained
or improved and a fairly good comparative tracking index (CTI) is achieved.
FR-1808 is particularly used in styrenics and engineering thermoplastics such as polyamide (PA)
66. Its good miscibility with styrenic copolymers has been explained by its total and irreversible
amorphisation and the closeness of its glass transition temperature to that of polystyrene. It has a
molecular weight of 707 and a decomposition temperature 50 C lower than brominated
polystyrene.
A different FR is suggested for glass reinforced PP. This is poly(pentabromobenzyl acrylate)
containing 70% of bromine, offered as FR-1025. The softening temperature of around 180 C is
optimal to provide both processing aid during injection moulding and high heat distortion
temperatures under load. Around 40 phr of FR-1025 are suggested for 40 phr glass content with a
quite high antimony trioxide presence, to obtain V-0 under UL94. The acrylate part of FR-1025
improves the compatibility between the glass fibre and the PP matrix to optimise impact and
thermo-mechanical properties.
FR-1210 can be used in PA6 applications, but it decomposes when applied in PA66.
FR-1025 is particularly suitable for polyamides, PET and polybutylene terephthalate (PBT), with or
without glass fibre reinforcement. As a result of its aromatic structure, high bromine content and
good thermal stability, FR-1025 has inherent advantages over other halogenated FR additives
offered for the same applications. Also polymers containing FR-1025 have good processibility. FR1025 is now produced by Dead Sea Bromine in a completely new facility that utilises the latest
polymerisation techniques. This step was taken to support the very high growth rate of its use in
engineering thermoplastics and has resulted in improved quality.
Relative to other FRs, FR-1025 has advantages through its high effectiveness and its contribution
to better workability of thin injection moulded parts, good impact strength, improved electrical
properties and better thermal ageing. After 1,000 h of thermal ageing at 190 C of glass reinforced
PBT containing FR-1025, tensile properties are maintained above 50% of their initial value while
non-flame retarded PBT would fail during this test. Similar effects of thermal stabilisation of PP by
brominated flame retardants are observed during thermal ageing at 150 C for 1 month; retention
being around 60%.
Connectors made with FR-1025 are found in patch cords for computers and in automotive
electronics as well as in various inner parts of domestic appliances. It also exhibits special
advantages in recycling since it is possible to add high amounts of reground old products (that
contain FR-1025) to commercial PBT resins without loss of properties.
Multi-layer epoxy laminates demand excellent electrical insulation and the high purity of FR-1524
(TBBA) used in their production. The flame retardant of choice for transparent, UV stable,
polyester resin sheet for the building industry is FR-522, a brominated aliphatic diol that guarantees
low discoloration of the sheets during long sun and light exposure.
Other brominated FRs from Dead Sea Bromine are reactive types that should be compatible with
any solvent system that is utilised as a polymerisation medium. So, aliphatic materials such as FR513 (in alcohol) and FR-522 (diol) have good solubility in the polyol or trichloropropylphosphate
(TCPP) systems used for the production of polyurethane foams.
19
Brominated polystyrene FRs are preferred when high values of tracking index are needed in
polyamide applications. For other BFRs, such as the FR-1808 or FR-2400, tracking index value is
improved by adding 10 to 20% of surface-treated magnesium hydroxide.
Tris(tribromophenyl) cyanurate, known as FR-245, has been studied for utilisation in styrenic
copolymers. It is a melt blendable material that combines good impact properties and UV stability
in styrenic copolymers and their alloys.
FR-245 is a joint development between Dead Sea Bromine and a Japanese company, Dai-Ichi
Kogyo Seiyaku (DKS), and aims to offer a balance of properties that include high melt flow during
injection moulding, excellent light stability, good impact strength, and high heat deflection
temperature (HDT). The chemical structure of this cyanurate combines a 67 wt% aromatic bromine
and a cyanurate segment to provide good FR efficiency and UV/light stability. FR-245 also
contains 4% nitrogen. It has a melting point of 230 C, and a molecular weight of 1067. Use of FR245 also enhances flow during moulding as it melts during the process. It is not related to diphenyl
ether chemistry and is designed to be environmentally friendly with no risk of dioxin or furan
formation.
In both ABS and HIPS, FR-245 offers an excellent combination of melt flow, impact resistance and
light stability. Recycling work on ABS flame retarded with FR-245 have shown that a loading of
50% scrap in virgin compound can undergo six recycling loops without any significant changes in
tensile properties. It is used in styrenic copolymers for copy machine parts, TV and video casings
and housings for kitchen hoods and similar devices. It is now preferred in PC/ABS alloys over
phosphate derivatives if a high heat distortion temperature is required.
Tribromoneopentyl alcohol (FR-513) is a reactive FR for applications in polyurethane foam
materials and is recommended for non-leaching flexible foam applications such as combustion
modified heat resistance (CMHR) products. It is also one of the preferred FRs for CFC-free rigid
PU foam. Both in flexible and in rigid foams, systems based on FR-513 fulfil the highest fire safety
requirements in Europe.
A new range of products from Dead Sea Bromine was fully introduced in early 2002. The PR-5000
series have been aimed at providing the market with tailor-made fire safety solutions for
particularly demanding applications. Some of the criteria met by them are:
Improved flame retardation properties and antimony trioxide-free systems,

Long-term thermal and UV stability,
Improved corrosion protection at high processing temperatures,
Dust-free systems,
Low smoke generation,
Improved melt flow in injection moulding.
PR-5104 containing 66% bromine is a dust-free, 100% active FR masterbatch for engineering
plastics. It is based on the companys experience of high-molecular weight polymeric brominated
FRs as carriers. This material provides good processibility, high temperature resistance and
outstanding compatibility between fibre reinforcement and the resin matrix.
PR-5127 is an aliphatic system with 63% bromine combining improved flame retardancy with
colour thermal stability and corrosion protection in UL94 V-2 HIPS and PP applications.
PR-5183 reaches class V-0 in UL94 without antimony trioxide in polyamide. It enables the
compounds to exhibit a good tracking index and low smoke generation.
20
PR-5371 contains 65% bromine and offers outstanding light stability. In PP compounds it can
produce UL94 V-2 with <1% bromine and no antimony oxide. V-0 is reached with <6% bromine
and 7.7% antimony trioxide.
4.1.1.2 Great Lakes

PH 73FF is a free-flowing form of tribromophenol, used as a fire retardant intermediate. It is
normally used to produce brominated epoxy oligomers for use in ABS and other engineering
polymers. In its standard form, the chemical is a low melting-point solid that tends to compact.
However, it is now available as a briquette that is both non-compacting and non-dusting. According
to Great Lakes, another benefit from PH 73FF is that the briquettes stabilise the colour of the
intermediate during transit and provide a more consistent colour in flame retardant products.
Firemaster 2100 is a general-purpose brominated compound not based on diphenyl ether chemistry.
It is supplied as a uniform white powder suitable for formulations requiring white or light-coloured
products. Use is foreseen in applications such as TV cabinets, foam insulation, wire and cable,
appliances and textiles.
Great Lakes produces its brominated styrene polymers in a different way from its competitors.
Competitive products are made by post-brominating the polystyrene polymer. This can be a
difficult reaction and sometimes by-products are formed that can reduce thermal stability in the
resultant material. To reduce the impurities, the competitors have developed additional steps that
then improve the thermal stability, albeit not entirely.
Great Lakes polymerises a brominated styrene monomer. This monomer can be either homo- or copolymerised. In this way, a variety of different products that vary in bromine content or in
molecular weight, can be made to address specific performance needs of the customer. This route
contains some inherent strengths but also weaknesses relative to competitive products.
PDBS-80 was the first in the series. This material is a homopolymer of dibromostyrene that
contains 59-60% bromine. Its primary applications are in high-temperature polyamides and
polyethylene terephthalate (PET) because it has excellent flow characteristics and very good
thermal stability. In addition, there are benefits of excellent colour retention. The main weakness of
this approach is the bromine content relative to the competitive material. Todays competition
contains around 68% bromine. This can translate into a 2-3 parts difference in the load level needed
in the protected polymer to give equivalent flame retardancy.
This deficiency was remedied by the introduction of a series of homopolymers based on a new
monomer containing 64-65% bromine. The first was Firemaster PBS-64, which is a homopolymer
of a dibromo, tribromo styrene monomer. This is aimed also at high-temperature polyamides and
the PET area. The molecules have been designed to retain excellent thermal stability and good flow
properties. PBS-64 is especially effective in high temperature polyamides where high thermal
stability, flow and colour stability are of prime importance, needed, for example, when making
small electronic parts under fast cycling, high shear conditions. High thermal stability is also
important when components are recycled at end-of-life, especially with regard to colour retention.
However, PBS-64 is darker and more expensive than PDBS-80.
A higher-weight version was developed for applications in PBT and regular PA6 and 66. PBS64HW is also a homopolymer of dibromo and tribromo styrene with ~64% bromine. The higher
molecular weight helps give the best physical properties, although flow is compromised albeit not
as low as the competitive brominated polystyrenes.
PDBS-80 typically is used at 22 parts with 7 parts of antimony trioxide (ATO) to give V-0 in a
30% glass filled PA66, whereas PBS-64 and the brominated polystyrene use about two-thirds parts
less and slightly lower levels of ATO.
21
Table 4.1 shows a comparison of PDBS-80, PBS-64 and a competitor brominated polystyrene in a
high-temperature polyamide resin. PBS-64HW does not feature, since it is not recommended for
the high temperature PAs due to its lower flow, which is a critical property in such resins.
Table 4.1 Comparison of brominated styrene polymers in 30% glass-filled HT polyamides
Properties
PDBS-80
PBS-64
BPS*
% FR / % ATO
22/7
20/6.4
19.5/6.3
UL94, 1/32" (0.8 mm)
V-0
V-0
V-0
Tensile strength (MPa)
160
168
150
Tensile elongation (%)
2.1
2.2
1.9
Izod impact (unnotched) (J/m)
560
651
507
* Competitive brominated polystyrene
Source: Speciality Chemicals Magazine, reproduced with permission.
One of the deficiencies of brominated styrene polymer FRs is that they are not very compatible
with the polyester or polyamide resins. Typically they are present as a discrete phase. It has been
found that by using certain copolymers instead of homopolymers, the compatibility of this type of
flame retardant can be improved.
A new product called Firemaster CP-44B uses this technology. CP-44B is a copolymer of PBS64HW and glycidyl methacrylate (GMA). Typically, 0.25-1% of GMA is required to give this
compatibility. The principal is that the copolymer has the ability to react with the acid end groups
that exist in the polyamide and polyester resin to better disperse the product throughout the
polymer phase. In addition, in some cases the level of synergist may be reduced yet still give the
same level of FR performance.
Another benefit of the new technology is an improvement in retained colours, but with a decline in
flow. It is important to control the molecular weight and the percentage copolymer to maximise the
compatibility effect without totally removing the flow advantage of these products. As they are
expensive they would only be recommended where they offer an advantage or give properties not
achievable by another product in the range.
In many formulations using Firemaster CP-44B, the synergist level can be reduced by 20-30% and
a strong V-0 performance still obtained. This is an advantage in a couple of areas. It can reduce the
cost of formulating the product and can also help reduce specific gravity. Physical properties are
comparable with PBS-64HW and competitive brominated polystyrenes. The copolymers are also
particularly effective in unfilled polyester applications. CP-44B gives a strong V-0 result, while
comparable levels of the competitive brominated polystyrene and PBS-64HW gave V-2 ratings.
Firemaster CP-44B and its companion 44C are highly compatible copolymers used in
electromechanical devices, business machine parts, power tool housings and appliances.
4.1.1.3 Albermarle
Albemarle offers a range of BFRs under its Saytex banner.
Saytex CP-2000 is widely used for printed wiring boards laminates made from FR4 epoxies. It is
reacted into the epoxy, so that there is no potential for leaching out of the resin. The FR meets the
German Dioxin Rule. It is environmentally acceptable, thermally stable at high temperatures and
does not disrupt resin properties when soldered. It can be used as an additive in ABS and also as a
raw material in brominated epoxy oligomers in ABS and high impact polystyrene (HIPS).
22
Saytex 8010 and Saytex BT-93 are diphenyl ether (DPE)-free and are not melt blendable. They
have fair to excellent UV stability, but have limitations in impact and injection moulding
properties.
Saytex 8010 is not toxic, does not concentrate in bio-systems, meets the German Dioxin Rule, is
effective at low loadings and does not disrupt resin properties. It is much more UV-stable than
traditional products.
Saytex BT-93 is also non-toxic and does not bioconcentrate. It meets the German Dioxin Rule and
has excellent recycling properties. It is effective at low loadings so not affecting compound
properties with again high UV stability. Saytex BT-93W is particularly useful in light coloured
formulations.
Saytex 102E meets the same criteria for utilisation in plastic compounds as the FR materials
already mentioned.
Albemarle offers a range of brominated polystyrene FRs, called Saytex HP-7010.
Only in recent times has Albemarle, the source of Saytex brominated flame retardants, revealed
more detail on the chemistry of some of their non-PBDE products. Saytex 8010 is ethane 1,2-bis
(pentabromophenyl), or EBP, commercially available only from Albemarle. It was developed so
that a brominated FR could be offered to the market that had a much-reduced likelihood to form
dioxins or furans during any subsequent combustion.
The key is the ethane bridge between the aromatic rings, versus an oxygen atom in
decabromodiphenyl ether (decaBDPE). The spatial arrangement of the rings does not allow easy
bond formation of the type necessary to produce dioxin or furan structures. EBP is a direct
replacement for decaBDPE in many applications such as HIPS for electrical and electronic (E&E)
products and offers performance benefits compared to the deca-compound in UV and thermal
stability. It displays bloom resistance. UL94 V-2 is achieved with 8% EBP and 3% Sb2O3, while
12% EBP and 4% Sb2O3 is needed to reach a V-0 rating.
Impact strength reduction compared to an untreated HIPS resin can be offset by the addition of
around 3% of a styrene-butadiene-styrene (SBS) rubber impact modifier. For black E&E
applications such as TVs the UV stability is no problem, but for lighter coloured goods this
becomes an issue. An appropriate stabiliser and pigment presence is required. The presence of EBP
also reduces the discoloration of HIPS after repeated cycles of regrind and further moulding and
has little effect on mechanical, physical or flame retardant properties over this period.
Saytex BT-93W can be used to flame retard PBT compounds for use in electrical connector
applications. It is EBTBP, also called EBT for short, which is ethylene bis(tetrabromophthalimide).
It is the only EBT on the market. It is compounded with antimony trioxide and provides excellent
impact strength, tensile elongation and UV light stability. Typically an 11% loading is
accompanied by 5% Sb2O3 to achieve UL94 V-0 rating.
EBT also offers the best UV stability for HIPS at the V-0 level, where the most stringent colourfast requirements are imposed by OEMs.
Both EPB and EBT can be used at lower loadings for a V-2 or in the Glow Wire Flammability Test
(GWFT). However, other options exist that have a higher efficiency for V-2 or Glow Wire ratings.
Saytex HP-900, hexabromocyclododecane (HBCD), or its stabilised version called BC-70HS,
provides V-2 at a dosage of 3.3%.
23
Saytex HP-800 is tetrabromobisphenol A bis(2,3-dibromopropyl) ether and is also very efficient.

5% combined with 1% Sb2O3 typically results in V-2 or Glow Wire 960 C rating at 1.6 mm.
A new product for V-2 applications in both HIPS and PP is Saytex 2100. It has a bromine content
of 70% and comes as a white powder or granules. In a stabilised form it can be processed at up to
240 C in PP and 250 C in HIPS. Typical loadings are 5% for V-2 HIPS or 4% for V-2 PP, plus
1% of Sb2O3 in each case. It provides good melt flow and impact strength, which are better than for
EPB. It does not bloom from HIPS and shows less blooming from PP than other widely used FRs.
Another new product is Saytex HP-7775. This is an extruded blend of brominated polystyrene (HP7010 from Albemarle) and Sb2O3 in a ratio of 77.5/22.5. It comes as dust-free, free-flowing
granules. It provides outstanding thermal stability and electrical performance, making it ideal for
polyamides and polyesters in electrical applications. It has excellent mechanical properties, flow,
non-blooming and, not least, recyclability, all similar to the basic brominated polystyrene.
4.1.1.4 Ferro Corporation

Responding to the need for thinner, smaller components in the electronics industry, Ferro Corp had
developed an advanced brominated polystyrene flame retardant under their Pyro-chek name for
high temperature glass-filled engineering polymers. Pyro-Chek 68Pbi is said to offer improved
thermal stability and colour for high temperature applications.
The product is suitable for both injection-moulded printed, circuit board mounted connectors as
well as for compounders using larger extruders that operate at higher temperatures. The French unit
of the company received much investment now enjoyed by the new owners, Albemarle. The
facility houses a pilot plant facility which has been focussing on expansion of the portfolio for use
in glass-filled polyamides and other grades for high temperature applications.
Pyro-Chek 68Pbi was developed for use in high-temperature polyamide and polyamide-polyester
alloys, but can also be utilised for faster compounding of PA66 in larger, hotter running, extruders.
The material is available in powder and compacted form.
4.1.1.5 Unitex Chemical Corporation

Unitex Chemical Corp. has entered the market with an identical product to Dead Sea Bromine's
bromophosphorus product FR370. This is called Uniplex BAP 370. This particular FR is unique in
that it frequently does not require any synergist present to provide good FR performance.
4.1.2 Chlorine Compounds

Chlorinated fire retardants (CFRs) are utilised in polyamides, epoxies and PBT. The use of mixed
synergists, that is antimony oxide plus another synergist, can lower the total loading of FR
additives to the formulation. With glass-filled polyamide compounds where a higher processing
temperature is sometimes required, the elimination of antimony oxide greatly improves the thermal
stability of the formulations.
Concerns about antimony oxide have led to a range of alternatives being explored across different
families of polymer resins. Different zinc compounds and iron oxides have been found effective
with CFR.
Polyamide 66 formulations are UL94 V-0 down to 1.6 mm with 16% CFR, 4% zinc borate and 2%
of either antimony oxide, zinc sulfide, zinc phosphate or zinc stannate. The most effective package
is zinc borate with iron oxide. Here, only 12% CFR with 1.5% zinc borate and 1.5% iron oxide
24
gives a V-0 material. The latter formulation gives an electrical CTI result at only 350 volts. The
best formulations for CTI have all zinc compounds as the synergists, giving 600 volts.
Higher loadings are needed for glass filled polyamide compositions to achieve V-0 or V-1 in UL94
tests and the CTI levels drop to around 325-350 volts.
Occidental Chemicals, or Oxychem, has long offered Dechlorane materials, one of which is
designated Dechlorane Plus 25, sometimes just referred to as CFR. This contains 65% of chlorine
and is a Diels-Alder adduct of hexachlorocyclopentadiene.
4.2 Phosphorus Containing Compounds
4.2.1 Introduction
Most phosphorus based FRs tend to promote char formation, which gives several desirable
benefits. The char is difficult to ignite, it acts as a barrier between polymer and flame, it restricts
oxygen access, and it reduces the rate of heat generation. This works well for polyesters, PU and
polyamides, but when it comes to styrenic polymers or polyolefins, there is often a need to combine
phosphorus systems with other additives.
Phosphorus chemicals can be compounded at up to 230 C, comfortably higher than ATH. Also,
moisture sensitivity is not a problem. However, although not suffering from the problems that
surround halogenated flame retardants, the view from outside the industry taken by
environmentalists about the retardants based on phosphorus chemicals, may be influenced by the
reputation of different organophosphorus chemicals in agriculture and other areas that have
received somewhat adverse publicity.
4.2.2 Polymer Modification

Flame retardants reacted with the polymer backbone usually provide protection at lower levels and
thus have a smaller, usually malign, influence on the compounds mechanical and physical
properties. In the case of phosphorus-containing chemicals utilised for FR purposes, there exists a
range of possibilities that are being explored.
Vinyl and allyl phosphonates can be used as comonomers in addition polymers. Also,
modifications of polymers with phosphorus-containing groups, such as phosphorylation of
polyvinyl alcohol, leads to improvements in flame retardancy compared to the polymers
themselves. Phosphorus-containing acrylates have adhesive properties as well as FR ones.
Acrylates containing phosphonic acid groups have some interesting and encouraging properties.
Other work has attached unsaturated phosphorus-containing compounds to unsaturated polyesters
to improve their flammability. Such compounds enter into copolymerisation with the polyesters
being modified at the curing stage. Glycol maleate phthalate polyester was copolymerised with a
di-ester of methylphosphonic acid.
4.2.3 Red Phosphorus

The safest and most convenient way of handling and processing red phosphorus (P-red), which is
flammable in powder form, is the use of concentrates or masterbatches in a wide range of resin
systems for a variety of applications. Quality standards are now being linked to the safety and
environmental effects of the additives polymer compounds contain. Consequently the toxicity and
environmental concerns about P-red have been under the spotlight recently.
25
Improved safety aspects as well as an upbeat classification for the product have given a boost to Pred chemistry in new applications. The material is now being introduced in polyolefin blends, HIPS
and PBT, as examples.
P-red is an active flame retardant as a single additive in nitrogen and/or oxygen containing
polymers such as polyamides, polyesters, polyurethanes, epoxies, isocyanates and polycarbonates.
It can be part of a package with carbon char-forming agents or metal hydroxides in olefins and
styrenics.
P-red is the most concentrated source of phosphorus, so it is an effective FR at a concentration
between 2 and 10 wt% of the polymer resin. It is generally used for meeting highly demanding
flammability requirements, reducing the formation of toxic smoke and providing good electrical
properties, such as high CTI values, with good mechanical characteristics. Restrictions on its use
are now only on the basis of colour, since it cannot be used for white or light coloured end
products, but it is widely applicable for items from black to medium grey and some dark reds and
browns.
High thermal stability enables P-red to withstand an extrusion temperature of up to 320 C without
decomposing and be particularly suitable for polyamides. During combustion, the combination of
the phosphorus with oxygen and nitrogen in the polymer produces intermediates that then
recombine to make an extended char layer as the flame retardant proponent.
It has been usual to microencapsulate and coat P-red, but even with this pre-treatment, the powder
is still flammable and can become a hazard during handling. It is now more accepted to prepare Pred in masterbatches for a range of polymers. When P-red is completely encapsulated in a polymer
matrix it cannot react with air or water. Improved techniques in the production process and
increased expertise in compounding now prevent the possibility of forming phosphine, which in
any case is rapidly oxidised to form harmless phosphates.
In a fire or during waste incineration, P-red is easily oxidised to phosphorus oxides, which do not
lead to phosphine production. The phosphorus oxides remain as polymeric phosphoric acid or
phosphates in the bottom ash or can be removed in the flue gas treatment system of incinerators.
The German Federal Environmental Agency defined P-red use as unproblematic (like ammonium
polyphosphate (APP) and ATH) in its risk assessment report on the most commercially important
FRs in August 2001.
One company that is involved with P-red compounding is Italmatch Chemicals of Genova (Genoa),
Italy. Developments by the company have increased the efficiency of stabilisation of the element to
such an extent that they estimate that three orders of magnitude less formation of unwanted species,
such as hydrogen phosphide or phosphoric acid, occurs during high temperature compounding or
processing in the presence of high moisture.
This change in the perception of P-red grades has been carried forward to new grades that increase
the range of applications into previously under-considered resins.
Loadings of 10-12% of Masteret 90450 from Italmatch in a 30% glass reinforced PBT achieve V-0
at 0.8 mm in UL94 and a CTI of 600V with maintained mechanical properties and hydrolytic
stability of the compound, even in the most severe tropical conditions.
P-red is also effective for unloaded polyolefins of all types. UL94 V-2 can be achieved at 3.2 and
1.6 mm and the formulation using grade M15460 B2XF at 7% is competitive against standard
halogen-based systems as well as other halogen-free ones. After-burning time is short and B1
classification is possible in the German standard DIN 4102. However, FR activity is not sufficient
to obtain V-2 in a talc filled compound.
26
In addition, P-red is effective with synergists to reach V-0 in polypropylene. It has to be used in
combination with a nitrogen-containing compound at a total loading of 20-25%. The same
approach can make HIPS compounds flame retardant to V-0 at 1.6 mm as the requirements for TV
sets now demand at least a V-1 rating due to safety regulations becoming more stringent.
4.2.4 Ammonium Polyphosphate

Ammonium polyphosphate (APP) is a fine-grained non-toxic white powder with average particle
size of 8m or 15m depending on grade. It uses the intumescent effect for flame retardancy. The
flame retardant material foams on exposure to heat or flames. The carbon foam layer protects the
host polymer structure through its heat-insulating effect and reduces further oxygen access to the
polymer fuel. This is generated by an acid dehydration of the polymer.
4.2.5 Phosphorus Oxynitride

Phosphorus oxynitride (PON) is the name for a family of closely related materials that have been
around for over 100 years. They are not well known but are thermally very stable and may be
considered as future flame retardants and for intumescent formulations since PON is analogous to
ammonium polyphosphate. It can be made from inexpensive starting materials such as ammonium
phosphate, melamine phosphate or urea phosphate just by prolonged and intensive heating.
Work in Belarus in collaboration with the Polytechnic University of Brooklyn has verified the
claims for use in polyamide systems but has indicated a less successful outcome in PBT
compounds.
PON prepared by heating phosphoric acid with urea and melamine to 750 C, is an efficient fire
retardant additive for polyamide 6. It increases strongly the oxygen index (OI), and in combination
with ferric oxide provides V-0 classification under the UL94 test. However, PON only slightly
increases the OI of PBT, either alone or in combination with other additives, and has no effect on
the UL94 performance.
PON promotes extensive charring in both PA6 and PBT, so different mechanisms are believed to
be at work in the two polymers. Upon thermal decomposition in the presence of PA6 and probably
of water evolved from the polymer, PON transforms into polyimidophosphoric acid, which reacts
with PA6 producing phosphoric esters. Intumescent char is formed by thermal decomposition of
the esters. Thus PA6 is involved in the charring. In the case of PBT, the charring occurs because of
retardation in the volatilisation of terephthalic acid fragments due to the formation of ammonium or
amine salts. However, the preferential evolution of highly combustible aliphatic fragments
observed at the initial stages of the thermal decomposition of PBT+PON probably works against
the flame retardant effect provided by the char.
4.2.6 Albermarle Corporation

Albemarle Corporation has introduced the first of their new NcendX range of halogen-free flame
retardants, which widens their portfolio into phosphorus-based products.
NcendX P-30, the companys new non-halogenated FR for PC/ABS blends and modified PPO,
comes from a new plant in the US. The new material is expected to be used in the market for
halogen-free plastics used in office automation and computer equipment. It is regarded as an
excellent complement to the companys Saytex brominated products for this same market. P-30 is
bisphenol A diphenylphosphate (BPADP).
27
NcendX P-30 offers excellent hydrolytic stability and low bloom for resin producers and
compounders. It is a colourless liquid, ideal for colour-critical applications. It provides excellent
UV stability, improves resin flow and has low volatility plus outstanding thermal stability.
4.2.7 Polymer Tailoring

Sometimes phosphorus systems do not work as well with other additives as they do without. An
example is the Antiblaze (formerly Amgard) NK and NP grades, which can be less effective with
zinc borate-based smoke suppressants than without. The additive pentaerythritol has been known to
cause problems in intumescent systems with the same grades. NK and especially NP, which are
used typically with loadings up to 30% of resin weight, usually tint the product. Amine oxides form
on the surface, but processing at lower temperatures can moderate the tendency. White shades can
be produced by using fine grades of titanium dioxide. Colouration may also be reduced by adding
antioxidants, such as a phosphite/phenolic blend, or a triazine hindered phenolic.
Dispersion of NK and NP in polyolefins is not straightforward because of the polarity of these
grades, so a silane coupling agent is recommended. The silane partially restores the elongation at
break of PP, which can otherwise be drastically reduced by the FR, although impact strength as
measured by Izod tests are maintained.
The global manufacturing and marketing of Antiblaze NP and NK have been taken over from
Rhodia Consumer Specialities by Polymer Tailoring.
4.2.8 Akzo Nobel Chemicals

Fyrolflex RDP is a resorcinol bis(diphenyl phosphate). It is a liquid that is designed for use in
engineering plastics such as polyesters, modified PPO as well as PC/ABS blends and HIPS. It has
low volatility and good thermal stability, meaning it can outperform triaryl phosphates, such as
triphenyl phosphate. Fyrolflex RDP is used either as a flame retardant or, in low doses, as a flow
modifier.
Fyrolflex BDP from Akzo Nobel Chemicals has been shown to exhibit higher thermal properties
and hydrolytic stability than other aryl phosphates, and to provide similar or better fire retardant
performance than RDP. It is a bisphenol A bis(diphenyl phosphate) compound that provides good
physical properties in formulations based on PC/ABS, HIPS and polyphenylene oxide/HIPS
blends. Upon thermal decomposition of the flame-retarded polymers, phosphorus tends to
accumulate in the solid residue, a result which indicates that the primary FR action of BDP is most
likely to be in the condensed phase.
Akzo Nobel has expanded its production of Fyrolflex BDP. Fyrol BDP would appear to compete
with Albemarles move into phosphorus-containing materials, called NcendX P-30.
To replace the pentabromodiphenyl ether that has been used in furniture foam but is now to be
phased out under current regulations, Akzo introduced an all-phosphorus FR for flexible
polyurethane foam. Fyrol PNX contains 18% phosphorus, which permits a lower loading in the
formulation.
4.2.9 Great Lakes Chemical Corporation

For use in flexible polyurethane foam, Firemaster BZ-54 from Great Lakes Chemical Corporation
is available. Compared with conventional chlorinated phosphate esters, it requires smaller loadings
and has lower plasticisation effects. Foams incorporating BZ-54 show low scorching when using
alternatives to freon-type blowing agents. It is also ideal when using flame bonding to prepare foam
laminates.
28
In addition Great Lakes has expanded its range of non-halogenated phosphorus-containing

materials. New to the Reofos range are bis(4-aminophenyl) phenyl phosphate (BAPP), a bisphenol
A diphosphate and 507, a butylated triaryl phosphate. Both of these materials are designed for use
in polycarbonate/ABS and polyphenylene oxide (PPO)/HIPS mouldings, such as computer
housings and monitors. The two Reofos additives are claimed to overcome the problem of stress
cracking, plate-out and juicing often associated with the utilisation of flame retardants in polymer
blends. They have a high degree of hydrolytic stability, which is increasingly important with the
growth of component recycling.
A more recent addition is Reofos NHP, a low-fogging additive for hot-moulded polyurethane (PU)
foam for automotive seats. This material offers an alternative to chloroalkyl phosphates to meet the
MVSS 302 standard.
An intumescent flame retardant has been recently introduced by Great Lakes. CN 2626, Reogard
1000, is a nitrogen and phosphorus-containing FR aimed at injection moulded polypropylene. It is
melt blendable at PPs processing temperature and is said to increase the HDT of the compound. It
is non-blooming, has good electrical properties and has a reduced tendency to absorb water. It is
recommended for use in V-0 PP homopolymers and low PE-content copolymers for a range of
E&E, appliance and mass transit applications.
4.2.10 Clariant
Exolit flame retardants from Clariant do not use halogens to produce flame retardancy. They have a
low smoke density and produce non-corrosive gases. Exolit materials can be combined with light
stabilisers to provide good UV stability in flame-retarded plastics. The Exolit AP series for
thermosets is used in combination with ATH to allow manufacturers to use UP and epoxy resins in
lightweight components for trains and buildings.
Exolit AP 750 is used in polypropylene injection moulding for the electrical and electronic sectors.
When combined with hindered amine light stabiliser (HALS)-type UV stabilisers, it has good
resistance to discoloration and embrittlement of FR-treated polypropylene items. External
applications include stadium seating. Exolit AP 751 has been especially developed for glass-fibre
reinforced PP. The addition of around 30% of AP 751 to a 20% glass by weight PP can achieve
flame retardancy to UL94 V-0 level. Exolit AP 752 is a special grade with particularly low water
solubility and high acid resistance, even at elevated temperatures.
Exolit OP products are liquid phosphorus polyols for polyether flexible and slabstock moulded
foams. They are used in the automotive sector as reactive fire retardants with low fogging values
and high resistance to migration. Exolit OP 1311 (TP) is used for injection moulding nylons. This
new grade yields a UL94 V-0 rating at 1.6 mm, at 15% content in a 25% glass filled compound.
The additive is a white powder, which is heat stable up to 310 C.
Exolit RP products are effective red phosphorus-based materials for applications where the highest
flame retardancy is required with the lowest amount of additive, and the properties of the polymer
are to be impaired as little as possible. RP grades are available as concentrates to allow for easier
processing.
Clariant has introduced new products based on their phosphonic acid metal salt technology that has
been under development for some time. This technology is aimed at engineering resins, the first of
which has been polyamides, and can be added at around 15% loading. This makes it more cost
effective than red phosphorus and even some brominated FRs used for the same applications.
29
4.2.11 Other New Developments

Ferro Corporation purchased the phosphate ester business of Solutia in 2001 and incorporated the
Santicizer plasticiser line into their own product range.
Unitex Chemical has introduced Uniplex FRX 47-88, an alkyl diphenylphosphate FR plasticiser.
This complements the existing Unitex offerings of Uniplex FRP 45, a brominated dioctylphthalate
(DOP), and Uniplex FR 44-57, a brominated chlorinated DOP for low temperature plasticiser
applications.
Polyurethane-phosphate combinations are known to form flame retardant intumescent systems.
However, the intumescent formulation cannot be permanent because of the water solubility of the
phosphate. This problem could be solved by the technique of microencapsulation. Microcapsules of
diammonium hydrogen phosphate (DAHP) with a PU shell are synthesised. Cotton fabrics can be
coated with PU formulations that enclose the microcapsules and show a significant FR effect.
4.3 Inorganic Minerals and Compounds
Some industrial minerals possess properties of flame retardancy and can be used in systems to
replace chemically prepared flame retardants. Hydrated alumina, magnesium hydroxide and borates
release water endothermically and create dilution in the gaseous phase, as is well-known.
Several minerals have a synergistic effect on organic halogenated and phosphorus-containing flame
retardants. In thermoset materials synergistic processes have also been observed, between borates
and other hydrated minerals. Minerals can be incorporated into intumescent formulations to
manage better the morphology of the expanded structure that develops on exposure to flame. With
brominated flame retardants, a partial substitution with minerals can lead to an improvement of
mechanical properties and reduce the opacity and corrosivity of the fumes generated. This in turn
makes it possible to reduce the environmental hazards arising from the incineration of such fumes.
4.3.1 Antimony Trioxide

Antimony trioxide is supplied as >99% purity white powder having specific gravity in the range 5.3
to 5.8. Some dusting does occur in the normal process of handling the material but the high specific
gravity causes fairly rapid settling of the dust. Nevertheless, environmental regulations relating to
dust problems associated with the use of antimony trioxide have promoted the introduction of nondusting grades, both of the damped and free flowing type.
The impurities, typically iron and arsenic depending on the source, influence the colour of the
oxide and may also affect the colour and stability of the plastic matrix.
A major consideration in the selection of the appropriate grade of antimony trioxide to be used in
any particular application is the effect of particle size on physical properties, dispersion and colour.
A variety of grades are commercially available with average particle sizes in the range 0.3 m
(ultrafine) to 10 m (coarse), with most companies offering intermediate grades specified as high
tint (average particle size 1.3 m) and low tint (average size 2.8 m). The high tint grades produce
a whitening effect at lower concentrations than the low tint grades and are therefore useful in light
coloured compounds, since less white pigment is required. In dark coloured compounds the less
expensive low tint grades are to be recommended since less colour pigment will be required.
As expected the coarser the grade of the filler the greater is the detrimental effect on physical
properties. The greatest effect is a reduction in the impact strength; the magnitude depends on both
the particle size and the loading. As noted, antimony trioxide requires the presence of an organic
halogen compound to be effective as a flame retardant, and, therefore, consideration must be given
30
to the effect this product has on colour and physical properties. In certain formulations the effect of
the halogen compound may be predominant.
Great Lakes has introduced new products based on antimony oxide. These are Fyrebloc 100 and
Fyrebloc 101. These materials are 100% active flame retardant formulations using a halogenated
FR carrier that has a high flow performance and excellent thermal stability. Because the carrier
already incorporates bromine, subsequent formulations require less halogen than would otherwise
have been necessary. These concentrates are pellets that eliminate the problem of dusting normally
associated with antimony oxide, making them particularly suitable for use in pneumatic feeding
systems.
In essence these products have been introduced to make FRs easier to use. They allow faster
production rates in compounding machinery due to their pre-dispersed nature.
4.3.2 Alumina Trihydrate (ATH)

The flame retardancy mechanism of ATH is based on its thermal decomposition reaction. Between
200-400 C ATH decomposes by giving off its chemically bound water and generating the
corresponding aluminium oxide. This decomposition reaction is an endothermic (energy
consuming) one. As a consequence, heat energy is removed from the burning zone. Generated
steam cools the compound surface and dilutes the atmosphere immediately surrounding the surface
by lowering the oxygen content and the concentration of burnable gases formed by thermal
decomposition of the polymer matrix. The aluminium oxide formed has a high specific surface,
which absorbs smoke and other, partially toxic, carbonised decomposition products.
Processing aids affect resins containing metal hydrate FRs. In polypropylenes it would appear that
fatty acid coatings are more effective than silane coatings as processing aids. Increasing amounts of
metal stearate coatings provide processing benefits. The mix of reacted stearate and the addition of
calcium stearate to the formulation is as effective as all other stearate coatings. They reduce the
amount of work done on the resin during the mixing preparation and so reduce the degradation that
takes place in the polymer. As may be expected, with increasing stearate content the final
compound becomes less stiff and processing becomes easier.
To allow ATH filler loads above 100 phr specially designed fillers are necessary. Unfortunately,
fine fillers have very large surface areas that makes wetting quite difficult even with specific
wetting and dispersing additives. However, judicious blending can prepare filler loads up to 300
phr with acceptable viscosities for moulding and pultrusion, for instance, with resins like
dicyclopentadiene or modified methyl methacrylates.
A blend with a broad particle size distribution from 1 up to 20 m with a median of 4-8 m could
be used up to 300 phr and still give a low viscosity increase. It is important to have the correct
wetting and dispersing additive in combination with an anti-settling additive. These should provide
for optimal filler wetting plus a stable resin matrix to ensure long shelf life without sedimentation
and/or viscosity increase, plus excellent air release from the mix on processing since large amounts
of air tend to become entrapped during dispersion.
Alcan Chemicals is one of the leading suppliers of alumina trihydrate, or aluminium trihydroxide
as the company call their Baco ranges of fillers. They can be surface coated specifically for the
polymer system under consideration. The Baco FRF range comprises general-purpose materials
with median particle size ranging from 80 m to 5 m. The Baco FRF LV products give lower
viscosity and range in particle size from 55 m to 5 m. Particle size distribution is closely
monitored so that significantly higher loadings can be achieved than for the standard FRF grades.
Much finer products are also available with median size well below 5 m. These are the Baco
Superfine and Baco Ultrafine products. The former cover materials with controlled surface areas
from 4 to 11 m2/g and the latter from 15 to 35 m2/g. Each range can be offered as E grades that
31
have been specifically prepared for electrical applications where low electrolyte levels are
essential.
Martinal aluminium hydroxide based mineral additives from Martinswerk are claimed to be
environmentally friendly and have processing temperatures of up to 200 C. For use in
thermosetting plastics and elastomers, products with a medium particle size are recommended.
These grades are produced by grinding coarsely precipitated aluminium hydroxide.
Earlier developments of ATH products had concentrated on filler purity and electrical properties
for the wire and cable industry, but more recent improvements have been in response to a growing
importance of continuous compounding techniques. The very fine precipitated ATH fillers used in
these applications have some drawbacks. Although the SG of ATH is 2.4, fine precipitated grades
have much lower bulk densities. These low bulk densities in combination with strong attractive
forces between the finely divided filler particles lead to poor flow properties and bridging. Poor
flow ability and low bulk density restrict output rates on continuous compounding equipment
because of bad conveying and dosing behaviour of the powder.
Large volumes of air that are entrapped by the melt via low-density fillers have to be removed
during compounding.
The wire and cable industry, for instance, looks for formulations that are easily extrudable and
show good physical properties. Low smoke, no halogen compounds are restricted in their extrusion
speeds due to the high addition levels of ATH fillers needed to fulfil the FR requirements.
Improvements to powder handling and rheological properties of the compound have been achieved
by chemical post-treatments of precipitated ATH products. While giving the anticipated benefits in
powder handling, mechanical and, more importantly, electrical properties have been detrimentally
affected. In addition, the chemical nature of the various coatings utilised restricts the width of
application of such products.
Some suppliers have tried physical compaction. This leads to better handling but does nothing with
respect to the consequent physical compound properties; especially melt viscosity which is so
important for extrusion.
One company has now commercialised a new generation of non-post treated fine precipitated ATH,
which has excellent processing behaviour and provides outstanding final-compound properties.
Especially notable are the low melt viscosities and high extrusion speeds achieved for cable
manufacture.
Customers had stated that inconsistent density was as much if not more of a problem than lower
bulk density as such. The company, Nabaltec GmbH, already had a compacted product designated
Apyral 40D. This gave better handling characteristics than a non-densified product Apyral 40E.
However, Apyral 40D changed density during transfer to the compounding lines. The new
generation as exemplified by Apyral 40CD does not show this drawback (CD stands for
consistent/constant density while D stands for densified). Apyral 40CD shows good discharge
and metering properties as well as outstanding conveying and dust behaviour. Highly filled LSZH
compounds with around 60% ATH produced with this new FR show very good mechanical
properties, as well as outstanding melt flow and rheological properties. This performance is
essential for wire and cable production and for the compounding sector as well.
4.3.3 Boron Compounds

As multifunctional flame retardants, zinc borates can provide the following benefits in polymer
systems:
32
They can function as a flame retardant, smoke suppressant, afterglow suppressant and as an
anti-tracking agent.
They can display synergistic/beneficial effect with other synergists or additives such as
antimony oxide, ATH, magnesium hydroxide, red phosphorus and ammonium polyphosphate
in both halogen-containing and halogen-free polymers.
The choice of optimal synergistic combination depends on the base polymer and halogen
source used. That is additive vs. reactive approach and aromatic vs. aliphatic halogen source.
Zinc borates alone can function as flame retardants in some polymers.
Alcan Chemicals make and supply Flamtard Z, which is a series of zinc borate materials with
surface areas from 10 to 15 m2/g. They are stable up to 290 C and promote the formation of a char
in the condensed phase. Flamtard Z grades have finer particle sizes than so-called standard zinc
borates.
Back in 1970, US Borax first showed that a unique form of zinc borate could be an effective flame
retardant synergist in plastics and rubber formulations. Firebrake ZB, the companys product has a
molecular formula of 2ZnO.3B2O33.5H2O and is stable up to 290 C, thus it can be used at high
processing temperatures. Its refractive index of 1.58 is similar to most polymers, which means that
it retains considerable translucency while allowing the use of lower pigment loadings. The
material, as developed, is an effective synergist that is multifunctional and cost effective. It
replaces antimony oxide and, by contrast, is a smoke suppressant, after-glow suppressant and antitracking agent. Polymer applications include PVC, polyamide, epoxy, polyolefins, polyesters,
thermoplastic elastomers and rubbers. In halogen-containing systems, the usage level is in the
range 3-25 pphr. In halogen-free systems, the recommended level is in the range 10-250 pphr,
normally used in conjunction with ATH, magnesium hydroxide or a silicone polymer. In halogenfree systems the borate is usually formulated with alumina trihydrate, magnesium hydroxide or red
phosphorus.
Firebrake ZB has a typical particle size of 7 m and has been used extensively as a partial
replacement for antimony oxide in flexible PVC used for wall coverings, wire and cable, roof
membranes, conveyor belts, carpet backing, vehicle upholstery, tarpaulins and tent fabrics. The
fine-grade version, Firebrake ZB-Fine has a smaller particle size around 3 m and has been used in
polyolefin wire and cables plus electrical components.
In PVC partial replacement of antimony oxide not only provides synergy for flame retardancy, but
also improves smoke reduction, which can be enhanced by addition of ATH. Just as important, due
to antimony oxides costing more, partial replacement by zinc borate can result in considerable
savings on cost, usually between 30 and 60%. Total replacement of antimony oxide in the presence
of a halogen containing system is possible. In polyamide, Firebrake ZB plus a compound like
OxyChems Dechlorane Plus maintains a V-0 rating in the UL94 tests.
In a halogen containing system, Firebrake ZB works as follows: during combustion, the zinc
component of the material catalyses the decomposition of the halogen source to promote
crosslinking and char formation. The borate component forms a glassy layer on the char to protect
the char from being further oxidised, it prevents any afterglow combustion. This strong char can
also prevent burning drips, and the water given off can cool the flame and promote the formation of
a highly foamy and insulating char.
The product also works in non-halogenated systems. It can be used with ATH, MgO, ammonium
polyphosphate, silica, silicone polymers or melamine compounds in polyolefins, urethanes,
polyamides and others. In the silicon containing systems, Firebrake ZB is understood to form a
borosilicate glass at polymer combustion temperatures.
33
Borates with zinc, calcium, magnesium, melamine or barium as the cation, combine char formation
with endothermic decomposition as a dual mechanism that provides an efficient flame retardant
system. Although the exotherm reduction is not as great as that achieved with ATH, there is enough
endotherm to delay the initiation of the polymer exotherm by as much as 100 oC in some systems.
It is this endothermic reaction in the polymer condensed phase and the formation of a glassy char
that makes borate products good synergists with the fire retardant antimony trioxide. 80% of the
boron from zinc borate remains in the char after PVC combustion.
As seen above, boron compounds, specifically inorganic borates, are currently used in some plastic
formulations as flame retardants but they are plagued by poor melt blendability, which weakens the
polymers mechanical properties. Boronic acids are known to release water upon heating, leading
to boroxine or boronic acid anhydride structures. These materials, if they contain more than one
boronic acid functionality, may form a network polymer system. Specifically, they may form a
boroxine network that could lead to high char formation upon burning. Work at South Carolina
University has developed a method to make boronic acid flame retardants using a nickel catalyst
and pinacol borane. Their use in polycarbonate results in V-0 rating in the UL94 flame test.
Joseph Storey, part of Banner Chemicals offers zinc borates, which have good fire retardant
properties with low toxicity, smoke suppression, anti-dripping and afterglow performance,
comparable to other materials in terms of char formation. Up to 50% of antimony trioxide can be
partially replaced in many halogenated systems. With alumina trihydrate, boron char formation
provides integrity to highly filled halogen-free formulations. Smoke performance in phosphate
systems can be improved using zinc borate.
Recent work has shown that magnesium borate provides good surface spread-of-flame performance
in PVC, suggesting the possibility of direct antimony replacement. A zinc-free borate has stability
advantages in PVC sheeting. Melamine borate is another recent development and is used in
phenolic composites to improve fire performance. Zinc borophosphate is also a new development
for applications as a smoke and flame retardant in PVC.
In recent years, due to the demand of high production throughput and thin-walled electrical parts,
engineering plastics are being processed at increasingly higher temperatures. To meet the market
demand of such plastics, US Borax has in recent times developed products to cope with greater
temperatures than Firebrake ZB. Firebrake 500 is an anhydrous zinc borate (2ZnO.3B2O3) that is
stable to at least 450 C and Firebrake 415 (4ZnO.B2O3.H2O) that is stable to about 415 C.
Firebrake 500 is recommended for use in engineering plastics processed at above 300 C, which is
the upper limit of Firebrake ZB. It is reported to be an effective smoke suppressant in
fluoropolymers for certain cable applications. This anhydrous material can replace antimony oxide
completely in high temperature nylon applications. For aircraft applications Firebrake 500 is also
reported to be effective in reducing the rate of heat release in polyether ketones and polysulfones. It
is also claimed to enhance laser-marking quality of flame-retardant engineering plastics.
Firebrake 415 has an unusually high onset of dehydration temperature of >415 C. It is
recommended for use in engineering plastics as a synergist of halogen sources. It can also be used
as a smoke suppressant in flexible PVC.
Firebrake 415, increasingly replacing magnesium hydroxide in an EVA formulation, can bring
about a reduction in the rate of heat release. Keeping total loading at 60%, the more borate present,
the greater the elimination of surface cracking in the resultant post-combustion residue. This
prevents the escape of volatile gases and so reduces the quantity of combustible material from
reaching the combustion zone.
Firebrake zinc borates display an interaction with metal oxide particles resulting from dehydrating
metal hydrates in flame retardant polyolefins. The interactions taking place show that surface
34
fracturing, mechanical strength of the degrading residue as well as the viscosity of the degrading
polymer surface can be significantly influenced by zinc borates. These phenomena should be useful
when devising improved flame retarded polyolefin materials based on magnesium hydroxide FRs.
The traditional use of zinc borates as a partial replacement for antimony trioxide and to increase
CTI can be extended to polyamide 66 compounds that contain brominated FRs. Their benefits can
expand to complete antimony trioxide replacement and improved melt stability during
compounding and injection moulding.
Firebrake ZB and a brominated polystyrene, such as Pyrochek 68PBI or Saytex HP-7010, can
provide a highly flame retardant PA66 formulation containing 25% of glass fibre reinforcement,
without the presence of any antimony trioxide. 24% loading of the brominated FR plus 7% of the
zinc borate produce V-0 at 0.8 mm in the UL94 test, with a CTI of 450 volts.
In general, the structure of borates is known to have anti-corrosive properties and secondary
antioxidant properties in polymer FR systems. Possible benefits of these zinc borates in FR
polyamide systems could be in reducing tool corrosion during compounding and moulding and
imposing better oxidative degradation resistance. Borate structures are known to absorb infrared
radiation with possible implications for laser marking properties of polymers. These properties
have not been much explored and potentially open the way to wider applications for borate
additives in polymer systems.
Continuing work by Borax Co. has explored other third-party additions to metal hydrateborate
combinations as FR packages.
Silicone as an extra ingredient to a magnesium hydroxide and Firebrake ZB flame retarded EVA
reduces the peak of heat release rate, for a total loading of 65%. It has been found that the residue
for samples with zinc borate and the silicone is multicellular, rigid and hard compared to that with
silicone and magnesium hydroxide alone. This shows how combinations of additives can be used to
influence the morphology of the degrading residue and subsequently lower the peak rate of heat
release.
A small amount of Melapur 200 (melamine polyphosphate) with a metal hydrate leads to a strong
reduction in the rate of heat release. The combination allows a lowering of the loading to 50%
instead of 65% and still retains the same peak rate of heat release as with 65% magnesium
hydroxide in EVA. The effect of Firebrake ZB has been shown to further reduce the overall level of
heat release and create a hard, cellular protective structure. In vertical burn tests like UL94,
however, this structure is not created and leads to a loss of classification. Current work is
endeavouring to improve vertical burning behaviour of these formulations.
Zinc borate (ZB) added to an ATH/nanoclay combination can convert a V-1 classification at
1.6 mm in UL94 to a V-0 rating. 5% of ZB replacing some of the 60% ATH present in EVA with
5% nanoclay has been reported.
4.3.4 Magnesium Hydroxide

4.3.4.1 Technology
Magnesium hydroxide is an effective mineral flame retardant. Metal hydrate compounds provide
effective flame retardance by several routes. First, they dilute the amount of fuel available to
sustain combustion during a fire. They contain a significant amount of bound water (31% in the
case of magnesium hydroxide) that is released at high temperatures (> 330 C for Mg(OH)2)
providing a blanket effect that limits the oxygen available for combustion. Magnesium hydroxide
decomposes endothermically at about the same temperature as that at which the host polymer
degrades during combustion, absorbing heat from the combustion zone, which reduces the prospect
35
of continued burning. It produces a char during burning that results in further flame retardant
protection and less smoke generation. Magnesium hydroxide also generates a magnesium oxide
coating during combustion, which deflects the flames heat away from the polymer or fuel source.
It is also a good smoke suppressant. The addition of 9% to polystyrene reduces the maximum
smoke density in the NBS Smoke Chamber from 2556 to 375. In a test on an EPDM compound, a
mixture of 75% magnesium hydroxide and 25% ATH produced significantly less smoke than ATH
alone in Smouldering Mode NIST (ASTM 2843) smoke chamber testing.
Magnesium hydroxide is low in toxicity and non-corrosive compared with halogen or phosphorus
containing compounds.
Magnesium hydroxide has several advantages over ATH. It has a lower hardness, which results in
longer processing equipment life. It produces more char than ATH, absorbs significantly more heat
from the combustion zone and allows for processing at temperatures up to 100 C higher. The latter
can improve processing efficiency by increasing extrusion speeds and decreasing mould filling
times.
The main problem with the use of metal hydrates is the need for high loadings of the filler in the
compound formulations. Up to 60% by weight is usual, with differing Oxygen Index values being
obtained depending on the exact nature of the hydroxide employed. This may reflect particle size
distribution, the presence of a coating or other factors.
The main sectors for magnesium hydroxide use are in elastomers and thermoplastics, since they
cause excessive thickening in the main thermoset application of unsaturated polyester systems. It is
also much more expensive than ATH with which it shares comparable properties and flame
retardancy, and so ATH will be preferred by processors wherever possible. As a result the principle
opportunities are in applications where the extra thermal stability is essential, mainly in PP and
polyamides.
Polypropylene and polyamides have much more rigid particle size and shape requirements than
thermosets. Specifically, the need is for a small particle size, with a low aspect ratio and minimal
surface area. The particle size distribution should also allow for good packing, as indicated by a
relatively low level of oil absorption in tests. Achieving such desired particle morphology has been
the main aim of supplier process development since the 1980s.
In principle, there are a variety of routes to generate a desirable form of magnesium hydroxide.
These range from milling of naturally occurring forms, such as brucite, to precipitation and
recrystallisation techniques. The target or guide is the property envelope of a typical finely
precipitated ATH as shown in Table 4.2.
Table 4.2 The effect of manufacturing processes on the morphology of magnesium
hydroxide
Average particle size
Specific surface area
(m2/g)
(m)
Desired range
1-8
0.5-5.0
5
30
Milled Brucite
6
10
2
18
4
Precipitated magnesium hydroxide
12
50
2
6
1
Precipitated and hydrothermal
2
3
Hydration of specially made oxide
3-10
1-3
Source: R.M. Rothon, Flamemag International, reproduced with permission.
36
This shows that only the hydrothermal and hydration techniques allow production of the optimum
particle morphology and these are the ones now in commercial production. There are also purity
considerations involved with the milled natural products and in the choice of oxide as the starting
material for the hydration process. A major drawback, however, is that the suitable processes are
the most expensive and, with the moderate scale of the sector this has led to the high prices of
magnesium hydroxide.
Metal hydrate FRs affect the polymer matrix in many ways. Firstly there is melt flow index (MFI).
This is significantly reduced with increasing filler level. Tensile strength is also affected, but not
nearly so much. The MFI of a 7 MFI polypropylene resin drops dramatically, above about a 45%
addition level of magnesium hydroxide the MFI has dropped to 2.2. To achieve higher loadings
without excess degradation of the polymer, then a higher MFI resin should be employed. To reach
a 65% loading in an EVA system, which enables a high LOI of 40 to be achieved, then a resin with
an MFI of over 100 is required.
Efforts to make magnesium hydroxide more appealing for use in PP compounds have focussed on
techniques for surface modification of fillers and the polymer resin to make compatibilisation
better and so allow a higher level of mineral filler without sacrificing impact and other properties.
Stearate coatings appear to be one route forward, giving increased melt flow and much increased
impact properties for a 60% filled compound. Fatty acids are extensively used as surface treatment
systems for particulate mineral fillers. As well as improved dispersion, reduced melt viscosity
results in lower shear degradation. Mechanical properties are affected through fatty acid treatments.
Fatty acids reduce adhesion between filler and matrix. In highly filled compositions this reduction
usually leads to an increase in toughness accompanied by a decrease in ultimate strength,
particularly in materials that do not yield or undergo strain-induced crystallisation.
Unsaturated fatty acid oligomers, such as oligomerised oleic acid, are becoming increasingly
available. Oligomer acids are claimed to be more effective than simple fatty acids for the treatment
of ATH and magnesium hydroxide for use in FR polypropylene compounds. Ricinoleic acid, made
from castor oil, is also said to be effective in this application.
Another modification for FR PP compounds is an in situ interphase modification system based on
phenylene bismaleimide (BMI). A 60% w/w filled PP so treated has a failure stress greater that that
of the unfilled matrix and a failure strain almost matching the yield strain of the unfilled matrix.
Flame retardant performance can be enhanced in some magnesium hydroxide protected systems by
the incorporation of clay or talc. In a polyethylene formulation the addition of 60% magnesium
hydroxide and 5% talc instead of 65% magnesium hydroxide, improved the V-0 rating from
3.2 mm to the thinner 1.6 mm level. More talc at the expense of further magnesium hydroxide
dropped the V-0 rating back to 3.2 mm.
Two routes to lowering costs have been reported. The first is to improve the FR efficiency of
magnesium hydroxide so that less is required in a compound. One of the methods investigated is to
incorporate small quantities of other metals during the hydrothermal process. This is said to aid
char formation. Another has been to find co-agents to boost the performance. Japanese companies
Kyowa Chemical and Kabushiki Kaisui KK have been involved in this work.
The second route has been to improve the process economics to make the appropriate materials in
the first place. Flamemag International has gone down this route and claim to have significantly
improved their hydrothermal process.
The proven success of one or more of these approaches is needed before there is a surge in
consumption of magnesium hydroxide for flame retardant purposes.
37
4.3.4.2 Commercial Products

Martin Marietta Magnesia Specialties offers in-process coated magnesium hydroxide grades that
facilitate processing and improve the physical properties of the final compounds. When coated in
process, which reduces costs, the company puts a stearate coating on the hydroxide particles before
they leave the production equipment. This differs from post-coating, which is done by coating the
often-agglomerated particles, after their preparation. The Magshield coated products include
standard and ultrafine grades with 1%, 2% and 3% stearate coatings, designated NB10, NB20 and
NB30. Martin Marietta has a databank of formulations developed on both small and commercial
sized plant, which enables a user to compound their Magshield products into polyolefins and
polyamide systems.
Martinswerk of Germany said that its Magnifin flame retardants have been specifically created for
applications as flame retardant additives, compared with other magnesium hydroxides that have
been manufactured from seawater with the pharmaceutical industry in mind. Magnifin is especially
recommended for situations where low smoke emission and a high thermal stability are required
from a halogen-free retardant.
Specific filler surface has an increasingly beneficial effect across a range of properties. Limiting
oxygen index has been shown to rise from 40 to 50 in an EVA formulation filled with 150 phr of
magnesium hydroxide, as the filler particle surface area has gone from 5m2/g up to 10m2/g.
Martinswerk has developed a proprietary coating for magnesium hydroxide that enhances various
properties including flame retardancy. Coating of magnesium hydroxide particles with surface area
of 5m2/g raises the LOI right up to 80.
Albemarle now owns Magnifin products. Special grades, with a surface treatment, are now offered
for polyamides. Magnifin H5 IV and Magnifin H10 IV are synthetic grades with a specific BET
surface of 5 and 10 m2/g and a mean particle size of 1.45 m and 0.8 m respectively. They do not
affect the colour of the product and are non-blooming fillers. The Magnifin products can contain
around 10-15% glass fibre and about 30-55 wt% of flame retardant. Depending on the PA grade, a
loading of about 55 wt% gives a V-0 rating at 1.6 mm. The special coating gives a better polymerfiller interaction and thus an improved performance. PA6 compounds, flame retarded with
Magnifin, pass the glow wire test in accordance with IEC 695, part 2-1, at 960 C.
In another development, JM Huber Corp. has been granted a patent, US 5891090, for a flame
retardant composition containing at least 25% magnesium hydroxide together with melamine and a
trace of novolac.
Compounders in the US, such as UVTEC Inc., have brought out metal hydrate concentrates under
the name Safe FR. These concentrates are loaded with in excess of 70% magnesium hydroxide and
find uses in polyolefin systems for wire and cable, building products market and in the E&E sector.
4.3.5 Other Inorganic Compounds

4.3.5.1 Iron Compounds
Iron compounds have been tested as flame retardants.
Commercial ABS polymers are very flammable, have a low limiting oxygen index (LOI) and
produce large quantities of smoke. The addition of PVC (which is inherently flame retardant) to
ABS has only a marginal effect on the low LOI and high smoke production of ABS. Work in this
field has been carried out at Northumbria University in conjunction with Anzon. When iron
peroxide was added to a range of ABS/PVC formulations, the LOI was increased, smoke
reductions were significant and the amounts of char formed were increased dramatically. The
possibility of producing flexible ABS/PVC blends, while still maintaining acceptable flame
38
retardant/smoke suppression characteristics was investigated. The addition of antimony oxide to

phthalate plasticised blends gave the highest LOI values, while the iron compound generally gave
the highest LOI values in phosphate plasticised blends. The iron-containing formulations also gave
the best smoke suppression.
A study of the relation between char formation and temperature in a number of ABS/chlorinated
PVC blends showed that in the presence or absence of the smoke suppressor FeOOH there is a
strong linear relation between char yield and the char formation temperature. The presence of the
FeOOH had no effect on the linearity of the char/temperature relation and did not decrease the high
values of the correlation coefficients. At all temperatures the char yield was increased when the
amount of CPVC and FeOOH was increased, but the CPVC level in both the iron-free and ironcontaining blends was the most important factor controlling the char yield.
The very significant smoke suppression effect of the FeOOH in the blends is explained in terms of
iron/chlorine compounds formed in situ. The maximum smoke suppression effect was obtained at a
blend chlorine content of about 20%. It was also shown that the char formation is directly related to
smoke formation and suppression in these polymer blends.
4.3.5.2 Molybdenum Compounds

Molybdenum and zinc containing compounds have been used as flame and smoke suppressants for
a variety of polymers. These metal containing species normally act to assist the build-up of char on
the polymer surface. This char is presumed to be the main method of flame retardancy.
Halogenated systems form a large proportion of the market for molybdenum and zinc compounds.
Although it is known that molybdenum can be vaporised by heating with HCl or HBr, most of the
metal remains in the char of the burned polymers that contained the original fire retardant additive
compounds. This is seen when char formation of PVC is increased when molybdenum is added at
low levels. A char value of almost 10% with no additive becomes nearly 24% with 2 phr of MoO3.
Over 90% of the molybdenum is found in the char. Likewise 63% of zinc from a zinc borate smoke
suppressant remains in the char. This contrasts with just 5% of antimony found in char from a
similar PVC compound containing antimony oxide.
It would appear that the molybdenum acts as a kind of catalyst to convert PVC degradation species
from becoming aromatic compounds (these burn to produce the familiar dense, dark smoke), into
more linear aliphatic species or carbonaceous char.
There can also be drawbacks with using some of the molybdenum and zinc-containing compounds
just discussed. Molybdenum compounds can destabilise the colour of PVC sheet and flexible
products and, under certain conditions, compromise dynamic heat stability. Zinc as borates, oxides
or stannates can also reduce the thermal stability and thus restrict the loading levels that should be
sensibly permitted. In demanding simultaneously low smoke applications with a high degree of
flame retardancy, relatively high loadings of these additives are required and the compounder
quickly comes across their stability limitations in halogenated polymers. Hydrated metal oxides
reduce processibility and affect final physical properties at the levels required for flame and smoke
suppression, an issue that is accentuated in non-halogenated FR polymers.
Smoke suppression in rigid PVC can also be accomplished by the utilisation of a copper and
molybdenum complex. A binary mixture of cuprous oxide and molybdenum trioxide reduces total
smoke production, the average extinction area and smoke production rate. Increased char is formed
and a reduced level of flammability in the PVC.
CHARMAX LS and FR products from FVI Polymer Additives Group in the USA claim to have
overcome some of these deficiencies. This has been achieved by the formation of stable complexes
that have good dispersion characteristics in PVC and other polymers. The optimisation has been
39
accomplished via two routes. First, the flame retardant and smoke suppressant efficiency is
increased by complexed elements being spread much more evenly through the polymer system in
smaller amounts than the elements themselves could be if compounded into the polymer as
standard products. These would be ammonium octamolybdate (AOM), zinc as zinc borate or oxide,
etc. Second, the detrimental activity of individual elements is reduced by being tied up in the
complex until thermal breakdown occurs at the elevated temperature of a real fire or fire test
situation.
CHARMAX LS are zinc-molybdenum complexes targeted as smoke suppressants in PVC wire and
cable, PVC plastisols and rigid PVC products. LS Z4A is used in a simple PVC jacket formulation.
Around 5% of such additives can replace up to 20% of AOM and reduce the afterglow sometimes
seen with antimony oxide containing formulations. Also CHARMAX products are cheaper by
weight than primary molybdenum and tin-based additives, AOM and zinc stannate, and lower
loadings provide the required level of flame retardancy or smoke suppression that may be
specified. The complexes may be used as partial of complete replacements for antimony oxides,
whose price and supply has been unpredictable in recent times.
Sherwin-Williams Chemical continues to develop molybdate-based smoke suppressants, used
mainly in PVC compounds. In addition to its standard product, Kemgard 911C, a molybdenum/zinc
complex, the company has introduced Kemgard PZC, which shows whiter colour and improved
stability in plenum cable applications.
4.3.5.3 Tin Compounds

Tin compounds, in particular (IV) tin oxide and zinc hydroxystannate have found applications as
flame retardant and smoke repressant additives for halogen containing polymers. Like
molybdenum, such tin compounds act predominantly in the condensed phase by a char-forming
mechanism. However, at sufficiently high chlorine/tin ratios extensive vaporisation of tin may
occur, so indicating a vapour-phase mechanism and allowing potential replacement of antimony
trioxide in halogenated polymer compounds.
Tin compounds such as zinc stannate are the alternative that most closely approaches a direct
replacement for antimony oxide in halogen systems. They do come at a cost premium, however.
Like molybdenum compounds, tin based ones have the key advantage of effective smoke
suppressancy.
Alcan Chemicals supply their Flamtard materials as alternatives to antimony trioxides for
synergistic action in conjunction with various polymer systems. Flamtard H grades are used in
halogenated polymer systems. They are thermally stable up to 200 C and are particularly suitable
for use with brominated polyesters, PVC and chlorinated PE. Flamtard S is thermally stable in all
polymer systems.
In the vapour phase, activity during combustion changes the flame chemistry to inhibit fire growth
by removing chemical free radicals that support combustion. Additional effects in the condensed
phase bring about changes not seen with traditional antimony trioxide systems. A hard
carbonaceous char is formed that further retards the flame propagation and reduces the amount of
smoke and carbon monoxide released during combustion.
Surface effects on particulate matter can provide improved flame retardant properties. Alcan
Chemicals has shown that surface chemistry can curtail some of the ever-increasing free radical
reactions that occur prior to ignition. Alcan has found that by heating at lower temperatures for
longer periods intermediate products are generated that exhibit significantly better flame retardant
and smoke suppressant properties than either the stannate or hydroxystannate. This slow roast
provides a material with a bulk composition between that of the two. This intermediate outperforms
either additive alone or any simple admixture. The following filled PVC compositions gave the test
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results in Table 4.3 at an exposure level of 40 kW/m2: PVC DS7060 195 parts, dioctyl phthalate 81,
epoxidised soyabean oil 10, ATH 75, Ultracarb 72, clay 75, stabiliser 10, tin additive 29.
Table 4.3 Cone calorimeter results for filled PVC formulation
Zinc
Roasted ZHS
hydroxystann
ate (ZHS)
Time to ignition (s)
84
86
Peak heat release rate (kW/m2)
87
78
Total smoke released
800
635
Average specific effective area (SEA) (m2/kg)
229
157
Source: Alcan Chemicals Limited, reproduced with permission.
Zinc stannate
75
122
1089
297
This suggests that the surface of flame retardants can be altered in ways that can improve their
performance, particularly ignition performance. Other additive systems may benefit, such as
crystalline ionic materials containing multiple cations such as calcium aluminate, zinc borate and
calcium/magnesium carbonates. Further research is underway and this should yield useful
information about the electron donor capabilities of certain materials and the role this plays in
flame retardancy.
Joseph Storey has introduced a zinc hydroxystannate flame retardant, which it found to be the
closest non-toxic alternative to antimony trioxide in halogenated systems. The new material also
has excellent smoke suppression properties. In halogen-free systems, tin char formation occurs,
leading to reductions in filler loadings and improved physical properties.
4.3.5.4 Talc
Work by the French company Talc de Luzenac, in conjunction with LEcole des Mines dAls, has
explored the area of industrial minerals as flame retardants. Emerging from the work in France is
an awareness that in talc containing compounds characteristics of the interface between the talc and
polymer influence the mechanical and ignition resistance of the material. Increasing the nucleating
effect produced by the mineral gives better adhesion of the polymer to the filler and so a stronger
reinforcing effect. This effect, which can be amplified by an increase of specific surface, leads also
to improved fire properties as a result of the energy consumed to make the crystalline melt and the
limitation of heat transfer produced by a layer of mineral particles of a strong specific surface ratio.
The use of pure talcs of fine particle and high lamellarity index, in combination with a new
generation bromohalogenated compound, makes it possible to obtain optimum mechanical
properties and fire resistance as well as limitation of emissions of corrosive products, compared to
traditional and more costly solutions. Specific talcs in the Luzenac range show high resistance to
flame in polyolefins in synergy with bromine compounds, and are recommended for various
applications, such as connectors in electrical installations and appliances.
Talc has also been used in combination with magnesium hydroxide flame retardant.
4.4 Other Materials
4.4.1 Coatings
Intumescent coatings, externally applied, have been available for many years, but originally only as
somewhat rigid, thick layers that were unsatisfactory for flexible substrates in the paper and board
industries.
41
Other sectors have initiated the search for products that are thinner, and plasticised enough to
maintain their flexibility in use. These water-based products have been applied within the
aerospace and shipbuilding sectors among others.
Another technology is based on epoxy systems that are 100% solids. These are very water resistant
in both fresh and salt water, and also resistant to most acids and alkalis. These coatings can be
moulded, brushed, sprayed or applied as the user requires and are fire retardant and intumescent,
producing low smoke in a fire. It has been shown that the resulting intumescent barrier is thick and
spongy, and continues to grow even when knocked off the surface, and eventually will smother the
fire. Such intumescence will exceed the original thickness of the coating by a thousand times.
These two technologies have created a new opportunity for the effective treatment of aluminised
polyester and other laminating materials, in addition to polyimide foam, materials that will shrink
when subjected to heat. A very thin layer of the new coatings may be sprayed on, leaving a
protected surface that is flexible, very light weight, and fire resistant.
Typically, one litre of the epoxy-based coating at 40 m thickness can cover nearly 40 square
metres and still be effective. A fibreglass barrier cloth would burn through within one second, but
by coating with an extremely thin coating of the intumescent formulation this burn-through may be
delayed for more than seven minutes. A multi-layer system protected by the epoxy coating
technique may survive for up to an hour or more, according to specialist company, Fire & Thermal
Protection Engineers, Inc., of Petersburg, Indiana.
Krona-FR is a fire retardant insulation material developed by Krona Industries and Fire & Thermal
Protection Engineers. It combines portions of Krona insulation with material coated with an
intumescent fire retardant. At 0.25" thick (~6 mm), Krona-FR is said to provide an R-15 rating of
insulation. The coated material can be fibreglass, paper, basalt, cotton or synthetics. When the outer
layer of Krona-FR is exposed to a flame, the intumescent coating activates immediately and
protects the fibreglass that would normally disintegrate within two seconds. The intumescence
combined with the melting fibreglass form a vitreous refractory silica that reportedly can withstand
temperatures up to around 2200 C.
A new US company based in Hudson, Massachusetts has developed intumescent coatings and
additives that enhance the fire properties of plastic and composite structures. Avtec Industries now
offer Thermashield mastic coatings that can withstand temperatures in excess of 1200 C for
sustained periods. The coatings material is non-toxic and does not flake, peel or chip. It is resistant
to water and chemical attack and is claimed to withstand multiple high-impact shocks.
4.4.2 Char Forming Polymers

Generally, intumescent formulations contain three active ingredients: an acid source, such as
ammonium polyphosphate; a carbonisation compound and a blowing agent. The first generation
carbonisation agents used in intumescent systems for thermoplastics were polyols such as
pentaerythritol, mannitol or sorbitol. Problems with this type of additive include
migration/blooming of additives, water solubility of the additives and reaction with the acid source
during processing of the formulations. There is little compatibility between the additives and the
polymeric matrix and the mechanical properties of the polymer are then comparatively poor.
Flame retardant intumescent formulations have been developed using charring polymers PA6,
thermoplastic polyurethanes (TPUs), and hybrid clay-PA6 nanocomposites as carbonisation agents.
The advantage of the concept is to obtain FR polymers with improved mechanical properties and to
avoid the problem of migration and solubility of the additives.
Polyvinyl alcohol (PVA) has been studied in a polyamide 66 based on the possibility of hightemperature acid-catalysed dehydration. The catalysis can be provided by the acid products of
42
nylon hydrolysis, and the dehydration would promote the formation of intermolecular crosslinking
and char. This has been called synergistic carbonisation, because the char yield and flame
suppression parameters of the PVA/PA66 blend are significantly better than those of the pure
polymers on their own. A pre-oxidised PVA via potassium permanganate achieved even better
results. It was found that manganese chelate fragments act as catalysts for char formation.
It is thought that polymeric char formers such as PVA, starch, glucose derivatives and
polyfunctional alcohols may present a new trend in the global search for ecologically safe flame
retardant systems.
4.4.3 Potassium Compounds

Conventional organic systems are based on the acid catalysed dehydration of carbonifics such as
dipentaerythritol. Metal oxides also have a use as catalytic flame retardants. For example, both
antimony and tin have been used to impart flame retardancy to cellulosics without any assistance
from halogen compounds. They appear to alter the condensed phase thermal degradation pathways
in such a way that more non-volatile char and less flammable gases are generated. It has been
found that low levels of potassium bicarbonate significantly modify the pyrolysis kinetics of a
cellulose to yield more char.
It has also been discovered that potassium carbonate enhances the charring of polymers containing
pentaerythritol-silica combinations as flame retardants. This has led to the discovery of basecatalysed intumescence of potassium bitartrate. Combinations of potassium bitartrate and
pentaerythritol show improved intumescence but carbon char oxidation by glowing combustion has
remained a problem. Base catalysis is an attractive alternative to conventional acid-catalysed
intumescent flame retardant systems as it could help to alleviate corrosion problems during
polymer processing. Unfortunately, strongly basic residues also catalyse the oxidative destruction
of the char-foam at high temperatures.
The 3M Company has developed a flame retardant based on potassium perfluorobutane sulfonate
(PSBK) for use in clear polycarbonate. PSBK is effective at 0.08 wt% compared to the 8-10 wt%
levels typically used for brominated species.
4.4.4 Melamine Compounds

Melamine-based flame retardants are a small but growing group of additives that are efficient and
halogen-free. They are non-corrosive so reducing mechanical problems and with low toxicity,
providing safe handling at all stages of production. They work through the heat-sink principle, the
formation of non-combustible gases, specific chemical reactions and their contribution to the
intumescent mechanism, forming a protective char. The heat-sink mechanism absorbs large
quantities of energy through melting, sublimation and decomposition of the flame retarded
formulation. This requires a fit between the polymer system and the flame retardant. Intumescence
sees the flame retardant and the polymer form a stable char together, which protects the polymer
from further flame propagation. The char builds up using significant amounts of the polymer and
prevents further decomposition and the transformation of the polymer mass into gaseous products.
Smoke reduction is a major advantage of intumescent flame retardant systems over standard
halogenated systems.
DSM (now Ciba) offers the Melapur range of melamine flame retardants.
4.4.4.1 Melamine Polyphosphate

The main advantage of melamine phosphate (Melapur MP) is its low water solubility compared
with ammonium-based phosphates. Applications range from thermoplastics to thermosetting resins.
43
Melapur offers a melamine polyphosphate specifically for use in glass reinforced polyamide 66
compounds. Melapur 200 lowers the smoke emission compared to bromine based compositions. It
gives a CTI of 350V and a corrosion behaviour much better than halogenated FRs, and there are
improvements in gas emissions and smoke opacity. It is a char former with the polyamide. It is a
white powder, providing new colour schemes for these materials. Formulations with 25-30 wt% of
Melapur 200 in glass reinforced PA66 achieve a UL94 V-0 rating at a thickness of 1.6 mm. The
balance between intumescence and thermal stability provides a processing window of up to 320 C.
It offers higher thermal stability than melamine cyanurate.
Melapur 200 is expected to have a good share of the market for the protection of E&E goods.
Melapur P46 is a synergistic formulation of nitrogen and phosphorus-containing compounds,
developed for polyolefins, particularly polypropylene.
An Italian company, Domus Industria Chimica SpA of Pedrengo, has developed a composition
produced by reacting melamine with piperazine and phosphoric anhydride. It comprises piperazine
diacid pyrophosphate, piperazine acid phosphate, melamine acid phosphate, melamine and possibly
an alkaline phosphate.
DuPont have patented a flame retardant composition based on melamine pyrophosphate, with or
without zinc borate, for use in a number of thermoplastic resins (US Patent 5859099).
4.4.4.2 Melamine Cyanurate (MC)

Good prospects seem likely to be fulfilled for melamine cyanurate (MC), which has appeared like a
material-in-waiting, with a global consumption of around 15,000 tonnes. Development in Europe
advanced quicker than elsewhere, mainly due to the presence of the raw materials in the region,
with the major outlet being for polyurethane foam. The expiry of a Japanese patent for MC in
polyamides should have an impact, but the most relevant development has been suitable
compounding techniques.
Whereas most FRs act by interfering with one of the three supports of combustion; heat, fuel and
oxygen, MC acts on all three. In the initial stage it creates a heat sink by endothermic reactions and
subsequent decomposition of melamine vapours. It provides only about 40% of the heat of
combustion of hydrocarbons, and the combustion then generates nitrogen, which acts as an inert
diluent.
It can also retard the loss of other FR components, such as bromine and phosphorus, capturing
these volatile components by the formation of salts while still showing FR activity at a later stage.
Finally, it can also make a considerable contribution to the formation of char in the intumescent
stage and a strong nitrogen/phosphorus synergistic effect is ascribed to the formation of N-P
substances that remain in the char. These provide protection against further oxidation. It can also
act as a blowing agent in the char, enhancing the barrier functionality of the char layer.
Melamine cyanurate, Melapur MC, is less successful in glass filled polyamide compounds than
Melapur 200, but works well in unreinforced PA66 or a mineral-filled formulation, achieving V-0
at 6-10% loading for the former, and at 13-15% in the latter.
Melapur MC can be used also in epoxy and polyester resin mixes as well as in PET, styrenic
compounds and polyolefins.
Melapur MC can provide cost-effectiveness, good electrical and mechanical properties, as well as
offering advantages in health and safety and colour performance.
44
Melapur MC is regarded as a workhorse for standard polyamide compounds, since it cannot

achieve V-0 due to lack of heat resistance in reinforced PA66 formulations. One of the other
problems facing all users of MC is the intrinsically low bulk density that follows the requirement
for a low particle size distribution. The solution is a free-flowing version designated as Melapur
MC XL.
4.4.5 Silicon Compounds

Work in Russia has shown that the use of elemental silicon plus tin chloride can enhance the flame
retardancy of both polypropylene and polyamide 66 compounds. Silicon tetrahalides are formed in
the gas phase of combustion and inhibit the chain reactions that develop in a fire. These silicon
halides do not act like halogen hydrocarbons in the atmosphere so there is no likelihood of
contributing to ozone depletion.
At levels of 3% silicon and 2% SnCl2 very little hydrogen chloride gas is created and, in any case,
it is consumed during the combustion that does take place.
Work based in Hungary and France has been examining the claims for a siloxane compound to act
as a synergist for the protection of polyolefins. Organoboroxo-siloxane (OBSi) is added with APP
and pentaerythritol to polypropylene. The material appears to increase the viscosity of the polymer
composition and provide some plasticity to the resultant intumescent char. The plasticity allows for
better prevention of char cracking and so provides improved flame retardancy. The increased melt
viscosity is created by the product of BSi-pentaerythritol, formed during the compound preparation,
and the improved char plasticity is the result of products formed at high temperatures from BSi and
APP.
4.4.6 Graphite
A new type of intumescent additive is expandable graphite. This material has already found uses as
a special effect pigment due to its metallic sheen and grey-black colour. Nord-Min has been
developed by suppliers Nordmann Rassmann with flame retarding of plastics in mind. It is a
halogen-free fire barrier additive from Chinese sources, based on natural graphite flakes with
intercalated acids.
Depending on the raw material and the acid treatment, the expansion rate is up to 250 times the
original volume. Grades treated with sulfuric acid begin to expand at around 200 C; with nitric or
acetic acids, expansion starts at about 150 C. This is too low for many technical thermoplastics
and a key development is to raise the expansion point to the 300 C mark.
Nord-Min is regarded as a fire barrier additive, not a flame retardant, in that it only functions
once a fire has commenced. It is often, therefore, used in synergy with other, conventional flame
retardants. The intercalation process, having utilised acids, is followed by neutralisation with either
ammonia or caustic soda. Final washing to remove all traces of these various water-soluble
reagents is necessary to avoid any interactions during processing in, for example, PU foams.
Graphite is a very soft material and has to be handled carefully. To avoid undue shear on the
material it should be added last during any mixing process.
Expandable graphite has been used in flexible PU foams for public transport seating, in trains,
buses and aircraft. Applications in the automotive sector are being examined, as are its uses in rigid
PU foam for insulating materials.
Expandable graphite acts mainly in the condensed phase as a smoke suppressant and an insulator.
Where the expanded carbon layers are too unstable, it is possible to combine the graphite product
with other FRs, such as those mentioned above, to form intumescent layers to stabilise the foam.
45
Expandable graphite can also work in the gas phase by releasing volatile matter and has a
synergistic effect with other types of FRs that work by thermal decomposition. Normally Nord-Min
is combined with halogen-free products, but it is possible to combine with halogen-containing ones
as well.
Graphites can be used alone as smoke suppressants giving a heat insulation effect but, for some
applications, the expanded carbon layers are too unstable and other FRs, such as zinc borate, APP
or ethylene diamine phosphate, can be used as stabilisers, to give a good span of properties and
applications.
Ucar Carbon Co of Cleveland, OH sells GRAFGuard expandable graphite flakes. Flame retardancy
is promoted by inserting an expansion agent between the carbon layer planes, to form an insulating
char layer when heated. The char layer provides a heat barrier, cuts off air and reduces the
migration of decomposition products.
A Swedish company has developed a wide-ranging product programme based on expandable
graphite (EG). International Carbide Technology, or INCA AB, based in Bromma, Stockholm has
been collaborating with Chin-Dow Ltd., and the Centre for Aviation and Space Technology, both
in Taiwan.
EG is very stable in normal conditions. However, when the temperature exceeds 200 C the EG
will expand rapidly up to several hundred times in volume. Owing to the fact that the vaporisation
point of graphite is above 3000 C, EG can sustain its integrity in the flame zone and provide better
fire protection than many other substances.
The expansion process of EG is a mechanical rather than a chemical process. When exposed to
fire it creates a crosslinked carbon char and small porous holes on the surface of the char contribute
to a better smoke suppressing performance. It is regarded as comparable to a carbon filter. At high
temperatures, the EG only emits water vapour. The pH is neutral and stable.
When used in a flexible PU foam, smoke and toxic fume emissions are greatly educed compared
with untreated foam or ones with halogenated FRs present. When utilised in a polypropylene
composition, the heat release rate is much lower than for a halogen- or a phosphate-based FR, with
a much-reduced peak.
In addition, EG prevents dripping of molten polymer, is environmentally friendly and does not
migrate.
The INCA programme includes fire retardants for rubbers, plastics and foams, covering
polyolefins, polyurethanes and other types; plus expandable smoke seals, fire stop putties and
sealants and intumescent coatings for metal, wood and GRP.
Computer simulations on the use of EG in various plastics components for automotives have shown
that for a fire started by a burning cigarette and the resultant spread there is, on average, a 20-30%
increase in the time before the fire ignites surrounding materials and so generating a serious
situation.
Another test scenario shows an increase in escape time from the cabin area, i.e., before flashover
to a conflagration occurs, of 50%, from 30 seconds up to 45 seconds.
The reduction of heat release rate and the prevention of dripping are the major properties offered by
these EG products for the improvement of fire safety.
Expandable graphite has potential as the flame retardant in polypropylene-flax composites under
consideration for vehicle trim, along with other natural fibres, and also in building applications.
46
4.4.7 Glass Flake

A new glass flake manufactured in the UK is substantially thinner and more consistent than
previously produced flake. A range of properties and performance benefits include an improvement
in fire retardancy. Research and testing by Glassflake Limited and various customers in different
industrial sectors has shown that the product, as used in rubbers, thermoplastics and thermosets,
acts as an intumescent, that provides improved flame and fire retardancy properties and reduces
drip and sag.
Incorporation of the flake can reduce smoke density, add to melt strength and give rise to an
intumescent charring effect. Glass flake materials performed excellently in smoke chamber testing.
The materials have been successfully incorporated into PTFE blocks as a replacement for the more
usual glass fibre used to produce a range of gaskets and bearings. Similarly, the glass flake has
been formulated into coatings for rubber sheeting as used for packing applications, where the
product adds to fire retardant characteristics, and in particular improves hold up when exposed to
a vertical spread of flame.
4.4.8 Low Melting Glasses

Another type of additive has been developed from the concept of low-melting phases as polymer
additives. In principle, low-melting glasses can improve the thermal stability and flammability
characteristics of polymers by:
Providing a thermal barrier for both undecomposed polymer and the char, if any, which forms
as a combustion product.
Providing an oxidation barrier to retard oxidation of the thermally degrading polymer and its
combustion char residue.
Providing a glue to hold the combustion char together and give it structural integrity.
Providing a coating to cover over or fill-in voids in the char, thus providing a more nearly
continuous external surface with a lower surface area.
In the 1980s a system for PVC was developed based on zinc, potassium and sodium sulfates. Lowmelting glassy systems containing other metals, such as calcium, caesium, nickel and cobalt were
also tested. More recently silica gel combined with potassium carbonate has been found effective
for a range of common polymers at only 10% loading. Polypropylene, polyamide, PMMA, and
cellulose were found to be retarded and, to a lesser extent styrenic polymers. The efficacy of the
additives in these inherently non-char-forming thermoplastics depends on the polymer, PP > PA66
> PMMA > PS. The proposed mechanism was the formation of a potassium silicate glass, but such
a material should not form until the temperature reaches 725 C; however, if sodium salts are
present, this temperature drops to 400-500 C.
4.4.9 Polymer Blends

Another trend is the modification of the physical structure of a polymer system by employing
blends of polymers. Some work on blends of polypropylene and ethylene-propylene copolymers
has been shown to generate char, whereas PP alone does not. Oxidative degradation and a change
in the kinetics of oxygen consumption by the blend have been found to provide a correlation
between char yield and limiting oxygen index. A 2:1 ratio of PP to the copolymer generates 3.4%
of char and increases LOI from 17 to 21. Such data indicate the solid-phase nature of the flame
retardancy in these blends. A modification of the polymer morphology is believed to lead to a
decrease in combustibility.
Another common example is the use of PVC as a fire retardant in ABS.
47
4.4.10 PTFE
Small amounts of PTFE, added to several polymers that are flame retarded with antimony-bromine
systems, can significantly improve their flame retardancy. The chemical reaction between PTFE
and Sb2O3 leads to the evolution of volatile Sb-containing species which, however, are not
responsible for the whole mechanism of flame retardancy as the improvement requires all
components to be involved; the polymer, the bromine system and, of course, the PTFE. It has been
found that SbF3 is the species of greatest interest since it is likely to be formed in high temperature
reaction between PTFE and antimony trioxide.
The combustion behaviour of ABS FR formulations containing SbF3 and PTFE separately has
confirmed that the SbF3 may well be an active flame retardant agent in the systems. In its presence
combustion is slowed down, yet a delay occurs before the flame is extinguished. As soon as
combustion develops, the additional effect of the fluorine-containing compound is no longer
significant and flame retardancy is due only to the bromine/antimony reactions.
It is believed that SbF3 plays a role in increasing the molecular weight of the ABS chains, for
example, catalysing the polymerisation of polybutadiene double bonds with an increase in thermal
resistance of the material and so a reduced rate of fuel being fed to the flame front.
4.4.11 Aluminium Flake

Silberline Limited a UK compounder that specialises in pigments has found a range of applications
for aluminium flakes beyond pigmentation. One of them is that such flakes, perhaps surprisingly,
cause fire retardancy in polyethylene, polypropylene and polystyrene, have no effect in
polycarbonates but accelerate combustion in polyamides.
4.4.12 Hindered Amine Light Stabilisers

Ciba Specialty Chemicals has been adapting an existing light stabiliser technology to offer a flame
retardant functionality. One of the companys types of hindered amine light stabilisers shows some
capability as a non-halogenated flame retardant, one example is Flamestab NOR 116.
A UV stable N-alkoxy hindered amine additive containing no halogen offers flame retardancy at
surprisingly low concentrations. It synergises with conventional bromine- and phosphoruscontaining FRs to provide improved performance in polyolefin fibre and moulding applications.
N-Alkoxy hindered amines (NOR) were first introduced as non-interacting light stabilisers for
flame retarded fibre and agricultural film applications. NOR hindered amines have low basicity and
are in a more active oxidation state than conventional hindered amines. In the film applications,
pesticides generate acidic species and deactivate conventional hindered amines. Similarly, hindered
amines are deactivated by the thermal or photo generation of HBr from flame retardants resulting
in inferior light stability. Studies encompassing brominated flame retardants, conventional HALS,
and NOR HALS confirm that NORs perform significantly better than conventional light stabilisers
in the presence of brominated FRs.
It was thought earlier that the non-interactive nature of NOR HALS with the halogens present in
FR additives positively influenced the performance. It was found that NORs alone provide flame
retardancy in their own right.
NOR-1, the first material tried by Ciba for this new role, did not always provide sufficient FR
properties to pass appropriate fire tests. The NOR stabilisers appear to work alone in high surface
area situations such as PP fibres, but not in mouldings without the presence of a conventional FR.
48
NOR-1 as a synergist with brominated or phosphorus FRs can provide flame retardancy in moulded
articles without antimony trioxide. V-2 formulations can be designed with lower levels of
conventional flame retardants. It is easily melt processible and does not weaken the mechanical or
physical properties of polyolefins, and also allows for safer use and recycling.
Further work by Ciba has shown that a UL94 V-0 rating can be achieved with NOR-1 and a
halogenated FR system. This rating was achieved with a three-component FR blend. The total
loading of the FR additives was 14.5 wt%. The V-0 rating is achieved with significantly lower
concentrations of the halogenated component and in the absence of antimony trioxide. V-2 is
achieved with only around 4-6% total loading for halogenated additives and with 17% for a
halogen free (phosphorus-based) system.
There are expected to be V-0 non-halogenated systems containing NOR-1 for polypropylene
mouldings in the future as the chemistries are explored and refined further. The lower levels of the
additives and the absence of antimony trioxide provide better processibility, lower density, lower
smoke emission and improved physical and mechanical properties. In addition, the new systems
meet environmental goals and provide even safer use and recycling.
Gabriel-Chemie, the Austrian masterbatch supplier, has reported on its ongoing developments,
which have led to combination packages of additives for polypropylene formulations destined for
outdoor applications such as stadium seating. Here attractive colour must be protected for UV
stability and, as a public place, for fire hazard as well. Aromatic BFRs have great thermal stability,
but high loadings may be necessary and they reduce the UV stability of PP. It is thought that
bromine radicals are released by photo-activation. These radicals then can react directly with the
UV stabiliser present and so deactivate the stabiliser.
Aliphatic BFRs are advantageous in this regard; yet lack much thermal stability, so a careful choice
must be made to match the converters chosen processing technique for the final product. Only
HALS stabilisers for UV have long-term efficacy in polypropylene and so the company, in
collaboration with Ciba Specialty Chemicals, has finally evolved a package. A multi-component
system has been commercialised that contains a halogenated FR, light stabilisers and correct
pigment regime for applications such as stadium seats. The system has been designated as the
PPSYS UVFR system of which no further details have been released to date.
4.4.13 Nanocomposites
The increasing usage of nanocomposites, based on layered silicate, or clay, mineral fillers has led
to examination of their effects on the flame retardancy of the resin systems that they reinforce.
Work led by the National Institute of Standards & Technology in the US would suggest that the
nanocomposites structures retain a reinforcing role during and after combustion by enhancing the
performance of the carbonaceous char that forms during the process. The multi-layered
carbonaceous-silicate structure may act as an excellent insulator and also a mass transport barrier,
slowing the escape of the volatile products generated during decomposition. A similar structure has
been found in the combustion residues of polyamide-6 and epoxy nanocomposites and also
polypropylene modified with maleic anhydride. These all used less than 5% of montmorillonite
clay (MMT). The delaminated versions of MMT-based nanocomposites also offer definite
improvements in a variety of physical properties. The intercalated versions also offer reduced
flammability, but with less improvement in the physical properties of the resultant composites.
In some types of nanocomposites the nature and aspect ratios of the assembled silicate structures
may affect their ability to resume a reasonably coherent structure during char formation. Such
structures would be less effective in reducing movement of volatiles and new fuel and so have a
reduced flame retardancy capability. This latter phenomenon was found in some polystyrene
nanocomposites that utilised fluorohectorite. PS composites using MMT did show a decrease in
flammability.
49
Early studies on silicate-polymer nanocomposites show that they have distinct advantages over
traditional flame retardants in problem areas such as production of soot and carbon monoxide
during combustion and the hampering of mechanical properties, as found with high loadings of
other FR fillers.
Relatively low concentrations, 2 to 5% of silicate, are necessary in nanocomposites, compared to
the amount of additive used in traditional filler systems. This allows silicate-polymer
nanocomposites to be processed by extrusion, injection moulding and casting in the same manner
as unfilled polymers. Commercial advantages resulting from the low loading of added silicate are
lower cost and ease of manufacturing a component.
Nanocomposites are an environmentally friendly alternative to some types of flame retardants, as
they contain no additional halogens, phosphates or aromatics above those contained in the chosen
polymer resin. The silicate remains intact at very high temperatures. In addition, whereas many
flame retardant compounds, particularly filler types, increase the carbon monoxide and soot levels
produced during combustion, no similar increases have been observed with nanocomposites flame
retardants.
Polymer colours are not affected by the presence of these silicates and physical properties are, in
many cases, improved as well.
Highly interesting properties exhibited by polymer-layered silicate nanocomposites include their
increased thermal stability and also their ability to promote flame retardancy at very low loadings.
The formation of a thermally insulating and low permeability char to volatile combustion products
caused by a fire is responsible for these improved properties. The low filler contents in
nanocomposites that account for the dramatic improvement in thermal stability are highly
attractive, since FR end-products can be made cheaper and be easier to process.
Depending on the nature of the filler distribution within the matrix, the morphology of the
nanocomposites can evolve from the so-called intercalated structure where a regular alternation of
the layered silicates and polymer monolayers is observed, to the exfoliated (delaminated) structure
where the layered silicates are randomly and homogeneously distributed within the polymer matrix.
The easiest and technically most attractive way to produce these types of materials is to knead the
polymer in the molten state with a modified layered silicate, such as montmorillonite.
Compounding on different machines, such as a Buss ko-kneader or mills, still produces essentially
the same morphology in the resulting nanocomposites.
It has been shown that composites of clay and polyamide 6 can be prepared easily by melt
blending. These nanocomposites have been shown to have an increase in mechanical properties by
over 40% along with a significant reduction in flammability.
Layered silicate clays like montmorillonite are being actively studied for their synergistic activity
with well-known flame retardant materials. A number of patents have emerged in this area. It is
known that standard FR materials often, in one way or another, degrade polymer properties while
clays improve them. Taken together, a synergy is expected that may generate novel products in the
years ahead.
Optimisation of the polymer interaction with the surface of the clay plates would appear to be the
key to obtaining the necessary dispersion of the nanoparticles in the polymer. The technology
employs cationic compatibilisers such as alkyl ammonium surfactants. These surfactants penetrate
between the clay platelets and are attracted to the excess negative charge embedded in the clay
lattice. The negative charge results from an isomorphic substitution of a lower-charge metal cation
for aluminium. Once separated, the platelets are ripe for penetration by molten polymer molecules,
thereby producing homogeneous nanocomposites. The NIST in the US has recently developed the
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use of imidazolium cationics, which have better thermal stability than the alkyl ammonium
surfactant treatments.
One exciting aspect of these emerging nanocomposites systems is that about half of the commercial
flame retardant can be removed and replaced with only 3-4% of nanoclay. This allows the use of
about 10% more polymer. Not only does the undesirable reduction of physical properties
sometimes produced by the flame retardant decrease, but the clay enhances stiffness and heat
distortion properties as well.
A commercially available layered silicate, Nanofil, is based on montmorillonite modified by
dimethyl distearylammonium cations and offered by Sd-Chemie in Germany.
An idea of the promise for these nanocomposite systems may be seen in the EUPEN work for cable
jacketing and the announcement by General Motors and Montell (part of Basell) regarding their use
in automotive door panels.
The use of graphite in nanocomposites has been reported for polypropylene and polystyrene
formulations. These are prepared by bulk polymerisation using potassium graphite. Although an
increase in thermal stability is observed, there is no increase in mechanical properties.
Polyamide/graphite nanocomposites can also be prepared by melt processing. If there is no acid
present, a slight increase in thermal and mechanical properties is observed, while those containing
acid show no change in thermal stability but a decrease in mechanical properties.
A greater understanding of graphite/polymer nanocomposites is required before they can take a
possible place alongside the better-understood clay-containing nanocomposites.
Sd-Chemie has developed a new series of flame retardants in collaboration with Alcan Chemicals.
These are a combination of Alcan's inorganic Flamtard AN and Sd-Chemie's nanoclays that offer
advantages for the cable sector such as a lower dosage and higher extrusion output compared to
existing products.
4.4.14 TSWB
TSWB, a flame retardant additive from Avtec, see Section 4.4.1, is a sandy-coloured particulate
material that may be mixed into various resins and applied to cured parts or incorporated directly
into resin systems. About 20-35 wt% loading is suggested and the additive has been assessed in
epoxy, vinyl ester, polyester and phenolic resin compositions.
The key material cited is a glass- and ceramic-based system including other ingredients to tailor it
for adhesion, flame retardance, flexibility and general compatibility. Avtec advise that it is
important to work with their formulation engineers to tailor a system to the customers
requirements, especially the chosen catalyst used to avoid any unwanted and unforeseen chemical
reactions. The effect on viscosity is minimal until a 30% loading is reached. A bonus appears to be
the enhancement of the appearance and overall aesthetics of moulded parts.
4.4.15 Noflan
A new arrival is a spin-off from space technology in Russia. Noflan is being distributed by CFB, an
Isle-of-Man company. Details available were very sparse, but the material is a white crystalline
powder, soluble in water but microencapsulated and water repellent for normal use. It acts by
forming a carbonised top layer on the polymer, reducing heat build-up and retaining decomposition
products. It can be used with polyolefins, polyamides, acrylics plus thermoset polyesters and
epoxies. Loadings are in the range of 14-20%, with 30% recommended for polyamides. LOI is 26
to 30%, rising to 35% for epoxies.
51
The carbonised layer becomes quite gas-tight and so Noflan does not release toxic substances
when exposed to fire and can even reduce smoke and fumes. It has a melting temperature of 200 C
and is thermally stable up to 250 C.
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5 Polymer Families and Their Flame Retardancy

This chapter covers most of the main plastics families and some of the methods to make them
flame retardant. Some producer-specific information is provided as well as more generic comments
on the various plastics types in commercial use.
5.1 Polyolefins
5.1.1 Polyethylene
Polyethylene ignites readily and melts and drips as it burns, leaving little or no residual char. The
incorporation of flame retardants into polyethylene is made difficult by the crystallinity of the
polymer, which impedes homogeneous distribution of the flame retardant and reduces its
effectiveness.
In the past, polyethylenes were generally flame-retarded with chloroparaffins and antimony
trioxide. Frequently PVC or chlorinated polyethylene was also added. Nowadays cycloaliphatic
(hexabromocyclododecane) and aromatic bromine compounds such as polybromodiphenyl ethers,
and in particular decabromodiphenyl ether are used. Antimony trioxide is also used here as a
synergist.
Further possible additives include aluminium hydroxide, magnesium hydroxide and magnesium
carbonate. Intumescent systems are increasingly promoted when a halogen free system is
requested.
The Chisso Corporation of Osaka, Japan has patented a flame-retardant resin laminate that includes
a layer of polyolefin containing ammonium pyrophosphate and a nitrogen-containing organic
compound. The laminate generates hardly any black smoke or toxic gas and has excellent
appearance, printability, weathering and scratch resistance (US 583052).
The Aicello Chemical Co. of Aichi, Japan has disclosed a flame retardant for polyolefins (US
5852082) consisting of melamine cyanurate, fine silica and a phosphoric acid ester. The material
emits no hazardous gases on combustion or incineration, needs no extra costs for treating ash, and
exhibits excellent flame resistance and strength.
ICC Industries has examined the difficulty of maintaining a UL94 V-0 rating while optimising the
impact strength of LLDPE. The research looked at the effect of the rotational moulding cycle on
the properties. The composition included a small quantity of functionalised silicone additive along
with antimony trioxide, PTFE and another flame retardant.
Zotefoams has added new F grades to its LD-15 polyethylene foam range to meet the needs of the
automotive and aerospace markets. The range of foams is the lightest available for crosslinked
foam with a density of 15 kg/m3, some 30% lighter than any other polyolefin foam, and is made in
LDPE and metallocene catalysed polyolefins.
Grade MP15FR Grey has been developed to meet the specifications of the major aircraft
manufacturers for smoke and toxic gas emission, as well as spread of flame. The specifications met
by the grade include ABD0031 for Airbus Industrie, CAA8 for the Civil Aviation Authority and
FAR for the Federal Aviation Authority. The material is specially formulated to impart improved
tear strength, tensile strength and elongation properties. This results in a grade with enhanced
toughness and abrasion resistance. The main applications are for insulation and seating areas.
Grade LD15FM meets the car industrys requirement for spread of flame in the FMVSS test at
3 mm thickness and above. Weight saving and cost benefits are also attractive to motor
manufacturers.
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5.1.2 EVA
Ethylene-vinyl acetate copolymers, usually known as EVA, are used in many applications, but
especially for low voltage cables. These polymers are easily flammable and flame retardants are
added to reduce their flammability. The classic solution is to incorporate aluminium hydroxide or
magnesium hydroxide that develop endothermic reactions when heated. Nevertheless, large
amounts have to be incorporated, often around 60% and this can lead to a loss of mechanical
properties in the compound. Intumescent technology that works well with polypropylene has also
been tried for EVA polymer systems.
EVA and Exolit AP 750 at 30% addition levels develops an intumescent coating between 200 and
460 C to give better thermal stability and good fire retardancy. Above 460 C, however, the
protection decreases.
The presence of polyethylenic chains is observed in the intumescent coating up to 460 C. Others
who have investigated other phosphorus-retarded polymers have found the trapping of such chains
in the shield. It was thought that these chains were responsible for the interesting properties of the
char. In contrast, the formation of aromatic and/or polyaromatic structures in the intumescent shield
is shown to occur from 300 C upwards. The latter structures condense when the temperature
increases (300 C < T < 460 C). A phosphocarbonaceous structure is formed in the shield; in
particular the presence of POC bonds with aromatic carbons that can yield good adhesion and
resistance to the coating. Also, the formation of polyphosphoric acid-like species and H3PO4 can
act as an additional protective glassy barrier at the surface of the coating, which reinforces the
intumescent protection.
Zinc borates are used as synergistic agents with ATH and magnesium hydroxide flame retardant
formulations of EVA. Botax has carried out studies in France. It has been found that while the
hydrated oxide flame retardants are decomposing to release their water molecules, ignition is
thereby delayed. Once combustion occurs, the polymer forms a crosslinked network and a
subsequent carbonaceous char. There is a reduction in the rate of heat release, when zinc borate
additives are also present. It is believed that decomposition of the zinc borate molecules in the
presence of the polymer leads to a vitreous phase, which renders the char more effective in
suppressing combustion rate and also smoke particle generation.
Further work by this French team has shown that the zinc borate slows the degradation of the
polymer, allowing the creation of the observed vitreous protective layer which can act both as a
physical barrier and a glassy cage for polyethylene chains.
A group in Italy has been exploring strategies for the EVA compositions that are used as cable
insulation. These have focussed on non-halogen systems. Attempts to increase char yield by
promoting the amount of crosslinking of double bonds have utilised either deacetylation of vinyl
acetate units or the dehydrogenation of ethylene sequences in the EVA. Palladium catalysed
dehydrogenation has proved unsuccessful, but the oxidative route of thermally decomposing
potassium permanganate appears promising.
Organic peroxides fail to increase the rate of crosslinking of deacetylated units. Better results are
obtained with the addition of an intumescent system. This is a combination of melamine phosphate
and phosphate-phosphonate substituted trimethylamine. The EVA is shown to play a substantial
role in the intumescence phenomenon, thus complementing the zinc borate work in France.
Work by the cable company BICC General Cables and a local university in England have also been
examining EVA compositions that include various fire retardant additives. A 26 wt% vinyl acetate
content resin was the focus of the investigation. ATH is a popular additive in EVA compounds
since they can take large quantities of fillers; however, the physical properties are modified by the
60% levels required to achieve worthwhile flame retardancy and when ignited such materials burn
54
with strong incandescence. Such an exothermic phenomenon represents a potential risk because it
may reignite the polymer some time after the extinction of the flame. Nitrogen- and phosphoruscontaining compounds are commonly utilised to provide suitable flame retardancy without the
drawbacks of ATH.
These are often melamine and derivatives or polyphosphate compounds such as APP. The mode of
action of melamine appears to involve endothermic sublimation, acting as a heat sink, vapourphase dissociation and also self-condensation under suitable conditions. APP achieves its flame
retardant effect by intumescence and char formation acting as a barrier to combustion reactions.
Since ATH, melamine and APP have different modes of action in a fire situation, the BICC
General programme has examined various combinations of these flame retardant additives in EVA.
Formulations containing APP burned with the formation of intumescent carbonaceous chars, with
EVA acting as a carbonisation agent. EVA materials containing 20% APP, plus a sufficient amount
of ATH or melamine, were superior to the non-intumescent ATH and melamine containing
formulations with regard to heat release rate, mass loss rate and smoke production. Melamine
showed some smoke suppressant effect and significant CO reducing properties. However,
melamine-EVA and melamine-ATH-EVA showed a very high heat release rate. It was found that
oxygen played a favourable role in enhancing the char formation by encouraging active
participation of the polymer matrix in the interaction with polyphosphoric acid.
The materials based on the combinations of APP with a sufficient amount of ATH or melamine
may be considered of interest for cable insulation based on EVA. These formulations burn with the
formation of a protective intumescent char and were superior to non-intumescent ATH-EVA ones.
The CO production for the APP-melamine containing EVA was also reduced to a marked degree
by comparison with the ATH-EVA system. However, in the case of the APP-ATH-EVA
formulation, the total CO yield increased to some extent by comparison with the ATH-EVA
mixture.
An acrylamide graft technique induced by plasma, developed in China, has been shown to increase
the flame retardant and smoke suppressant properties of an EVA compound. Time to ignition was
extended and char residue increased. This indicated that the CONH2 side group in the grafted
layer could not only be charred in the thermal degradation, but could also promote charring of the
substrate polymer. The smoke density observed was lowered in the acrylamide-grafted EVA.
Other amide containing formulations can provide useful improvements to the mechanical as well as
fire properties of EVA compounds. These new intumescent formulations use PA6 and a PA6 clay
nanocomposite hybrid as carbonisation agents. Work in both France and the US has shown that the
clay allows the thermal stabilisation of a phosphoro-carbonaceous structure in the intumescent char
which increase the efficiency of the shield and, in addition, the formation of a ceramic that can
act as a protective layer.
Studies on various fillers in EVA compounds for comparison with ATH and magnesium hydroxide
have found that hydrotalcite has promising FR effects. 50 wt% of hydrotalcite in EVA has a very
low heat release rate and a low evolved gas temperature. The layered structure of hydrotalcite may
provide an explanation. The formation of a char layer was observed, which retains an intumescent,
fairly compact, surface during combustion conditions.
The major approach now for EVA compounds, especially those designed for cable jackets, is the
introduction of nano-clays to the mix. As little as a 3% loading of a nanofiller produces a marked
effect on heat release. 5% of nanofiller reduces the peak heat release rate by almost 50% as well as
shifting that peak towards longer time-lapse. The flame retardant properties are due to the
formation of a char layer that acts as a firm insulating layer and dramatically reduces the emission
of volatiles towards the flame front. The silicate layers not only play the active role in char
55
formation, their presence also strengthens it and makes it more resistant to cracking. It was found
that ATH could be reduced to only 45% of the composition. The reduction in the total amount of
the fillers results in improved mechanical and rheological properties of typical EVA-based cable
compounds.
5.1.3 Polypropylene
Only about 1% of PP volume consumed employs any flame retardancy additives. Flame retardant
applications for PP are proportionately much less important than for other resins such as styrenics
and engineering thermoplastics; less than 5% of the total FRs consumption is used in PP.
This is mainly due to the difficulty and cost in reaching the high standards of flame retardancy
required in electronics and building industries with PP compounds. The cause of this difficulty is
the high crystallinity and flammability of PP. FR PP applications are found in various fields such as
electrical, covering lamp sockets, coil bobbins, connectors, TV yokes and, to a lesser extent wire
and cable; pipes for water discharge; fibres in textile products; film and sheets for roofing.
The addition of decabromophenyl ether plus antimony oxide is the current standard method of
adding some flame retardancy to polypropylene, but during burning there is a large increase in
smoke density. It has been found that the addition of hydrated magnesium calcium carbonate
dramatically reduces the smoke density and also improves the LOI slightly. So, combining these
two flame retarding systems can make for a strongly flame retardant polypropylene compound
without a serious increase in smoke density.
Work in Italy by Montell (now part of Basell) and Turin University examined the optimum mix of
melamine with other mineral fillers to obtain the best balance of properties. The addition of
melamine to mineral FRs for polypropylene improves flammability behaviour as measured by
UL94 and eliminates the afterglow phenomenon. However the melamine is not sufficiently
thermally stable and requires special precautions in processing. It does, though, lower the
compound density, which is an economic advantage and allows use of cheap inert fillers such as
clay or talc.
The LOI decreases with increasing amounts of melamine, and it was found that for all fillers tested
40% melamine to 25% mineral mixtures, totalling 60 phr by weight, showed the best compromise
between LOI and UL94.
Great Lakes have found that tetrabromobisphenol A bis (2,3-dibromopropyl ether) is an effective
flame retardant for PP homo- and copolymers plus talc filled systems. It provides for UL94 V-2
rating and Glow Wire 850-960 C requirements with additions of antimony trioxide in the
compounded systems.
Varying degrees of fire retardancy have been noted for PP formulations that contain APP as a char
former, plus the presence of thermoplastic polyurethanes of different chemical compositions. The
nature of the polyol employed to make the TPUs would appear to have a significant influence. The
morphology of the intumescent material, its growth and eventual degradation can be well evaluated
from the measurement of viscosity. The loss of the protective character, i.e., reduction of heat and
mass transfers related to the superficial foam morphology, may be explained by change of the
viscosity of the charred material under stress.
Work in China has shown the synergistic effect of silicotungistic acid (SiW 12) on polypropylene
flame retarded by an intumescent FR (NP28 phosphorus-nitrogen compound). The tungsten
compound increased the thermal stability of the PP formulation at temperatures above 500 C. The
SiW12 could efficiently promote the formation of compact intumescent charred layers with
phosphocarbonaceous structures.
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5.2 PVC
Until very recently, almost all PVC cables were stabilised with lead salts. These gave good thermal
stability and electrical resistance, with low water absorption. When the cable was required to have
better flame resistance than inherent in PVC, a small part of the calcium carbonate filler was
replaced by antimony trioxide. All such cables perform well and have done for many years. Now,
however, the need to focus on ecotoxicity has caused the lead salts to be replaced by a non-heavy
metal system, usually a calcium-zinc complex. Likewise, the role of antimony is being questioned
and formulators have come up with other solutions.
The traditional filler used in cables is calcium carbonate. Replacement of this by ATH, Mg(OH)2,
magnesium carbonate or minerals in which these occur gives flame retardancy without increased
hazard. Zinc borate provides a capability of smoke suppression.
Where better fire resistance is required, part of the plasticiser may be replaced by a suitable grade
of triaryl phosphate, with a very low toxicity.
A study on a range of commercially available flame retardants and fillers in rigid PVC
formulations was carried out by European Vinyls Corporation (EVC). Rigid PVC has a high
inherent flame retardancy, but additional additives are needed to pass very severe fire regulations.
The M1 classification of the French Building standard using the Epiradiateur Radiation Test is one
such; and the forthcoming SBI test to be introduced under the EU Building Products Directive is
believed likely to be another.
The key requirement for PVC when it is eventually made to burn is the minimisation of the dark
smoke levels emitted. Antimony, zinc and molybdenum compounds were incorporated as well as
hydrated aluminium and magnesium fillers. The fire testing covered Limiting Oxygen Index, heat
release parameters and smoke emission. General heat stability (integrity) and mechanical impact
tests were also performed.
It was found that zinc hydroxystannate (ZHS) gave the best overall fire performance. In the oxygen
index test, formulations containing ZHS gave an average improvement in LOI of 18 units, which
was the highest increase observed. In the cone calorimeter, ZHS gave the highest increase in time
to ignition (6 min) and the greatest reduction in peak rate of heat release (80 kW/m2). The average
reduction in smoke parameter was 79 MW/kg. There were no synergistic effects between ZHS and
either of the fillers, ATH or magnesium hydroxycarbonate (MHC). However, there was found to be
an interaction between ZHS and ATH that resulted in a significant increase in smoke emission.
Also the formulation containing a combination of ZHS and ATH showed a significant reduction in
time to decomposition in the thermal stability test, although ZHS had no effect on the heat stability
of rigid PVC in combination with either of the other fillers. In terms of its effect on mechanical
properties, ZHS gave an average improvement of 2.5 kJ/m2.
Formulations containing ammonium octamolybdate (AOM) also showed good fire performance,
particularly with respect to reductions in heat release rates and smoke emissions, although the
increase in time to ignition was significantly lower than that for ZHS. However, AOM caused a
reduction in the time to decomposition in the thermal stability test of 9 minutes, and a decrease in
Charpy impact of 4 kJ/m2. It is also more expensive than ZHS.
Zinc borate gave good performance as a smoke suppressant in the cone calorimeter, but was not as
effective as either ZHS or AOM in reducing rates of heat release. Also it had no effect on time to
ignition. It was not found to affect the heat stability of rigid PVC, unless used in combination with
ATH. The grade of zinc borate used gave a reduction in whiteness of the test pieces and a reduction
in impact of 7 kJ/m2.
57
Antimony trioxide, widely used in PVC formulations, gave a reasonably good fire performance but,
as expected, increased the smoke emissions detected. It was not found to affect the thermal stability
of the rigid PVC, and had no effect on either the colour or impact properties of the extruded PVC.
The flame retardant fillers, ATH and MHC, gave disappointing results in all the fire tests. It was
concluded that at levels of 10 phr there were no benefits in replacing calcium carbonate with FR
fillers. Neither were there any consistent synergistic effects between ATH or MHC and any of the
flame retardants. Furthermore, ATH was found to depress the heat stability of the rigid PVC when
used in combination with the FR additives, and MHC reduced impact strength by around 3 kJ/m2.
The conclusion of the EVC work was that ZHS had excellent fire retardant and smoke suppressant
properties in a rigid PVC compound, with no detrimental effects on key physical or mechanical
properties; and so merited further detailed study for rigid PVC formulations.
Further work on ZHS was carried out to determine the optimum level required. There was found to
be a threshold loading of 3 phr of ZHS, which gave a dramatic increase in the time to ignition. It
was concluded that it is essential to add a minimum level of 3 phr to realise the materials ignition
prevention capabilities. Increasing the addition level from 3 to 4 phr does provide some extra
benefits in terms of reduced rate of heat release and reduced smoke generation, but, for these rigid
PVC formulations, there is no advantage in adding more than 4 phr of ZHS.
Ning and Guo of Sichuan University found that incorporating small quantities of zinc borate or
ATH or both greatly increases the limiting oxygen index of rigid PVC and reduces the smoke
density emitted from the PVC during combustion. Such additions also increase the char formation.
The quantity of aromatic species released during combustion decreases whereas that of aliphatic
by-products is seen to increase as a result of a series of crosslinking reactions during the
combustion process.
Another Chinese study found that copper and molybdenum oxides were influential in the smoke
behaviour of burning PVC. Cu2O and MoO3 have different effects, with the molybdenum oxide
increasing smoke generation, yet the combined oxides reduced smoke emission. In combination or
individually, they effectively reduced smoke emission during hydrogen chloride elimination. It was
proposed that the metal oxides promote crosslinking of PVC and stabilise the backbone. Synergism
was observed that resulted in an increased char residue.
The German Federal Institute for Materials Research & Testing has concluded that antimony oxide
in plasticised PVC may be replaced to a certain degree by zinc sulfide. They studied 5% total
loadings of the additives either alone or in mixtures. Synergism was observed for the mixtures. ZnS
alone appeared to have no effect, yet a 50/50 mixture gave an equivalent flame retardancy as
antimony oxide alone.
Formulating lead-free flexible PVC containing Firebrake ZB (from Borax) with excellent heat
stability is possible with Ca/Zn based stabilisers. An LOI of about 30 can be obtained with 30 phr
of ATH and 6 phr of Firebrake ZB. These can be improved when part of the diisodecyl phthalate
plasticiser is replaced by a phosphate plasticiser and calcium carbonate is present as an additional
functional filler.
Similar formulations, with magnesium hydroxide in place of ATH were compared. Results showed
that the ATH/ZB combination provides an increased LOI over that containing Mg(OH)2 as well as
increased time to ignition, a reduced rate of heat release and reduced smoke.
The use of Rheofos 90, a phosphate ester plasticiser, as part of the formulation improves the flame
retardancy even more. Firebrake ZB can replace antimony trioxide in flexible PVC formulations to
improve smoke performance while maintaining good fire performance and good heat stability
characteristics.
58
Unplasticised PVC products such as pipes, windows and cladding do not contribute to fire
propagation and most rigid formulations will pass most flame tests without the need for FR
additives. However, the higher the level of organic additives such as impact modifiers and
processing aids in a rigid PVC compound the less flame resistant it becomes. The EVC study used
a lead-stabilised window profile formulation containing 7 phr of acrylic impact modifier.
There may be cases where FR additives will be required in order to pass severe fire specifications,
like the M1 classification of the French Building Standard using the Epiradiateur Radiation Test.
Also, under the EU Building Products Directive there is now a move to harmonise national fire
legislation and testing. The new spread of flame test or SBI test may require some increase in the
fire retardancy of current rigid PVC formulations.
5.3 Styrenics
Styrenic copolymers such as HIPS and ABS are used widely for the production of TV housings,
computers and office equipment. These polymers burn easily and so flame retardant systems have
been evolved over the years that provide much improved performance under fire conditions. This
has been achieved mainly by the use of brominated flame retardants with antimony trioxide as a
synergist. At one time the main standard applied for flame retardancy in electrical goods was UL94
V-0 from the US. This standard requires that the plastic does not burn or drip under vertical
exposure to the flame. In the early 1990s, under political pressure from Green parties and other
environmental groups, some European producers started a downgrading and are using the less
severe standard IEC 65 that permits a slow horizontal burning of the plastics.
European experts in flame retardancy and fire hazard chemistry consider this new tendency
dangerous. TV sets can cause severe fire quite easily when made under these less stringent
materials requirements. A massive TV recall by one manufacturer came after a series of fires in
private dwellings; it appears that no flame retardant was utilised in many of the sets they sold into
the European market. This trend in the European market is particularly unacceptable since several
brominated FR systems are tailor-made for styrenic copolymers.
Suppliers such as Dead Sea Bromine have introduced newer brominated systems that do not
contain any of the brominated diphenyl ether types targeted for their potential toxic attributes when
used as FRs in polymers.
FR-1808 is a brominated indane containing 73% bromine and is suitable for application where
good flow and good impact properties are needed. This combination of properties makes possible
the use of short cycle times and enables production of large parts with thin sections.
Other products of interest from the same company are the F-2000 and F-3000 series based on
brominated epoxy oligomers. They are offered for applications requiring good UV and light
stability. Their polymeric nature is the root of better efficiency as flame retardants. Their bromine
content is between 50% and 55% and since they are melt processible, they do aid the injection
moulding of compounds in which they are incorporated. These flame retardants have good thermal
stability allowing processing temperatures above 260 C.
The producers of computers, printers, monitors, copiers and keyboards would all like to utilise
environmental labels like the Blauer Angel (Blue Angel) or the TCO99 to their equipment. A
feature common to all the award guidelines is that they largely exclude the use of plastics
incorporating flame retardants that contain halogen.
Apart from dispensing completely with flame-retardant materials, which will generally require at
least design modifications to the products containing them, the growing importance of
environmental labels has led to an increase in demand for polystyrenes with halogen-free FRs. Two
59
products from Atofina provide suitable properties. Lacqrene 851 attains UL94 V-0 and a 5VA
rating; and Lacqrene 852 gives a UL94 V-2 rating.
Fine grades of antimony trioxide are utilised with brominated FRs to protect ABS formulations. A
sub-micron particle size product is effective with TBBA or with bis (tribromophenoxy)ethane. The
ATO product has little effect on impact properties and only a slight detrimental effect on flexural
properties.
A range of ABS blends with PVC was developed in the late 1980s for use in the business machine
and consumer electronics sectors. The PVC brings UV stability and inherent flame retardancy to
the blend, while ABS offers heat resistance, good impact strength and flow properties. The
blending of a cheap, easily processible polymer, which is flame retardant, into a useful engineering
material was regarded as a more efficient method of achieving appropriate levels of retardancy than
the use of large quantities of expensive additives.
5.4 Polyamides
Polyamides (nylons) melt and drip on ignition so that when held horizontally they tend to be selfextinguishing. However, the molten drips can continue to burn. Grades reinforced with glass or
minerals tend to have increased burning rates.
The first methods of providing flame retardancy consisted of bromine-based retardants plus an
antimony synergist that continue to be utilised. However in recent decades nitrogen or phosphoruscontaining additives have been used, which promote char formation and so delay the combustion
process. These range from elemental red phosphorus to various phosphate and phosphonate species
of additive. Melamine compounds and most recently magnesium hydroxide are also increasingly
used, especially when neither halogens or phosphorus-containing formulations are regarded as
desirable.
The use of injection moulded polyamides in many industries has increased over the years, and the
need for flame retardancy has grown with this market. In the automotive industry reinforced
polyamides have replaced metal components and another important sector is electrical connectors
where a high tracking index (CTI) can be achieved.
Several FR systems have come to the market from various sources. 58% are halogenated products
preferred for their better thermal stability. 42% are non-halogenated types used when a high CTI is
specified; these can be broken down into 22% red phosphorus products, 16% melamine cyanurate
and the remaining 4% of magnesium hydroxide.
As seen from the market share, red phosphorous is widely used and is cost efficient. A loading of
around 7% gives classV-0 in glass-reinforced polyamide but processing conditions are critical to
avoid auto-ignition with the subsequent production of highly toxic phosphine. Another major
limiting factor of red phosphorus is that it is not possible to achieve light-coloured materials.
The mechanism of flame retardant action of phosphorus-containing additives in aliphatic nylons is
similar to their mode of action in other polymers. The phosphorus-containing additives seem to
affect the processes occurring in the condensed phase. Phosphoric and related acids formed during
combustion may catalyse dehydration or deamination of the nylons and promote char formation.
These acids may form a thin glassy layer on the surface of the burning polymer, thus lowering
oxygen diffusion and heat and mass transfer between the flame and the condensed phase. It has
been shown that phosphoric acids react with nylons upon heating to give phosphoric esters, which
are char precursors. Although phosphine oxides or esters or salts of phosphonic or phosphoric acids
have been discussed as potential candidates for flame retardant nylons, it seems that only red
phosphorus and melamine pyrophosphate are really used on an industrial scale.
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Polyamide compounds with reduced flammability may be produced by the introduction of

melamine. 15-20% parts of melamine in PA6 gives suitable properties. These compounds have
good mechanical and flammability characteristics, and have potential in many applications within
electronic and automotive fields.
Melamine cyanurate is another candidate for utilisation in polyamide compounds but it is restricted
to unreinforced polyamides due to its limited thermal stability. A loading of 12% can give V-0
rating for UL94. There is also the possibility of some plate-out or blooming with MC.
Melamine cyanurate powder, containing nearly 50% of nitrogen can be used as an additive to
polyamide 6 at the melt stage before fibre spinning or plastics production. The addition of MC
lowers the specific tenacity of the fibres but decreases the flammability. This latter effect is
stronger in solid plastics than for fibres.
A new polyamide material has been developed by the University of Massachusetts in Boston that
has strong implications for the safety of aircraft. The polymer is called polyhydroxyamide (PHA),
which decomposes into a rigid flame-resistant substance, polybenzoazole (PBO) when it is heated
to around 200 C. As it does so, it releases water vapour that helps to suppress a fire. Once PHA
has decomposed into PBO, it remains strong enough to maintain its integrity and remain stable in
temperatures of up to 900 C. This should vastly improve the time period in which a structure such
as an aircraft interior can retain its shape and allow evacuation before its eventual collapse.
Bergmann Kunststoffwerk of Gaggenau, Germany, part of the PolyOne and designated Engineered
Materials Europe within the group, has introduced a range of polyamide compounds that do not
rely on halogens or phosphorus for flame retardancy, aimed at the electrical industry. Although
non-halogen compounds have been around for some time, polyamide compounds for the electrical
sector have often contained red phosphorus, particularly in reinforced grades. However, although
this gives good flame retardant characteristics with good electrical properties, degradation in
processing and environmental concerns have led to pressure from users to move away from these
grades. They are still recommended where it is essential to maintain mechanical and electrical
efficacy, especially Comparative Tracking Index.
The new compounds are based on Bergamid PA 6, 66 and 66.6 copolymer. Examples are given in
Table 5.1.
Table 5.1 Flame retardant polyamide compounds from PolyOne
UL94/
Comparative
Base polymer Filler
Example
Glow Wire
Tracking Index
Test
B700
600
V2/960C
Bergamid PA6
B700UF
600
V0/960C
B70G/Mi20UF
500
Glass/mineral V2/960C
B70G15UF
600
V0/960C
Glass
Mu133
Bergamid
V2/960C
600
AB700UF
PA66.6
Bergamid
V2/960C*
600
A700
PA66
Glass
V0/960C
425
A700G30U SO
ABO Tio-35
* no FR additive needed to achieve UL94 V2
Source: PolyOne Th. Bergmann GmbH
Notes
UL Listed
UL Listed
UL Listed
UL Listed
UL Listed
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Dechlorane Plus, with 65% chlorine content, has been used in polyamide applications for many
years but has become superseded by newer FRs. It is very good for UV stable applications but is
somewhat costly and has limitations with regard to its thermal stability.
Brominated trimethylphenyl indane, seen as FR-1808 from the Dead Sea Bromine Group, is now
finding increasing application as an alternative in polyamides. It has several inherent advantages as
a result of its high bromine content, suitable thermal stability and melting range. It can be
processed up to 300 C and decomposes around 150 C below the self-ignition temperature of
PA66. When processed above its melting range, FR-1808 behaves as a melt blendable FR and has
important beneficial effects on properties such as impact strength and flow. Enhanced flow is
particularly crucial for electronic devices made of glass-reinforced polyamide, which are often
designed with thin-wall dimensions.
There are also cost advantages for moulders of polyamide parts, which come from the high
bromine content and FR efficiency of FR-1808, and the processing aid effect during moulding that
reduces cycle times and lowers power consumption. Production of thin-walled parts results in a
reduction of weight and light coloured materials can be achieved if desired.
Surface treated magnesium hydroxide is now offered as an alternative flame retardant for
polyamides. Synthetic grades do not affect the colour of the product and are non-blooming fillers.
Depending on the PA grade a loading of around 55 wt% gives a V-0 rating at 1.6 mm. The additive
itself contains from 30 to 55 wt% of magnesium hydroxide. The special coating gives a better
polymer-filler interaction and thus an improved performance. PA6 compounds, flame retarded with
a product such as those from Magnifin, pass the glow wire test in accordance with IEC 695, part 21, at 960 C.
In todays PA applications, miniaturisation of E&E components imposes higher thermal stress on
the melts during injection moulding. In addition, the densification of conductive paths on electronic
components due to miniaturisation demands increasing resistance against material degradation
caused by electrical stresses. Resistance against degradation caused by electrical stresses is
commonly classified by testing for Comparative Tracking Index (CTI). Historically, there appears
to be a perception in the market that the benefits of zinc borates are mostly linked to CTI
improvement of PA compounds containing a cyclo-aliphatic chlorinated FR such as Dechlorane.
In glass-fibre reinforced PA66 compounds a brominated FR present with a zinc borate and no
antimony trioxide can produce a high FR performance and also an improved CTI. So, PA
compositions with a CTI >400 volts and a UL94 V-0 classification at 0.8 mm can be developed
using Firebrake ZB as a single active FR synergist with a brominated polystyrene. These materials
show improved thermal melt stability.
Pyrochek 68 is a brominated polystyrene with 68% Br content with a high thermal stability but a
high loading is needed because of its lower FR efficiency. Owing to its high softening range, PA
compounds containing it have limited melt flow properties. It does however allow for a high CTI.
5.5 Modified PPO (m-PPO)
Flame retardancy of m-PPO is improved by incorporating thermally stable phosphorus based
additives, such as red phosphorus and organic phosphorus compounds like triphenyl phosphate,
triphenyl phosphine and triphenyl phosphine oxide. The mechanism would appear to be gas phase
activity rather than reactions in the condensed phase for all except red phosphorus where both are
seen.
Both triaryl phosphate and zinc borate are effective flame retardants in m-PPO, but not in HIPS.
The m-PPO is a higher heat polymer than HIPS, with m-PPO processed at temperatures where
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HIPS undergoes degradation, despite the presence of HIPS in the PPOHIPS blend alloy. Higher
decomposition temperatures lead to different flame retardant chemistries.
Zinc enhances the flame retardancy of triaryl phosphate in m-PPO, leading to the highest LOI
values. Zinc powder, however, is coated with zinc oxide. Work has shown that zinc oxide enhances
the decomposition of m-PPO. Thus a zinc coating (zinc arc spray) is perhaps more representative of
the effect of zinc with triaryl phosphate than zinc powder, with the latter having a greater zinc
oxide surface.
In m-PPO the FR triaryl phosphate has a particular role in smoke formation. Zinc borate is an
effective smoke and flame retardant with or without the presence of triaryl phosphate. With zinc
borate, low heat release and smoke release m-PPO materials are possible. It is interesting that in the
latter case, LOI values are low and the zinc borate deactivates triaryl phosphate in those materials
that contain it. Since LOI only measures ease of extinction, it will not necessarily correlate with
other flammability properties.
In more recent times GE Plastics has upgraded their Noryl range of PS-modified polyphenylene
oxide materials without recourse to halogens. Improved flame retardant properties are found in the
new Noryl GTX 4110 series, which uses a proprietary flame retardancy system free from halogens
and red phosphorus. The compound has high heat and chemical resistance.
5.6 Polyurethanes
Rigid PU based foam insulation materials received a boost when a programme of work by IVPU,
the German association for rigid PU foam makers, showed that compared to competing materials,
the risk of smouldering and glowing with PU is very low. A study in 1998 examining Fire risks of
smouldering and glowing in thermal insulation materials in flat roofing involved mineral wool,
rigid PU foam, wood fibre, and expanded perlite. Testing was carried out to DIN 4102 part 7A. UP
rigid foam board in building materials class DIN-4102-B and with a thin mineral fleece facing
on both sides, showed no evidence of risk as a result of mouldering or glowing. The risk with noncombustible rock wool insulation boards was found to be immensely greater than the risk for
moderately flammable PUR rigid foam insulation boards.
Haloalkyl phosphate esters are well-established effective flame retardants for flexible polyether
based PU foam. It is believed that the phosphate materials interact with the PU material to generate
a phosphate related species that is the direct retarding agent. It was once thought that the ester
decomposed under heat to phosphoric or polyphosphoric acids, but specific testing has not found
the presence of any of these acids during careful pyrolysis of foams. Polyether foam carefully
treated with a coating of free phosphoric acid was confirmed as receiving retardant properties, so it
is surmised that with both commercial esters and the experimental acid each reacts with the foam to
create the direct retarding species.
Mica and ATH have shown good properties when incorporated into TPU compositions. Results
indicate that 70-80 phr of ATH presents good flame retardancy. The use of mica does not impede
the fire resistance behaviour of the composites where the ATH has had a surface treatment.
The traditional additive flame retardant added to PU rigid foam formulations is tris-(chloropropyl) phosphate. Now, however, customers, especially in Germany and Scandinavia are
demanding FRs that are halogen-free and do not migrate. Ammonium polyphosphate, which is
successful in flexible foams, has now been introduced for rigid PU foams to meet these
requirements. Although ammonium polyphosphate is a solid, it can be easily dispersed in the
polyol and is less abrasive than melamine and calcium carbonate. This makes it easy to use in the
foaming process and meets the requirements of insulation materials within the building industry.
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Flexible moulded polyether foam is widely used in the transport, furniture and packaging sectors.
In many cases flammability is of great importance and so the effects of suitable flame-retardant
agents on such foams has been widely studied. One piece of work by Chestnut Ridge Foam in
Pennsylvania, using Cone Calorimetry, studied the heat release characteristics of various
combinations of commercially available additives, plus the CO emission and time to ignition.
Unfortunately nearly all FR formulations generated more CO and smoke during the test programme
compared with the basic foam. Halogenated phosphate ester compounds appeared to extend time to
ignition by the greatest factor and also reduce the peak heat release rate by a substantial margin of
33%. The reduction rises to 43% with the addition of antimony oxide, but at the sacrifice of shorter
ignition time and more CO. Silicone powder, in the form of an amine functionalised siloxane, also
provides for a 40% reduction in peak HRR, with very low CO emission, but sacrificing time to
ignition.
The same company has developed a new generation of highly flame resistant open cell flexible
PU/CR hybrid foam materials. The polyurethane and chloroprene are prepared using a brand-new
technology called Foam-One. This is a batch process for making flexible slabstock under variable
pressure that may range from 1 psi to 25 psi. PU base foams are post-treated with a
polychloroprene compound to obtain the hybrid grades.
The technology enables the making of low-density foams without using auxiliary blowing agents
such as methylene chloride. The process is utilised to incorporate a specifically designed fireretardant package into the base PU foams so that the post-treated foams easily meet all US federal
requirements for aircraft seat cushion, contract furniture and mattresses for hostels, prisons, and
other multi-occupancy public institutions, etc. They also satisfy naval and military standards as
well.
At Salford University in England a team has developed a powerful tool for examining behaviour in
the so-called dark flame region behind the flame front in polymer fires. Laser Pyrolysis generates
combustion in polymer materials that it is now believed better represents real fire scenarios than
previous, slower, techniques. Time-of-flight mass spectrometry then analyses the chemical species
present over time both qualitatively and quantitatively.
Interesting observations have emerged from the work on PU foam systems. Rigid foam
formulations can vary in isocyanate index (amount and distribution of NCO groups) and the
molecular weight of the polyols utilised. The flame retardancy of these materials has been shown to
increase with increasing isocyanate index and weight fraction of isocyanate. Laser pyrolysis
experiments show that the major volatiles evolved are dominated by monomer and oligomers of the
polypropylene glycol used to form the foam, plus lower molecular weight species of which carbon
dioxide appears to be a significant part. An increase in isocyanate index results in a reduction in the
extent of monomer/oligomer evolution and an increase in the low molecular weight species. In
phosphorus retarded rigid foam, the mechanism for the activity of the dimethyl methylphosphonate,
added at a low percentage, is believed to be a reduction in the evolution of fuel from the foam
material.
Some workers in Taiwan have reported making flame retarding polyalkyl phosphate type polyols
from ethylene glycol or 1,4-butanediol, and then reacting them with isocyanate to form
polyurethanes.
Solutia has patented cyclic phosphorus (1,3,2-dioxaphosphorinanemethan) amine compounds as
flame retardants in polyurethanes (US 5844028).
Changing methods to produce flexible foam, by the replacement of fluorocarbon blowing agents in
many cases with carbon dioxide, have brought consequences for the choice of flame retardant
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additives for these newer formulations. In addition, the need to reduce automotive fogging has also
brought a new perspective to these choices.
With regard to fogging, relevant tests are conducted at increasingly high temperatures, which
means manufacturers have to stop using volatile additives that condense on cool glass surfaces.
When carbon dioxide is utilised, it is very difficult to use solid additives with CO 2 processing
equipment. Although small quantities of extremely fine pigments may be used, solid flame
retardants such as melamine and ammonium polyphosphate do not process satisfactorily.
Automotive foams account for the largest flame retardant usage in flexible polyurethane foams in
Europe. Halogenated FRs continue to be the choice for their best cost/performance ratio. The
standard FR for automotive foams is regarded as tris dichloropropyl phosphate (TDCP).
Unfortunately, this additive doubles the fogging factor compared to no additive. A recent product
from Great Lakes is an improvement, in that it only increases the fogging factor by one third.
Firemaster BZ-54 is a liquid brominated benzoate ester, introduced as an alternative to
pentabrominated diphenyl ether, which is to be phased out of use in Europe through legislation.
BZ-54 has a significantly higher molecular weight than TDCP.
The relative contribution of a FR additive to fogging will increase with the introduction of lowervolatility catalysts and polyols. As volatile FRs are found to be major contributors to fogging, they
will in future be replaced in flexible foams by either higher molecular weight or reactive FRs.
Halogenated FRs tend to be more effective than halogen-free types, since either a higher loading is
needed or more expensive phosphorus-containing ones are needed.
Different FR additives are used for furniture foam, where the only flammability requirements in
Europe remain those in the UK and Ireland, to pass BS5852 source 5. The traditional approach to
meet this standard has been tris monochloropropyl phosphate (TMCPP) and melamine combined.
Efforts to remove solid melamine from these foams to improved physical properties continue;
however, the relatively low cost of the combination has made melamine all but indispensable.
This has to change with the introduction of the carbon dioxide blowing agent. Solids are
particularly difficult to process on the appropriate machinery and melamine is especially difficult
since large qualities are utilised and a coarse particle size is required for optimum FR performance.
Melamine-free or all liquid formulations are increasingly preferred, but halogen-free FRs will
have limited use in furniture foams since higher addition levels are required to counter their lower
efficiency. These levels, in turn, adversely effect foam physical properties and finally costs.
The efficiency of APP in polyurethane coatings is well known as a fire retardant treatment. The
addition of APP to PU accelerates the decomposition of the matrix but leads to an increase in the
amount of high-temperature residue, whether under an inert or oxidative state. This stabilised
residue acts as a protective thermal barrier during the intumescent fire retardancy process.
Examination and analysis of the charring materials help to understand the carbonisation and
intumescence process. It has been shown that the char resulting from PU consists of an aromatic
carbonaceous structure that condenses and oxidises at high temperature. In the presence of APP, a
reaction between the additive and the polymer occurs, which leads to the formation of a
phosphocarbonaceous polyaromatic structure. Moreover, this char is strongly paramagnetic. Large
radical species present, such as polyaromatic macromolecules, can trap free radicals, and so
enhance the fire retardant performance of the PU/APP formulations.
Polyurethane-modified polyisocyanurate (PIR) foams have a reputation for being the most flame
resistant of the PU related foams used for insulation. They are increasingly being made from an
aromatic polyester polyol (APP) and the isocyanate is most often MDI. Unlike polyurethanes,
however, the amount of MDI is comparatively high. Isocyanate indices of 250 or higher are used
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with an excess of MDI, as much as 50% is typical. This excess can be made to react with itself to
yield trimeric isocyanurate. It is this trimer that imparts the excellent FR properties to the rigid
foam.
The combustibility of PIRs is related to the release of volatile flammable products during the early
stages of decomposition. Because PIR foams have outstanding thermal resistance, they are less apt
to decompose and burn. Typical PU linkages decompose at ~200 C, with char yields less than
20%. In contrast, the isocyanurate ring structures in PIR systems decompose at ~325 C, with
typical char levels of 50%.
This char has low thermal conductivity and high resistance to oxidation. This means that that it not
only protects the underlying material but, because the surface can withstand higher temperatures, it
can re-radiate a large fraction of the incident heat load. While the trimeric isocyanurate structure
gives PIR foams their thermal stability, char formation is also influenced by the polyol type.
Consequently, the ideal polyol is one that promotes char formation through the urethane linkage. In
addition, it has been found that char yields are directly related to the number of aromatic ring
structures bonded into the polymer backbone. Accordingly, the choice of polyol in PIR and
modified PIR systems is extremely important. This is the major reason for the rapid growth in the
use of aromatic polyester polyols, or APPs.
A further way of improving fire performance and also the dimensional stability of PIR foams is by
incorporating glass fibres into the foam laminates. This technique was developed and patented in
the US over 20 years ago, but the costs are higher than for PIR foams made with APPs.
5.7 Thermosets
As a result of their three-dimensional crosslinked structures, thermosets do not soften or flow when
burning. The tendency to form gaseous decomposition products is also less than with
thermoplastics. Heat may cause surface charring that can prevent ignition. Unsaturated polyester
resins and epoxy resin systems require flame retardants to meet the fire protection standards in the
construction, transport and electrical industries where such resins are mainly used. The
flammability of epoxy resins is greater than comparable thermosets since they have a reduced
tendency to carbonise. After removal of an ignition source, once alight they continue to burn on
their own.
Phenolic resins have a great tendency to char thus reducing the formation of volatiles and so they
extinguish if the ignition source is removed. The high nitrogen content of urea and melamine resins
acts as an inherent flame retardant.
Phosphorus-containing FRs influence the reaction that occurs in the condensed phase and so their
effectiveness depends on the polymer structure. They are particularly effective in materials with a
high oxygen content, like polyesters, polyurethanes, epoxies or cellulose.
Ammonium polyphosphate and red phosphorus are excellent flame retardants for all types of
thermoset resins. In most cases the combination of a phosphorus-based FR with ATH passes high
levels of flame retardancy at relatively low filler loadings: ~50-70 phr compared to 150-250 phr
using ATH alone. The low filler levels reduce the viscosity of the formulations and also the
laminate density.
Pultruded components for buildings and transportation systems are made by Exel (formerly
Menzolit-Fibron) in Vrde, Germany. These are made flame retardant by a combination of APP
with specially treated ATH that enables appropriate processing to occur, without the need for
halogenated species being present.
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A new approach to render fibre-reinforced rigid composite materials flame retardant is undertaken
by the utilisation of complex fibrous-intumescent chars. The use of flame retarded cellulosics
fabric, surface coated with an interactive intumescent as an additional reinforcement in an
otherwise conventional structure has been studied. Thermal analysis has shown that when heated,
all components decompose by chemically interactive mechanisms leading to a char-bonded
structure and the residual mass of char formed is higher than expected above 450 C, even in the
case where polyester resins are present. Not only are greater fractions of char formed above 450 C
but the chars formed are more resistant to oxidation than the respective components (resin,
traditional fabric and coated cellulose). Thus composites comprising these various components will
have significantly improved fire performance.
5.7.1 Unsaturated Polyesters

The flammability of unsaturated polyester resins can be reduced by incorporating halogencontaining species. Reactive FRs of this type are hexachloroendomethylenetetrahydrophthalic
(HET) acid or its anhydride, tetrabromophthalic anhydride or dibromoneopentyl glycol.
Ethoxylated TBBA is also used as an additive with antimony oxide as a synergist. When
halogenated resins do burn, they generate smoke and toxic fumes, which are unacceptable for some
applications, especially in mass transit systems. ATH may be used in halogen-free formulations,
yet to raise the fire properties of polyester compounds to match or better those of phenolics, high
loadings of ATH are required. Disadvantages are the increase in resin viscosity for processing and
an increase in density. However, suppliers have been introducing coated and other improved grades
to address these concerns.
The use of ATH is also limited when high glass contents, over 30%, are required. The levels of
ATH necessary to pass some stringent specifications are so high that the component suffers a
serious loss of mechanical properties.
Polyester resin in which dicyclopentadienol (DCPD) is present as grafts on chain ends is more
stable than those without. In a fire scenario, ignition takes place more or less at the same time in
both cases. Material degradation, at first, takes place faster in the DCPD tipped resins. This lasts a
brief period, as the consumed material becomes a char that keeps the subsequent rate of heat
release at a lower level than pertains in the non-tipped versions for the remaining duration of a fire.
No char is seen in the non-tipped resins. No other flame retardants were present in these
formulations.
The German company, Lurgi Zimmer, has patented a process for producing flame resistant
polyesters that involves using carboxyphosphinic acid as a co-monomer (US Patent 5859173).
Phosphorus compounds are often combined with silicon rather than nitrogen, as in European Patent
899301 from General Electric, in which a polyester moulding compound is flame retarded with an
organoclay, a polymeric siloxane composition and a boron and phosphorus containing material.
Phosphorus containing compounds offer another route to provide halogen-free flame retardancy in
thermoset composites. Ammonium polyphosphate materials promote carbonaceous chars that are
bound into a vitreous coating formed by the polyphosphate decomposition products. The smoke
density emitted from such systems in a fire easily satisfies the requirements of the German
Bundesbahn, the French Epiradiateur test for irradiated surfaces, and Airbus requirements for
smoke and toxicity.
Clariant has found that use of APP, such as Exolit AP422, and red phosphorus, Exolit RP65x
family, in combination with ATH allows useful formulations to be prepared that meet these
standards with relatively low loadings of fillers. These can be around 50-70 phr in place of the 150250 phr for ATH alone. The low viscosity of the resin mixes allows processing by all the
conventional methods, such as RTM, hand lay-up, pultrusion etc.
67
Exolit AP740 from Clariant is a recent ammonium polyphosphate blend that can be incorporated
into gelcoats as well as the main polyester resin. For hand lay-up, spray techniques and RTM it is
recommended to add AP 740 to the gelcoat, but is not necessary for SMC or pultrusion
applications.
By varying the polyphosphate content of a 30% glass fibre polyester composite, usually in a range
from 30 up to more than 70 phr, fire tests of differing stringency, including those for German
transportation requirements, may be passed.
The Exolit grades of polyphosphate can also serve to provide UP-resin and epoxy-resin gelcoats
with flame resistance and intumescent characteristics. The use of an intumescent gelcoat can very
often enhance markedly the fire-safety of the component as a whole. The gelcoat, when thus flameretarded, can take on the major role of protection against fire. The layer of foam generated is not
only a fire barrier, but prevents the heat from gaining access to the underlying layers. This makes it
an interesting proposition for sandwich structures consisting of laminates and foam cores, which
are often more difficult to flame-retard than the individual constituents.
For components made by the RTM method, the use of intumescent gelcoats offers the possibility of
adding less-effective liquid flame retardants to the laminating resin and adding solid additives to
the gelcoat only. The composite consisting of laminate and intumescent gelcoat can comply with
fire and smoke requirements, whereas the laminate with standard gelcoat would not.
Such considerations lead to the possibilities of concentrating the flame retardant protection at
critical locations of a design and so also allow glass fibres for strength and other additives for
processing and fire protection to be married together for the overall improvement of the final
products. It would also allow design applications for which GRP composites have not hitherto been
possible or appropriate.
The range of Exolit phosphate additives are becoming widely used in reinforced plastics designed
for European railways. They allow the materials to pass various DIN German standards for flame
and smoke retardancy such as DIN 4102: B1 and DIN 5510: S4 SR2 ST2, that previous halogenbased systems could not meet.
Work in Poland has shown that zinc stannate and zinc hydroxystannate are the most efficient
ignition and smoke retardants for GRP laminates, with antimony trioxide also being a good smoke
suppressant. This appeared to be irrespective of the presence of other flame retardant additives. The
resin systems also contained halogen additive or retardant components on the polyester backbone.
The most well-known fire performance standard for composite and other materials in the UK
building industry is BS 476, Parts 6 & 7. There are a number of ways in which resins can be
modified to meet the ignition and flame propagation requirements of these standards, each with
their benefits and limitations. Retardant fillers limit the processibility of resins and so limit the fibre
content and structural performance. Also, some fillers may produce toxic fumes during a fire.
Unfilled flame retardant resins rely on technology to incorporate chlorinated and brominated
species on the unsaturated polyester resin chain. As a result many composites based on resins of
these types can achieve Class 1 surface spread of flame ratings when tested to BS476 Part 7 and
ignitibility resistance when tested to Part 6, which enables them to meet UK Building Regulations
for use in the construction of non-combustible buildings. Requirements in other European countries
can vary, although there is a general correlation between the various surface spread of flame tests.
The French NFF-16-101 test requires an assessment of smoke and toxic fumes with the F (smoke)
rating made up from three components:
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Smoke density measurement;

Opacity (light obscurity) measurement;
Toxic fume measurement.
Few unsaturated polyester resin-based laminates can achieve better than the F2 level with most
only able to reach F3. However, in recent years, developments in resin technology have resulted in
M1 (the best surface spread of flame requirement in the French test, which is equivalent to BS476
Part7 Class1), and F0 classifications with some filled resins (Scott Bader Crystic 343A). The major
limitation is a maximum fibre content, by weight, of just 20%, which limits applications to semi- or
non-structural components only. Hence, such materials can be used for many decorative internal
components and cladding panels supporting their own weight.
The introduction of the new common European legislation to reclassify all building materials
should change nothing in terms of practical usage and specification for polyester composites, but
just place all construction materials onto a common register.
Mass transit systems now often employ polyester composites made with low smoke, low toxicity
resins now on the market. One such is a Synolite resin system from DSM Composite Resins. It can
be formulated with ATH as the sole flame retardant, from Martinswerk.
The pultrusion process only allows for limited filler loads due to the large quantities of glass fibres
that are incorporated. New formulations have been developed that use ATH and/or polyphosphates
to achieve a high degree of flame retardancy with acceptable glass loadings. These have been
successful in fulfilling standards required for building and construction as well as public transport
applications.
5.7.2 Epoxy Resins

Epoxy resins are usually flame retarded with bromine, either in the chain or as additives. Some
novel ways of increasing the flame retardancy of epoxy resins have been explored in recent times.
The major brominated flame retardant used with epoxy resins is TBBA. This is a reactive
halogenated intermediate incorporated during resin preparation. However, other bromine
containing species plus phosphorus containing monomers or curing agents may be reacted with the
main epoxy resin components during polymerisation. The latter may be alkyl or aryl phosphates.
The best appear to be phenyl phosphate derivatives.
A large number of organic phosphorus compounds are available to provide flame retardancy.
However, it is known that such additives do not generally provide sufficient protection in epoxy
resins. They are not resistant to migration and affect the mechanical properties. As a consequence
epoxies are often protected by bromine containing types.
Flame retardant epoxy laminates are used often now in vehicle construction and for these Exolit AP
422 (Clariant) is available to provide flame-proofing properties.
The new Exolit AP 750 is useful for epoxy coatings and gelcoats, with around 20-50 phr normally
added.
A team at Cheng Kung University (Taiwan) has found that a phosphorus containing reactive
material produces less fumes and contributes to greater thermal stability than conventional systems
containing TBBA. The material 2-(6-oxido-6H-dibenzo(c,e)(1,2)oxaphosphorin-6-yl)-1,4benzenediol, known as ODOPB, was converted into a phosphorus-containing epoxy material for
use in an electronic encapsulation application.
Later work by the same team compared ODOPB and bis(3-dihydroxyphenyl) phenyl phosphate
(BHPP) as reactive flame retardants in o-cresol formaldehyde novolac epoxy resin. Since the
ODOPB has a rigid, cyclic side chain structure, the resultant phosphorus-containing epoxy resin
had a higher Tg, better flame retardancy properties, a higher modulus, and increased thermal
69
stability compared with the conventional TBBA-containing epoxy and the linear, main chain BHPP
epoxy resin.
With ODOPB, a UL94 V-0 rating was obtained with a phosphorus content as low as 1.1% in the
cured resins with no fumes or toxic gases detected. In contrast, 12% bromine is needed for the
TBBA resin and 2.2% P with the BHPP approach.
Another investigation in Taiwan has shown that the incorporation of silicon into epoxy resins
provides an improvement of their flame retardancy. A silicon-containing oxirane, triglycidyl
phenyl silane oxide (TGPSO) and the corresponding silicon-containing epoxy resins possess a
higher char yield as well as higher LOI than commercial epoxy resins.
Shell Oil has a patent covering the use of red phosphorus in a curable epoxy resin, US 5859097;
and Hoechst have also disclosed phosphorus-based epoxy resin compositions in US 5854371.
Another approach has been postulated in Taiwan, where a phosphorus-containing bisphenol is
incorporated into naphthalene epoxy resins. A high Tg of 237 C was obtained with a tetrafunctional naphthalene-containing epoxy and the use of a phosphorus-containing diol was better as
a flame retardant than TBBA. Phosphorus-containing thermosets in air at 800 C had a char yield
of 11.5-22.2% whilst TBBA networks oxidatively decomposed with almost zero residue. It was
concluded that the combination of a tetrafunctional naphthalene-containing epoxy resin with a
cyclic phosphine oxide diol gave a high Tg and a high limiting oxygen index of 35.
Alpha Owens-Corning offers a flame retardant vinyl ester resin that meets ASTM 84 Class 1 flame
spread and smoke rating. The resin is a highly brominated bisphenol-A epoxy based vinyl ester. It
provides a unique combination of good flame and smoke resistance and inherently good
mechanical properties. The flexural strength of 34% glass composite is 5100 psi (35 MPa) and
flexural modulus is 450 ksi (3.1 GPa).
Epoxy resins can be made flame retardant with reactive halogen-free FRs attached to the polymer
matrix. To achieve this the compounds must be miscible with commercial epoxy resins. Schill &
Seilacher Struktol of Hamburg offer just such a material. Their reactive organophosphorus
compound Struktol Polydis PD3710 can produce UL94 V-0 with 2-4% phosphorus in the polymer
matrix. At the same time, a reduction in smoke density is achieved.
This product is an example of what is termed a combination compound, based on cyclic
organophosphorus chemistry, since it incorporates flame retardant properties with being a curing
agent for the system. Indeed, it has toughening properties as well, making the compound a trifunctional entity. These combination compounds represent a modular system, in which the resins
reactivity and subsequent properties can be adapted as appropriate. These may entail glass
transition temperature, fire-smoke toxicity (FST) properties and toughness.
Epoxy systems cured with combination compounds have low curing temperatures and improved
FST properties. Because of the latency of the curing agent, combination resins offer the easy
handling of one-component systems. This type of curing agent does not affect the basic viscosity of
the resin used. The curing reaction can be triggered below 140 C, whereas amine systems
employed for aerospace composite primary structures require a temperature of at least 180 C.
These new combination curing agents have good handling properties in storage and processing.
They can be stored at ambient temperatures; at which the compound is liquid and so can be
metered and stirred easily. Because of the latent reactivity, it is possible to reduce curing
temperatures and so reduce production costs.
70
5.7.3 Phenolics
Cellobond phenolic resins are available from Borden Chemicals in the UK. These resole resins are
made with an excess of formaldehyde to produce a water-based polymer capable of crosslinking or
curing purely by the application of heat. A range of grades is available for processing via the full
range of composite techniques into inherently fire resistant products without the addition of flame
retardants or fillers.
They achieve Class 0 under BS476 Part 6 and Class 1 for flame spread under BS476 Part 7. The
oxygen index is >55% and laminates pass the 3 m Cube Smoke Test as category 1. Under the
French NFF 16-101 tests laminates are rated as M1F1 for flame spread and smoke/toxicity
respectively.
These factors, combined with the minimal levels of smoke and toxic emissions that are produced in
a fire, make phenolics the product of choice in many areas where public safety is important.
In the few cases where phenolic resins require a flame retardant addition, such as in paper and
textile containing compounds, reactive flame-retardants like TBBA or additives such as
organophosphorus compounds are used. Ammonium polyphosphate is also effective.
5.7.4 PU Casting Systems

High amounts of ATH can be added to the polyol stream where PU casting systems need flame
retardancy. To pass the UL94 V-0 test about 300 phr are required. The addition of red phosphorus
and ATH is much more effective and does not affect the insulating properties of the resins. A
typical formulation would have 100 phr of ATH and 20 phr of red phosphorus.
Encapsulation resins from Dow Chemical are solvent-free systems sold under the Voratron name.
Flame-retarded halogen-free versions are available that meet UL94 V-0 requirements. These
polyurethane crosslinked resins are both insulating materials and act as a construction material
and housing for fixing electrical components in power distribution, transformers and cable joints.
5.7.5 Acrylic Resins

MODAR Modified acrylic liquid resins have been available since the mid 80s and are used in
closed mould and pultrusion technologies. When combined with ATH they offer low smoke; low
toxicity fire performance in composites. These resins are more accurately described as
oligourethane-methacrylates dissolved in methyl methacrylate solvent monomer. Crosslinking,
through the methacrylate functionality on the backbone and the solvent is initiated in the same way
as for unsaturated polyester resin by decomposing an organic peroxide, either thermally or
chemically with an accelerator.
Flame retardant laminates are produced by introducing ATH into the resin, the higher the loading,
the better the performance. However, increased loadings lead to higher dispersion viscosity that can
lead to processing problems. Since MODAR resins have a low inherent viscosity quite high
loadings can be formulated, in conjunction with BYK W996 dispersing agent, and still achieve
excellent fire performance and processing ability. The level of glass present will of course,
influence these properties. Glass mat at 17 vol% is a typical composite. Table 5.2 shows the
minimum ATH loading to meet some of the European fire specifications.
71
Table 5.2 Fire performance of MODAR 835S laminates with 17 vol% random glass mat
National Bureau
Minimum ATH
Dispersion
of Standards
Fire requirement
(NBS) Smoke
required *
viscosity
(Dmax)
BS 476 parts 6 & 7
200 cps
70 phr
Class 2
115
1500 cps **
208 phr
Class 1
116
2500 cps **
250 phr
Class 0
French NF-P92-501
M2
50 phr
200 cps
117
M1
150 phr
700 cps
102
German DIN 4102
B2
50 phr
200 cps
117
B1
150 phr
700 cps
102
German DIN 5510
S4/SR2/ST2
100 phr
300 cps
114
Italian CSE RF3/77
Classe 1
150 phr
700 cps
102
* Alcan LV63 or Martinal ON904 + 2 wt% BYK W996
** Maximum dispersion viscosity for resin transfer moulding is accepted as around 1000 cps. So,
under ambient conditions, these 2 dispersions are only suitable for wet press and vacuum moulding.
Source of data: Ashland Specialty Chemicals
5.7.6 Dicyclopentadiene
Dicyclopentadiene (DCPD) with or without a saturated polyester as a low smoke low profile
additive can pass various building fire tests such as the German Chimney test or the British and
French spread of flame tests at the highest or next but one classifications. Likewise an unsaturated
polyester blended with methyl methacrylate can achieve such levels with either 120 phr of APP,
225 phr ATH and 25 phr APP, or with 300 phr of ATH. Similar formulations also pass German and
US railway tests with 100 phr of ATH and 10 phr APP. Not only are these formulations highly
flame retardant but they also fulfil smoke density and toxicity requirements as severe as those
demanded by the aircraft industry.
5.8 Thermoplastic Polyesters
PBT is one of the fastest growing engineering thermoplastics, driven mainly by the automotive and
electronics markets, accounting for the majority of its use. This has occurred as PBT continues to
replace thermosets in many electrical applications. The material has good dimensional stability,
strength, low moisture absorption and excellent electrical properties. It is however, easy to ignite
and so has to be flame retarded. This is usually achieved by relatively low loadings of brominated
flame retardants in combination with antimony oxide. Electrical connectors are one of the largest
volume applications of PBT and can be formulated to meet the V-0 class of the UL94 ignition test.
Around 8% bromine content in the final PBT compound is sufficient to achieve the V-0 test rating
for all types of brominated flame retardants, but some affect the physical and mechanical properties
of the resultant materials more than others. Polymeric brominated styrene additives would be
preferred in glass-filled compounds. Brominated polystyrene, such as Saytex HP-7010 from
Albemarle Corp. and poly(dibromostyrene) are such materials. They retain excellent properties
after heat ageing. High impact strength and excellent electrical properties are especially noted for
HP-7010 due to the additives high purity and low aliphatic halogen content.
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Several recent patents concern thermoplastic polyesters for electrical goods. DuPont has disclosed
a moulding composition for PBT, to which is added a reinforcement and a mixture of melamine
pyrophosphate with an aromatic phosphate oligomer. The physical properties are reported to be
good (EP 903370).
BASF has a US patent (US 5712336) in which a thermoplastic polyester is flame-retarded with
decabromodiphenylethane and two more additives. These are:
a metal oxide or metal sulfide or metal borate or a mixture of these, and

an ester made from a carefully specified acid and alcohol.
Along with the makers of other polymers that are utilised in the electronics industry, PBT
manufacturers have been concentrating on flame-retardant product grades that contain neither
halogens nor antimony, since there is a reduction of electrical properties such as tracking
resistance, plus the growing debate about potential toxicity hazards. Phosphorus-based systems
(such as Ultradur B 4000 from BASF) are now available that have an incandescent wire resistance
of up to 960 C plus outstanding CTI values and meet the V-2 classification for UL94 down to a
wall thickness of 0.4 mm.
PBT from BASF in the form of Ultradur B4520 can be made flame retardant with a combination of
cyclic diphosphonate ester (TPMP) and melamine. TPMP is available as Antiblaze 1045 from
Albright & Wilson and comes as a colourless highly viscous liquid.
TPMP modestly improves the flame retardancy of PBT. LOI rises from 21.9 to 23.5 or 26.7 at 10
or 20% loading and achieves V-2 in UL94. Co-addition of melamine to the TPMP leads to a strong
increase of the LOI to 31.8 and helps to obtain V-0 rating. The optimum ratio between TPMP and
melamine is 2:3 at a 20% total loading. There appear to be interactions between the additives as
well as between the additives and PBT.
It is likely that the combination of TPMP and melamine provides a dual mechanism associated with
the condensed and gas phases. In the condensed phase, interaction between TPMP and melamine
results in the formation of phosphorus-nitrogen containing solid residue. This residue, even at a
relatively small yield can be very efficient because of its glassy-like performance providing
superior barrier properties. On the other hand, TPMP + melamine significantly modifies the
mechanism of thermal decomposition of PBT towards formation of amides rather than acids. The
amides undergo dehydration, the water from which then cools the flame. White smoke is seen as
the material self-extinguishes and is found to be benzonitriles that crystallise very rapidly and
probably trap the free radicals in the flame.
For flame-retardant polyester fibres the copolymerisation of phosphorus retardants is the most
common method. However, a serious difficulty is that the phosphorus-containing polymer is easily
hydrolysed. Work by the Toyobo Company Limited in Japan has shown that two identical PET
fibres can offer differing properties depending on where the phosphorus compound is situated
within the polymer chains. One has the addition as a side chain and the other an identical
phosphorus compound in the polymer backbone. Both fibres had almost the same physical and
flame retardant properties, yet the main-chain type hydrolysed around twice as fast as the sidechain type, and led to an immediate drop in toughness.
This difference in hydrolysis properties is found to depend on whether a phosphonate ester bond is
placed in the polymer backbone or a pendant site. In the case of the main-chain type, the scission of
the polymer backbone occurs by hydrolysis of phosphonate ester bonds, whereas in the case of the
side-chain type, this does not occur. The results of this investigation show that the polyester fibre
with the side-chain modifier gives sufficient flame retardancy and excellent hydrolysis resistance.
73
Work at North Carolina State University has shown that an inclusion compound melt processed
into PET film provides substantial flame retardancy. The compound was formed between betacyclodextrin and the phosphorus-based flame retardant Antiblaze RD-1. The properties were much
better than films containing the separate constituents on their own.
GE Plastics non-halogenated, FR PET grade V9760NH contains 30% glass fibre reinforcement
and is free of halogens and red phosphorus. A dedicated technology was developed for this material
that combines its excellent plasticity with a wide processing window.
5.9 Polycarbonates
Polycarbonate blends are a major constituent of computer housings. Traditional brominated FRs
used in some markets are being replaced by fillers such as inorganic phosphates, as a nonhalogenated alternative. High inorganic loadings, however, can degrade mechanical properties. An
environmentally benign approach through using lower inorganic loadings can be achieved using
nanocomposites. One combination that has been studied is PC with montmorillonite clay (MMT).
Blends made by extrusion have created difficulties and show a degradation of the molecular weight
with development of colour. Processing leads to more exfoliation of platelets in the clay that causes
two competing effects. A reduction of the peak heat release rate (HRR) because of the exfoliated
platelets, versus degradation processes that increase the peak HRR. The dominant effect in low ash
and/or low shear situations is reduction of peak HRR. The opposite is true with high ash or high
shear since the peak increases.
PC/ABS blends can be made FR with high efficiency brominated products that maintain high heat
distortion temperatures and can obtain V-0 and 5VA ratings with no blooming or plateout on
moulds. The loadings required will depend on the PC to ABS ratio of the formulation used.
Plate-out has been a long-term problem with certain PC/ABS formulations, especially when based
on triphenyl phosphate (TPP). Resorcinol diphenyl phosphate (RDP) brings some improvements
versus TPP, but a better option is bisphenol A diphenylphosphate (BPADP). This shows excellent
stability plus good flow with low volatility. It has a better melt stability and hydrolytic stability
than RDP.
Bayer has been developing grades of Bayblend, polycarbonate/ABS, based on a proprietary FR
package free of bromine, chlorine and antimony synergist. A second generation is targeted mainly
at business machine housings, kitchen appliances, personal care products, and home items such as
vacuum cleaners. Although available as a developmental product for evaluation, it has been fully
commercialised as Bayblend FR90. Eliminating halogens has improved thermal and light stability,
and also helps avoid bloom and plateout. Avoiding antimony trioxide is important since, in the
presence of heat and moisture, it can catalyse or accelerate the degradation of polymers like
polycarbonate. The material has a UL94 V-0 rating at 1.4 mm thickness.
Bayer offer a flame-retarded version of their Bayblend PC/ABS series that is halogen-free and
suitable for extruded and thermoformed components destined for the E&E market plus the
construction and automotive sectors, also extrusion grades. These can be readily made flame
retardant with organophosphorus compounds.
The good flow properties of these alloys have made them ideal for a wide range of injection
moulding applications, such as thin-wall articles, within the E&E and IT sectors. Until the last few
years, these very properties, including the plasticising effect of the FRs used, prevented adequate
melt stability from being achieved and so precluded their use in extrusion.
Bayer and GEP, with their Cycoloy range, have now introduced FR alloys of PC/ABS in extrusion
grades. Bayblend FR3030 is offered with a required melt stability as created by use of non-
74
Newtonian high molecular weight polycarbonates and specific, low-plasticising FR additives based
on phosphorus. The new grades have excellent light stability, high heat resistance, good stresscracking and chemical resistance plus giving parts with excellent surface quality.
These extrusion grades produce low levels of smoke, around half of a comparable PPO alloy, and
on a par with rigid PVC, often the main material chosen for many extruded electrical components
such as ducts, conduits, etc. Bayblend FR 3030 even satisfies the Airbus Industrie demands on
toxic fumes potentially released in aircraft cabins. It also achieves V-0 at 1.6 mm in UL94 and
1 mm components pass the glow wire test at 960 C. The materials pass the Epiradiateur test for
building panels and the German Bundesbahn test for parts in railway vehicles.
There is potential as a replacement for rigid PVC over which it has a 30 C advantage for use in
electrical installations, and also has a 20% lower density (1.18) over the same material, thereby
offering weight reductions for similar components.
Samyang Corporation of South Korea has a phosphate based PC/ABS compound for use in
domestic appliances and automotive interiors (US Patent 5864004).
Borates are central to the formulations disclosed in Patent EP 892010 from Daicel Chemical
Industries Inc. of Osaka, relating to polycarbonates.
General Electrics Patent EP862185 concerns flame retardant based on an aryl-containing silicone,
which may contain triphenyl or diphenyl groups, together with a diorganic polysiloxane compound.
It is claimed to improve the flame retardancy of polycarbonate without losing the transparency.
Dow Corning Toray Silicone in Japan has proposed the use of a silicone-based FR for
polycarbonate compounds. A heat treatment at 380 C for polycarbonate containing the silicone
material has been shown to generate a phenyl silyl ether linkage that appears to lead to flame
retardancy for the formulation.
5.10 Other Thermoplastics
Phosphorus may be incorporated into PMMA to reduce flammability. Work carried out at Salford
University has shown that MMA may be reacted with diethyl(methacryloxymethyl) phosphonate
(DEMMP) to form a copolymer that provides a better flame retardant performance than a
compound to which diethyl ethyl phosphonate (DEEP) has been added. DEEP has a similar
structure to DEMMP and it might be expected that the two compounds confer a similar degree of
flame reatardancy to PMMA at similar loadings. The rise in oxygen index is similar, 17.5 up to 22
at 3.5% of phosphorus in each case. However, the MMA/DEMMP copolymer is more thermally
stable and gives better FR properties. It turns out that the DEEP plasticises PMMA whereas the
copolymer has similar physical and mechanical properties to unprotected PMMA.
Fortron polyphenylene sulfide is utilised in lamp holders and adaptors. The Ticona family of
materials have high heat resistance, inherent flame retardancy and good electrical insulating
properties. Fortron 1140L4 is used in strip-lighting systems for low-voltage halogen lamps, while
grade 61665A4 is injection moulded into insulating rings for lampholders.
The US Federal Aviation Administration (FAA) has studied the fire behaviour of the engineering
plastics that are now used as cabin materials. These would have a significant effect on postcrash
fires that can pose the most serious threat to passenger safety. The results form part of a
flammability and smoke properties database and create a benchmark for new fire safety systems.
The materials examined included polycarbonate, polyetherimide (Ultem), polyamide-imide
(Torlon), polysulfone (Udel), polyphenylene sulfide (Techtron), polyetheretherketone (PEEK)
75
(Ketron), polyimide (Vespel SP-1), polyphenylsulfone (Radel R) and sintered polybenzimidazole

(PBI) (Celazole). These materials were unfilled or neat without any flame-retardant additives.
Except for Ultem, none of the materials is widely used for aircraft interior applications. They were
tested in a cone calorimeter under differing heat flux levels. Several materials did not exhibit
sustained ignition at 35 kW/m2; neither Vespel nor PBI ignited even at 50 kW/m2.
Blistering occurred with all samples plus a swelling of the top layer with the formation of a gas
bubble. This bubble eventually released volatile gases that then ignited. Soon after flaming ignition,
all materials showed char formation accompanied by surface swelling.
The total heat release (THR) values of Ultem, PEEK and Torlon were significantly lower, by a
factor of 10 when compared to PC, Udel, Radel R and Techtron. The charring character of the
polymers greatly affects the heat release rate. Although a single peak HRR value cannot be used to
assess overall fire performance, worthwhile comparisons can still be made if all materials exhibit
similar burning behaviour. Torlon, PEEK, Vespel and PBI produced low HRR at high external heat
fluxes between 50 and 75 kW/m2 and showed high char integrity. Polymers having low
flammability either due to lower heats of combustion or heat release rates, also show lower smoke
production rates. Total heat released and effective heats of combustion appear to be better
parameters for assessing the relative fire performance of polymers.
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6 Suppliers and the Consumption of FR Additives and

Compounds
Chapter 6 reviews the supply chain and discusses the source of materials used by the resin suppliers
and compounders. The market for flame retardant additives is discussed and some statistical data
presented.
6.1 General Comments
Various factors are affecting the growth of the additives industry, many of them business rather
than technically related. Among them are foremost, the growth of plastics consumption and intermaterial competition, followed by a demand for shareholder value; pressure on margins;
globalisation; health and safety issues; and plastics recycling or disposal.
Major activity has been seen over recent times in acquisitions and divestments. This is driven by
the need to increase shareholder value. While certain companies are focusing more closely on their
core technologies, others are extending their current portfolios into related areas.
Witco and Ciba had product swaps plus allied distribution agreements to enable each to concentrate
on their individual technological expertise yet, at the same time, offer customers the benefit of
one-stop shopping.
Extending ones product line has expanded Great Lakes and OxyChem into antimony oxide flame
retardants through the purchases of Anzon and Laurel respectively in the late 1990s, so allowing
them to offer these synergies along with their core halogenated flame retardants.
Clariant had taken Albright & Wilsons red phosphorus business on board back in 1997. Then
Rhodia eventually topped Albemarles share offer for A&W, after a bidding war in 1999.
Some health and safety issues are perceived to exist with certain plastic additives, such as
halogenated flame retardants, along with some heat-stabilisers for PVC and various phthalate
plasticisers. At present there have been no restrictions on any halogenated flame retardants, but
there are some voluntary agreements limiting usage; more in Europe than in North America. Some
suppliers are looking at non-halogenated replacements, such as inorganic hydroxides, melamines
and various inorganic and organic phosphorus compounds. Growths of fire retardants is seen on a
global scale to be 3-4% per year.
The spread of chemistries that a combined group would offer become important for a specialised
chemical company as customers are increasingly demanding the one-stop shop for their
requirements. Customer overlap is one driver for acquisitions plus the complementary product
areas of flame retardants, surfactants, fine chemicals, water treatment and tertiary amines. It was
estimated that only 40% of A&W sales, at most, are in markets served by Albemarle.
Bromine suppliers are still looking for acquisitions in the non-halogenated sector to help spread the
risk if the worst happens in the regulatory arena.
Market consolidation of the chemical industry has resulted in 5 players accounting for more than
half of US sales, these are:
Great Lakes,
Albemarle,
Occidental (OxyChem),
Dead Sea Bromine and
Akzo Nobel.
77
In addition we are seeing increasingly a move away from a specific chemistry by the main
suppliers. For instance Great Lakes, the No. 1 brominated company, has added phosphorus and
antimony products through their acquisition of FMC Process Additives and Anzon respectively.
Trends seen in customer markets for engineering thermoplastics are the need for higher thermal
stability because of miniaturisation, interest in non-halogens and the wider use of polymer blends
to achieve FR performance. Thermoset requirements will include non-halogen FR-4 printed circuit
boards, higher heat distortion temperatures in polymers and the impact on FRs of the changes in
PU blowing agents, plus the use in PU foams of non-diphenyl ether types of FR. Trends in PVC are
perceived as increased concern over smoke generation and the need for greater low temperature
flexibility in wire and cable.
6.2 Suppliers
This section provides comment on the major manufacturers and suppliers of flame retardant
additives and materials. Table 6.1 lists suppliers of different types of flame retardants.
Since the mid-1990s, when even the biggest flame retardant suppliers were specialist companies, at
least within the plastics industry, there have been many consolidations and the biggest companies
now have a wider range of FR types within their portfolios.
Another change is that during this period, some of the larger FR suppliers now either belong to
larger additive manufacturers, like Ciba and Clariant, or themselves have become multi-additive
companies in the manner of Great Lakes Chemical Corporation.
Flame retardant type

Brominated materials
Chlorinated materials
Antimony trioxides
Alumina trihydrate
Magnesium hydroxide
Zinc borate
Phosphorus materials
Intumescent materials
Melamine
Silicones
Other inorganic materials
Table 6.1 Suppliers of flame retardants

Suppliers
Albemarle Corporation, Dead Sea Bromine Group including their
subsidiary Eurobrom, Great Lakes Chemical, Atofina, Ferro,
Clariant, Toso
Atofina, Clariant, Occidental, Akzo, Ineos Chlorine
Campine SA, Mines de la Lucette, Ferro, Great Lakes (took over
Anzon)
Alcan Chemicals, Martinswerk (part of Albemarle), Great Lakes,
Solem Europe, Alcoa, Climax, Huber Engineered Materials, Ciba,
Nabaltec, Omya
Alcan Chemicals, Eurobrom (Dead Sea Bromine), Martinswerk,
Premier Periclase, Solem Europe, Britmag, Flamemag International,
Martin Marietta Magnesia Specialties, Kyowa Chemical, Huber
Borax Consolidated, Climax Molybdenum, Joseph Storey, Alcan
Chemicals
Albright & Wilson (now part of Rhodia), Akzo, Clariant, FMC
Corporation (now a subsidiary of Great Lakes), Olin, Bayer,
Italmatch Chemicals, Solutia, Unitex Chemical, Nordmann,
Rassmann
Clariant, Himont
Ciba, Akzo, Chemie Linz, Cyanamid, Atofina
Dow Corning, GE Bayer
Alcan Chemicals, Amspec, Anzon (subsidiary of Great Lakes),
Climax, Morton International, Sherwin-Williams
Companies traditionally operating with brominated compounds continue to expand their product
lines with non-halogenated retardants, such as boron and phosphorus compounds. In early 2001
78
Great Lakes Chemical Corporation inherited the Reoflam line of phosphate ester FRs after
acquiring the process additives division of FMC Corporation. Albemarle Corporation introduced its
new phosphorus-based range with NcendX P-30 from an 11,000 tpa plant in Orangeburg, South
Carolina. The company has also teamed with the Borax Corporation to develop halogen and
halogen-free flame retardants, as well as supply zinc borate flame and smoke-suppressing agents to
Asian markets.
The rest of this section provides further background about the supply chain.
6.2.1 Brominated Flame Retardants

Since the decline of dibromoethane as a petrol additive, the major use for bromine has been in fire
retardants, mainly in plastics. In 1997, production of Br was 470,000 t.
The largest volume brominated flame retardant, accounting for about half the market is
tetrabromobisphenol-A (TBBA), used in printed circuit boards. The second largest, taking about
10% of the market, is decabromodiphenyl ether, widely used in casings for TVs and computers.
Mixtures of polybrominated diphenyl ethers are also found in treated furniture. A third major FR is
hexabromocyclodecane, used primarily in polystyrene foam and also in textiles.
Production of the raw material, elemental bromine, is dominated by the three major companies;
Albemarle, Dead Sea Bromine and Octel, part of Great Lakes. This production is concentrated in
the US and Israel, The former has over 50% and the latter around 30%. China, the UK, France and
some Central Asian republics are other sources.
The US and Israel produce bromine from brines that are far more concentrated than the oceans,
especially the Dead Sea with 14,000 ppm compared to only 65 ppm in the former. The leading
makers of BFRs are Albemarle and Great Lakes in the US, Atofina in France, Dead Sea Bromine in
Israel and Tosoh Corporation in Japan.
US company Albemarle has been very much to the fore in the development of processes to reduce
or eliminate risks associated with the production of BFRs. The middle of 1997 saw the completion
of 3 years of research into a new process that eliminates methyl bromide, a highly regulated
compound, as a by-product in the production of certain brominated compounds. Albemarle built a
worldscale plant of 50,000 tonnes in 1999 for the production of TBBPA at Magnolia, Arkansas that
uses the new process.
At the end of 1998 Albemarle, Jordan Dead Sea Industries (Jodico) and Arab Potash Company
(APC) signed a JV agreement to make and market bromine and bromine derivatives from a world
scale complex to be built in Jordan near the Dead Sea.
The new company, Jordan Bromine Company, has units to manufacture bromine, TBBPA and
calcium bromide near to the APC site. Bromine containing brines are provided from APCs
existing solar evaporation pans. Chlorine, which is used in the manufacture of bromine, will be
sourced from an adjacent plant.
Albemarle will provide the venture with process and engineering technology in addition to
marketing, customer service and manufacturing expertise.
Ferro Corporation sold its Pyro-Chek named products business, made in both the US near Chicago,
and France, to Albemarle Corporation at the beginning of 2000, along with the French plant.
Investment in the French unit, at Port-du-Bouc, by Ferro ensured that new developments in the
brominated polystyrene FR family were completed and the new owners also benefit from the
additional environmental improvements to achieve reduced atmospheric emissions during
manufacture.
79
Great Lakes Chemical Corporation has generated new offerings from all parts of its FR portfolio.
Two relatively new materials are Firemaster PBS64 and PBS64HW, based on its unique
dibromostyrene monomer. These are aimed at engineering plastics such as polyamide and
polyesters for small parts including connectors. The new materials offer improved flow
characteristics and higher thermal stability.
The Dead Sea Bromine Group has formed joint ventures in both China and Japan to enhance its
presence in world markets. In China it has teamed up with Ochean Chemicals, the largest Chinese
producer of bromine. The second JV is with DKS of Japan to produce and market worldwide
products based on DKSs technology. Dead Sea Bromine has also started up a large facility for the
manufacture of poly(pentabromobenzyl) acrylate, a flame retardant used in polyamides and
thermoplastic polyesters.
Albemarle is adding 37,500 tonnes of TBBA capacity at Safi, Jordan through its JV with Arab
Potash, due to start up at end 2002.
Globally bromine capacity in 2000 was 570,000 tonnes, with the top three having 35% at Dead Sea
Bromine, Great Lakes 30% and Albemarle 20%. Over all FR products Great Lakes is the worlds
largest manufacturer, with Albemarle in second place.
6.2.2 Melamine
Melamine production capacity in Europe is around 360,000 tonnes. DSM had the largest capacity
with around 25% in 1999. Agrolinz Melamin, producing in Italy and Austria has expanded from
100,000 tonnes to 130 kt by the end of 2000. This means they have claimed the first spot from
DSM. BASF has 65 kt capacity and Atofina around 26,000 tonnes. Most is used for thermoset
resins and adhesives, but a significant proportion goes into flame retardants. Further capacity exists
in Romania and Poland.
Melamine FRs are a small but growing market. In 1996, DSM merged the melamine FR activities
of DSM Melamine and the fine chemicals operation of DSM Chemie Linz to form DSMs Melapur
BV, which became the largest producer of such additives in Europe.
Ciba Specialty Chemicals increased its flame retardants portfolio in May 2002 by purchasing DSM
Melapur Flame Retardants, a leader in melamine-based technology, mainly utilised in engineering
plastics for the automotive and electrical & electronic sectors. This complements their Flamstab
technology, used for polyolefins. Ciba will retain the Melapur trademark and the two companies
are expected to work together to find new flame-retardant methods based on melamine chemistry.
6.2.3 Phosphorus Flame Retardants

The 1999 purchase of FMC Corporations Polymer Additives Division has resulted in about half of
Great Lakes Corporations $800 million turnover being in flame retardants. These cover bromine,
antimony and now FMCs phosphorus expertise.
FMC had two sites, one at Trafford Park, Manchester, England and the other in Nitro, West
Virginia, US. By extending their product platform, Great Lakes now offers halogen and nonhalogen based flame retardants. In conjunction with their other additives for polymers, such as antioxidants and stabilisers, the company provides customers with a comprehensive portfolio of
integrated additives second to none in the market. A major benefit from the combined flame
retardant range to Great Lakes is FMCs ability to meet the FR needs of polymer applications such
as PC/ABS blends for office equipment.
80
Consolidation has continued among producers of flame retardants. Apart from the Great Lakes
activity recorded above, Akzo acquired the phosphorus FR activities of Courtaulds. Albright &
Wilson (A&W) sold their red phosphorus business to Clariant. The next year A&W accepted an
offer from Rhodia via an Austrian company, ISPG to acquire the phosphorus chemistry activities,
including FRs. This was the outcome of a bidding contest between Rhodia and Albemarle. The
A&W purchase makes Rhodia the worlds largest operator in speciality phosphate chemicals.
Akzo has been increasing capacity for Fyrol PCF, its trichloropropyl phosphate, both in Germany
and the US.
Great Lakes has produced Firemaster BZ54 for the flexible PU foam market and offers advantages
over conventional chlorinated phosphate esters, such as lower loadings. It is well suited to the
requirement of non-CFC blowing agents, exhibiting lower scorch than when alternatives are
utilised. Reofos BAPP, a bisphenol A diphosphate and Reofos 507, butylated triaryl phosphate, are
other new grades aimed at overcoming problems in engineering thermoplastics such as stress
cracking and plate-out sometimes found with FR packages used in PC/ABS and PPO/PS blends.
6.2.4 Mineral Filler Flame Retardants

The market for antimony oxides is dependant on PVC and brominated FRs, since the trioxide
works as a synergist with halogens, whether in the polymer itself or as an additive. Raw materials
are a key cost at around 80% of the product. Bolivia and Guatemala have closed their antimony ore
mines due to low prices and China is now the leading source of antimony ore.
Alcan Chemicals Europe, a major source of flame retardants, mainly mineral based aluminium and
tin compounds, has been put up for sale by parent Alcan Canada.
Magnesium hydroxide has to compete with ATH as a mineral filler FR.
ATH is widely used in thermoset polyester and some elastomers, but is finding increasing use in
EVA and other ethylene copolymers. Prices range from as low as 20p/kg up to 80p/kg for
specialised grades. By contrast, magnesium hydroxide, used in PP and PA that are processed at too
high a temperature for ATH, costs from 60p/kg up to 1.50/kg. Magnesium hydroxide is used in
wire and cable, roof membranes and a widening list of specific polyolefin applications.
A proper comparison has to be with the fine precipitated grades of ATH for which the worldwide
market is around 100,000 tonnes, compared to about 20,000 tonnes for magnesium hydroxide.
Currently, producers in Japan are seen as Kyowa Chemicals Industry and Tateho of Japan. Kyowa
have a combined capacity of around 18,000 tonnes since opening a second plant in the Netherlands
during 1999. Tateho have a recently opened plant of 12,000 tonnes capacity.
In addition, Magnifin, a JV between Alusuisse-Lonza and Veitscher Magnesitwerke, has a 10,000
tpa plant in Austria; and Dead Sea Periclase has a 6000 tpa in Israel.
Flamemag International has a pilot plant in Australia to prove a new hydrothermal process, with
plans for a 10,000 tpa commercial unit to be built around 2002. Flamemag is another JV, between
Queensland Metals Corp. and Mines de la Lucette the French company.
Great Lakes has brought out uprated antimony oxide-based grades. Fyrebloc 100 and Fyrebloc 101
are 100% active formulations using a halogenated carrier giving excellent flow and thermal
stability that improve processing and handling.
Albemarle purchased Alusuisse Martinswerk GmbH, based at Bergheim, Germany, from Alcan Inc
of Canada in mid-2001, this sale being one of the conditions to comply with the European
81
competition requirements for Alcans purchase of the Alusuisse-Lonza Group during 2000.
Martinswerk also has a 50% stake in Magnifin Magnesia Produkte GmbH based at St
Jakobs/Breitenau in Austria. This stake has also passed to Albemarle. This has made Albemarle the
leader for ATH and MDH mineral FRs.
6.2.5 Borate Flame Retardants

At around the beginning of 2000 Albemarle began a joint development programme with Borax
Corporation to create new, more versatile flame retardant technologies. These were to be new
options in both halogenated and halogen-free systems for polymers. A challenging target was set to
explore borate FR chemistry and the broader use of borates in polymers beyond the traditional
outlets in PVC, polyamide and epoxy potting compound applications. Future growth opportunities
in styrenics, engineering plastics and other resins would take advantage of the low toxicity and FR
performance of zinc borates.
Borax had been planning to grow this aspect of their business and felt that Albemarle was an
excellent partner who has an extensive background in FR chemistry and long-standing ties with the
polymer industry. Equally, a link with Borax provides another strand for Albemarle as they
broaden their FR capabilities. Albermarle has expanded its inorganic bromide capabilities at its
production operation in Thann, France.
6.2.6 General
Saytex and NcendX are the cornerstone of Albemarles portfolio from the late 1990s with a 50,000
tpa expansion for Saytex RB-100 material, demand for which had been increasing at 7-10% a year.
A more recent addition has been Saytex CP-2000, a continuous process, and high quality
tetrabrominated product and NcendX P30, a bisphenol A based phosphate product being targeted at
the PC/ABS materials, with a 12,000 tpa unit opened in early 2000.
Albemarle Corp. is involved in a JV in China for the manufacture of various polymer additives
including flame retardants. The US company and Jinhai Chemical & Industry Co. will jointly sell
and export these products from the new enterprise.
Non-halogen FRs for styrenics and new brominated platforms are part of the Great Lakes strategy
for future developments. For polyolefins, the priorities are non-blooming, no plate-out materials as
well as non-halogen materials.
6.3 Consumption and Market Data
As reported before, the publication of dedicated statistics for the consumption of flame retardant
additives is intermittent and mostly retrospective, with few current estimates. However, various
consultancies do regularly issue reports covering plastics additives as a whole, in which are
included figures for FR materials.
Estimates for the world market for BFRs at the end of the 90s was around 1m tonne/year, with the
US and Europe taking more than 70% of global consumption, Japan around 14% and the rest
elsewhere in Asia. Global growth rates are said to be 7-8% with Asia the fastest sector of all.
Comprehensive figures have been issued by Townsend Tarnell (Table 6.2). Townsend Tarnell in
1996 said that FR growth worldwide would average 5% to 2001.
82
Table 6.2 World market for flame retardants in plastics in 1996 (tonnes)
Material type
Europe
North
America
Asia
Antimony-based
18,000
20,000
35,000
Brominated
53,000
67,000
97,000
Chlorinated
16,000
16,000
11,000
ATH
90,000
150,000
75,000
Phosphorus65,000
48,000
30,000
based
Others
15,000
13,000
7,000
Total
257,000
314,000
255,000
Source: BRG Townsend Inc., reproduced with permission.
Rest of
the World
Total
2,000
7,000
2,000
10,000
75,000
24,000
45,000
325,000
Growth
pa 19962001
%
3
6
1
5
5,000
148,000
little
26,000
35,000
852,000
7
5
In the US, Business Communications Corporation (BCC) predicted 5% growth in FR consumption

until 2003. The highest growth was expected for phosphorus-based FRs, at 7%, and brominated
FRs with 8.5% (Table 6.3). BCC data show that ATH was the largest volume market.
Table 6.3 Estimated consumption of Flame retardants in the USA (tonnes)
Annual growth
Product type
1998
2000
2003
(%)
Antimony-based
27,670
29,030
30,845
2.2
ATH
135,173
143,790
157,400
3.1
Brominated
94,350
111,130
142,000
8.5
Chlorinated
36,740
38,100
40,825
2.1
Phosphorus-based
40,370
46,267
56,700
7.0
Magnesium-based
3,175
3,630
4,080
5.0
Others
6,350
6,800
7,710
4.0
Total
343,828
378,747
439,560
5.0
Source: Business Communications Co. Inc.
A more recent study by Freedonia for the US market gives growth there to be a little less, at 3.7%
pa; from 450,000 tonnes in 2000 up to 540,000 tonnes by end 2005. Details are shown in Table 6.4.
Table 6.4 USA demand for flame retardants 2000-2005 (000 tonnes)
Annual growth
Type of additive
2000
2005
(%)
ATH
156
177
2.5
Bromine compounds
120
147
4.2
Phosphorus-compounds
70
86
4.3
Antimony oxides
33
43
5.4
Chlorine compounds
27
29
1.6
Boron compounds
23
27
3.7
Others
26
34
5.3
Total
455
543
3.7
Source: Freedonia Group, reproduced with permission.
European consumption in 1998 for flame retardants has been given as 27% of the market with
North America at 31% and the Asia-Pacific region taking 38%. BCC estimated that in 2001
83
404,000 tonnes of FR were consumed in Europe, to rise by 4% pa to 491,000 tonnes in 2006.

Growth may increase if stringent fire safety requirements are established for the E&E sector.
Frost & Sullivan in a European study gave FR additives at a volume of 261,000 tonnes in 1995, up
to 291,000 tonnes in 1998, with an estimated growth of 3.8% a year to become 377,000 tonnes in
2005.
Estimated volume shares and changes to 2005 were listed as follows:
ATH 45% in 1995 unchanged by 2005

Brominated types 25% drop to 20%+
Antimony oxide from 7.5% down to 5.7%
The drops will be made up by several other families, mainly melamine, magnesium hydroxide, zinc
borate and zinc stannate. There are about 30 players, according to Frost & Sullivan, in the
European market (Table 6.5, Figure 6.1).
Table 6.5 Revenue breakdown of the European flame retardants market (2000 and 2003)
2000
2003
Brominated flame retardant
32.4%
31.8%
Phosphorous based
29.7%
28.8%
Aluminium trihydroxide
14.7%
16.1%
Antimony trioxide
10.9%
10.4%
Chlorinated flame retardant
4.4%
4.2%
Melamine based
3.6%
3.6%
Magnesium hydroxide
2.5%
2.9%
Zinc borate
1.4%
1.6%
Zinc stannates
0.32%
0.43%
Others
0.10%
0.14%
Source: Frost & Sullivan 2001, reproduced with permission.
Melamine based
3.6%
Chlorinated flame
retardant
4.2%
Magnesium
hydroxide
2.9%
Zinc borate Zinc stannates

1.6%
0.4%
Others
Brominated flame
0.1%
retardant
31.8%
Antimony trioxide
10.4%
Aluminium
trihydroxide
16.1%
Phosphorous based
28.8%
Source: Frost & Sullivan
Figure 6.1 Total flame retardant chemical market:

percent of revenues by product type (Europe), 2003
84
Freedonia, a US research company, estimated that FRs for plastics accounted for 440,000 tonnes of
material in the US in 1998, worth some $725 million. Growth in value terms is given as 7% a year
as regulatory and environmental factors spread.
About 25 million tonnes of PP are consumed worldwide with an average growth of 7% annually.
Only about 1% of this PP consumption volume is flame retarded. Until 1998 the market
requirement for the standard of flame retardancy was estimated as:
UL94 V-0 @
UL94 V-2 @
DIN 4102 B 1 @
others
63%
23%
12%
2%
Since then, a range of applications now calls for V-0 rather than V-2, which has increased the call
for further high flame retardancy. The average growth for FR PP is around 8% per year.
Brominated FRs are the most widely employed for PP. The use of non-halogenated FRs is limited
because of insufficient thermal stability during processing or the high loading needed to obtain
good flame retardancy that may compromise the resultant physical properties of the compound.
Estimates of consumption of the different FR families gives:
Non-halogenated
TBBA derivatives
Decabromo and similar
Other Br/Cl types
24%
19%
29%
28%
Flame retardant applications for PP are proportionately much less important than for other resins
such as styrenics and engineering thermoplastics; less than 5% of the total FRs consumption is used
in PP.
This is mainly due to the difficulty and cost in reaching the high standards of flame retardancy
required in electronics and building industries with PP compounds. The cause of this difficulty is
the high crystallinity and flammability of PP.
Brominated FRs had sales in 2000 of $900 million (global). Market shares are:
Great Lakes
Albemarle
Dead Sea Bromine
Others
31%, @ $271.7 million

23%
22%
24%
In 1998, FRs accounted for roughly 13% of the global additives market, at almost $2 billion.
In 1999, the total plastics additive market was $15.5 billion
Global growth for FRs is estimated to be 5% a year:
North America @
Asia-Pacific @
Latin America @
6% as average of 4-7% (to be 1.5 billion lb by 2003)

7-9%
6-8%
US demand for flame-retardants was expected to grow by over 4% pa to 1500 million pounds
weight by 2003. Plastics account for almost 80% of this demand, according to Freedonia.
85
The three most important markets for FR plastics are construction, electrical and electronic devices,
and motor vehicles. The best opportunities lie in the electronics sector where strong growth in
consumer electronics and wire and cable applications is driving the demand for higher-value,
speciality grades of flame retardant plastics.
Environmental concerns over brominated, and other halogenated products will negatively impact
on their future growth as end users pursue less controversial substitutes including non-halogenated
phosphorus, magnesium hydroxide and silicone compounds.
SRI Consulting issued a new study on flame retardants in November 2002, in which they give the
total market for flame retardants in the United States, Western Europe and Asia in 2001 as more
than 1.2 million metric tons and valued at almost $2 billion. This market is expected to grow at an
average annual rate of about 3.0-3.5% per year on both a value and a quantity basis over the 20012006 period, exceeding 1.4 million metric tons valued at just under $2.4 billion. The United States
has been the largest consuming region with 32% of the total, followed by Western Europe (29%),
Other Asia (21%) and Japan (19%). Flame retardant consumption reached a peak during 1999/2000
but has suffered severely with the economic downturn of 2001. Although the economic conditions
affected all products, durable goods requiring flame retardants were hit especially hard. These
include electronic and communications equipment, construction and transportation markets.
Asia Pacific, excluding Japan, represents the most rapidly growing market for flame retardants
since manufacture of consumer goods requiring flame retardants has been migrating to this area.
Currently, most use is in printed circuit boards and housings for consumer electronics and business
machines for export, so these products must meet the flame retardant regulations of the destination
countries. However, as the standards of living in the Asia Pacific countries continue to rise as the
area recovers from recent economic downturns, both rapidly increasing regional demand for the
products themselves and domestic regulations requiring flame retardancy are expected to follow.
The major flame-retarded resins in this region are epoxy and phenolic resin (for printed circuit
boards) plus acrylonitrile-butadiene-styrene (ABS) and polystyrene (for consumer electronics and
business machine housings). The growth in Japanese flame retardant consumption is expected to be
less than Other Asia because of a shift in production to those areas.
The Bromine Science and Environmental Forum in Brussels gave the global FR market as worth
$2.2 billion in 1998. Brominated compounds made up 39%, inorganics took 27% and phosphorusbased compounds at 24%. Chlorinated compounds took 6% with the remaining 4% taken by
melamines.
Other, US firms, including Merrill Lynch arrived at a similar value total, but gave a slightly
differing breakdown of types. The market for flame retardants in 2000 globally was estimated as
$2.16 billion. This was broken into bromine 34%, phosphorus 22%, antimony oxide at 17%, ATH
14%, chlorine-based at 7% and others on 5%.
When fillers and colourants are excluded then flame retardants take about 12 wt% of the global
tonnage for performance additives on 2001 figures of roughly 8.5 million tonnes. This is second
only to plasticisers that take a massive 59%, mainly in PVC.
In tonnage terms more than 900,000 tonnes where sold in 2000 (Table 6.6).
The market for flame retardants depends as much on the overall growth of plastics consumption as
it does on any increase in FR requirements within a plastics application per se. There is anticipated
growth of 5.5% a year for the rest of the decade in plastics consumption (in Europe).
The European market for FRs came to around 380,000 tonnes in 2000, with a value of around 275
million euros.
86
Table 6.6 Worldwide demand for flame retardants - 2000

Type of additive
%
ATH
42
Bromine-containing
21
Phosphorus-containing
17
Antimony oxides
8
Chlorine-based
6
Melamine
3
Magnesium hydroxide
2
Others
1
Source: Filler Consulting, Austria
6.4 Compounding for Flame Retardancy

It is important to realise/remember when formulating a compound with a particular type of flame
retardant that other additives included may have adverse effects on the efficacy of the FR
capability. The presence of carbon black, mineral fillers, UV or antistatic additives may well alter
the behaviour of the resulting compound. Oils or organic pigments may likewise have detrimental
effects and so need to be excluded or replaced in the final formulation.
One important reason why these additives may have a negative impact on flame retardant
properties is that their chemical structure inhibits the formation of halogen radicals, when a
bromine or chlorine containing FR is employed. If these radicals are trapped before they are able to
curtail the material degradation process, there is a dramatic reduction in the efficacy of the flame
retardancy. It is always advisable to carry out tests when generating new formulations.
Table 6.7 gives some examples of other additives giving problems with specific FR agents:
Table 6.7 Impact of other additives on flame-retardant materials
Flame retardant
Detrimental additives
Chlorinated paraffins
Carbon black
Antimony trioxide
Calcium carbonate (at low levels)
Brominated compounds
Ethoxylated amines (antistatic) at high levels
Phosphorus-based compounds
Comonomers such as EVA
ATH at levels >60%
Specific organic pigments
Intumescent systems
Mineral oils at high loadings
Borates
Stearates at high loadings
In preparing compounds with FR content, it is necessary to achieve a certain metering accuracy, if

the main polymer resin has not already been purchased as an FR grade. Uniform dispersion of the
FR additives is also most important for coat efficiency. The percentages added may fluctuate from
quite low levels to very high ones for inorganic, dependant upon the required level of FR
performance and the type of polymer used.
If the amount of additive is so high that a masterbatch or concentrate cannot be used, then
traditional mixing is employed. The advantage of working with a mix is that it is possible to
produce a finished compound with all the required properties, such as UV resistance, suitable
colour and high elastic modulus, for example.
The drawback is that the concentration of the additives in question is pre-determined and any
corrections have to be introduced at the development stage of the formulation. Masterbatches are
used in applications where a high degree of dispersion of a low, final concentration of an FR and/or
87
other additives is required. Here, the advantage is that it is possible to make corrections to the
concentration.
Flame retardant additives are no different from any other plastic additive. There are a number of
characteristics that must be known and understood to properly use any plastics additive. Structure
and the molecular weight for a specific FR additive affects the toxic nature of the product, the
inherent physical properties and the ultimate use of the FR additive. Important attributes include
melting point, particle size, decomposition temperature, and solubility among others. Most
halogenated FRs suitable for use are monomeric molecules. Although oligomeric and polymeric
FRs do exist commercially, they are generally used in higher heat engineering resin systems.
When selecting a FR for a thermoplastic is to best match the melt point of the FR with the
processing conditions of the polymer. Also it is sensible to select the FR that has a decomposition
temperature similar to the combustion characteristics of the polymer.
A promising approach toward reducing flammability of polymer systems is to alter the condensedphase chemistry at elevated temperatures. Structure modification can alter the decomposition
chemistry to favour transformation of the polymer to a char residue. Such an increase occurs when
thermally induced stable crosslinking structures and/or aromatic rings are produced. Work by the
Brooklyn Polytechnic in New York has examined systems such as polystyrene, aramids, PF resins
and nitrile polymers such as SAN.
Styrene-acrylonitrile copolymers are strong, rigid and transparent. They have excellent dimensional
stability, high craze resistance, but their flammability requires retardation for designed end-uses.
The effect of zinc chloride decreases the initial thermal stability of SAN but char yield was
significantly increased. High temperature FTIR showed that zinc chloride complexes with the
nitrile group. This, in turn, induced a modified degradation mechanism leading to thermally stable
triazine ring formation which crosslinked the main chains.
One shortcoming of the so-called fire-smart polymers approach to flame retardancy is that
polymer manufacturers usually prefer to optimise their product for properties other than flame
retardancy, so that introducing structures to favour flame retardancy may mean a compromise of
other properties. Moreover, putting in specialised functional groups often means increased cost.
Therefore a good strategy would be to try to utilise, as crosslinking sites, those latent functional
groups that are already present in commercial polymers.
88
7 End-User Market Sectors

7.1 Automotive
Automotive foams may be made more flame retardant by the incorporation of phosphorus polyols
that are bound to the foam matrix by hydroxyl groups. Clariant offers grades of its Exolit range that
are non-halogenated additives for flexible polyether slabstock and moulded foams. Benefits of the
Exolit range are low emissions, high ageing resistance, good odour characteristics and high
efficiency.
Exolit OP 550 is a low-fogging additive that is recommended for moulded and high-density
slabstock foams where flame retardant efficiency is uppermost. OP 551 (TP) is a low-fogging
liquid flame retardant for slabstock where a lack of discoloration is critical.
Exolit OP 560 (TP) has appropriate emission characteristics to satisfy the latest VOC values to
comply with the standard Daimler-Chrysler PB VWT 709 test procedure. This product gives a
good balance between high efficiency and good ageing performance and exerts only a slight
influence on mechanical properties.
The Exolit OP range can be used in conventional production facilities by direct injection into the
mixing head. The products should not be pre-mixed with polyols or polyol formulations because
they are only partially soluble in polyether polyols with low hydroxyl numbers and they hydrolyse
slowly in the presence of water.
Materials in car interiors need to meet a horizontal flame spread rate of no more than 4 in/min
(102 mm/min), when tested according to US Federal Motor Vehicle Safety Standard 302 (FMVSS
302), however, the results of this test have been shown not to predict fire hazard. Fire fatalities in
highway vehicles, although occurring in much smaller numbers than in buildings, do represent
significant numbers. In 1997, there were 88 such cases in the UK and 450 in the USA.
Careful studies by respected fire performance specialists have examined typical plastics materials
taken from a random selection of current vehicles, such as dashboard components, door and
headliners, seats and other trim, plus a further selection of commercial plastics available on the
open market for any and all applications.
Results indicate that while there are significant differences among vehicles, the large majority of
car interior materials tested (a random yet indicative cross-section) represent a fire performance
that is, at best, mediocre. Moreover, the comparison between the two sets of materials shows that
car interior plastics are likely to ignite much faster than commercially available plastics and release
heat almost twice as fast.
The fire hazard consequence of the analysis is that flashover in the vehicle interior does not require
large ignition sources. Thus, even very small ignition sources can generate a large enough fire so
that ease of exiting the vehicle is going to be severely hampered.
In 2001, influential groups such as the US Fire Retardant Chemicals Association and the US
National Association of State Fire Marshals had at last started to consider ways to develop
alternatives to test requirements based on FMVSS 302, or its equivalent ISO 3795.
Fire test requirements for the acceptability of automotive interior materials should be changed so
that materials with improved fire performance are used in future. Since the fire performance of
typical car interior materials seems to be poorer than that of conventional plastic materials that can
be found commercially in the market place, then improvements in automotive materials fire
performance should be easily achievable. This can result from either using intrinsically safer plastic
materials or from adding flame retardants to existing materials.
89
7.2 Other Transport

Composites are increasingly becoming the material of choice in the manufacture of rail vehicles.
The reasons for this are varied and include high strength to weight ratio, low maintenance costs,
ease of installation and the facile reproduction of complicated designs. Common in-service
examples include toilet modules and interior panelling. Phenolics have an advantage over other
resin matrices due to their unique chemical structure that makes them inherently fire resistant. They
do not readily burn and if involved in a fire, produce minimal levels of smoke or toxic fumes.
Phenolic resins are traditionally orange/brown in colour and will progressively darken on exposure
to UV light. To overcome this, phenolic surface pastes or in-mould primers are used to maintain the
fire performance of the final composite whilst providing a smooth, pinhole free surface onto which
fire retarded paints can be applied.
It is this system that is used for the most stringent of applications the interior of underground
trains which are designated as Category 1a under BS 6853, the 3m cube smoke test. Rolling stock
within this classification is defined as having Substantial operating periods in a single track tunnel
with no side exit to walkway and escape shaft, or, sleeper cars which operate underground for
significant periods, or, trains that operate without staff.
Railway companies all over Europe and in the USA now use trains containing phenolic
components; both internal for panels, luggage racks and toilet modules; and for external parts such
as massive front ends, window frames and, more recently, for panels made in a sandwich of PVC
foam cores and phenolic skins. Window frames for the Madrid Metro meet the M1F1 French
standard and parts made by Mitras Composites UK conform to Category 1b of BS 6853 for
ADtranz, a major rail vehicle manufacturer.
Fire safety is now taken extremely seriously for underground and enclosed-space applications. The
London Underground rail system has taken to using silicone glass and phenolic glass laminate
materials. They both are approved to specification SE 970 and have excellent properties under fire
propagation and spread of flame test conditions, plus low toxicity. Silicone glass is used for many
insulation jobs underground and both materials are finding widespread use in critical locations on
the London network.
Lower loadings of halogen-free flame retardants are to be welcomed in the transport sector where
low smoke density is required and lighter weight composite components are increasingly specified.
The European railway sector has been anticipated to double its use of reinforced plastics between
2000 and 2005, up to at least 100,000 tonnes. The biggest growth is expected in glass-reinforced
polyester composites, in above-ground rolling stock; but they must have a low heat emission rate
and low smoke and toxic fumes in the event of a fire.
To avoid halogenated resins, which generate smoke and toxic fumes during combustion, ATH has
been utilised, yet high loadings are required leading to mechanical and processing difficulties.
Phosphorus-based retardants are effective in thermoset resins, by dehydrating the pyrolysing
polymer, forming unsaturated compounds with subsequent charring. The non-volatile polymeric
phosphates thus formed provide a glassy coating for the carbonaceous layer that is forming at the
same time. This coating inhibits the pyrolysis reaction and shields the underlying polymer from
oxygen and radiant heat.
In the company of special synergists, a protective coating in the form of an intumescent layer can
be formed in the case of a flaming situation; and flame-retardants based on phosphorus are also
good suppressors of after-glow and smoke. Such properties are of particular interest to formulators
of gelcoats. Exolit AP 740 from Clariant meets the demand for halogen-free materials for various
composite-processing routes; such as resin transfer moulding and pultrusion, at fairly low addition
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rates. 50 pphr of this additive can allow the Epiradiateur test, NF 92-501 to be passed by a
composite with a rating of M1, compared with the need for 250 pphr when aluminium hydroxide is
used.
Only 20-50 pphr of AP 740 are required in epoxy resins to reach the same low level of smoke
density as is produced with polyester laminates. The aviation standard FAR 25.853 can be passed
with a loading of 25-35 pphr. A liquid version of the additive is available for circumstances where
a powder additive cannot be utilised.
Red phosphorus flame-retardants are effective in thermoset resin systems and also elastomers,
often combined with ATH, or magnesium hydroxide in elastomers. A wide range of treated red
phosphorus in dispersion or concentrate form, offered by Clariant, is easier to handle and safer to
transport, compared with powder grades. Such phosphorus additives do not affect the electrical
properties of the composite, and they have little impact on the physical properties of the laminates
manufactured.
Work has been progressing to devise a test method for a European standard for rolling stock, prEN
45545. This task has been much more difficult for railway vehicles than for other areas due to the
large discrepancies between the various national standards. The operators of public transport in the
UK enforce the strictest requirements across Europe. German specifications are lax in comparison.
French requirements cover both fire and smoke development. Harmonised fire regulations are
needed as the railway system accommodates more and more transnational high speed trains such as
the Thalys that runs between Cologne, Brussels and Paris. The focus of fire prevention is
passenger safety and so special attention is attached to smoke development and its toxicity.
Modern GRP systems offer solutions based on both coated ATH and polyphosphate additions to
meet the varying requirements of the different standards. Intricately shaped interior trim on the SBahn suburban railway in Berlin features flame retarded SMC materials.
7.3 Electrical Components
All materials employed in electronic equipment operating under electrical load have to be flame
retardant. Traditional printed circuit boards utilise epoxy resins retarded by reacting TBBA into the
liquid resins before laminate construction (FR4). To comply with UL94 V-0 specification, the
resins contain about 20% of bromine. In case of fire or smouldering, brominated epoxies evolve
corrosive decomposition products that can damage the surrounding electronic equipment. This can
be avoided by use of phosphorus flame retardants.
It has been found that the addition of finely divided red phosphorus can result in the required flame
retardancy with no effect on the thermal and electrical properties of the laminates.
As with other sectors, an increasing number of OEMs in the electrical world will insist on halogenfree systems for their products. This extends to the printed circuit boards (PCBs) used to make
them. Even the phosphorus systems mentioned above are likely to come under scrutiny as well.
The thermal stability of FR4 brominated resins is poorer than non-brominated (G10), although it
has been improved over the years. Limitations of FR4 can be overcome by using a G10 resin with
ATH and the effect of heat ageing this combination provides a V-0 performance.
Once subjected to a fire, all the various options that contain phosphorus or nitrogen can generate
toxic species such as cyanides, phosphorous acids etc., but carbon monoxide and dioxide are the
most lethal gases, and tend to be present in far larger quantities once a fire has taken hold.
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The TBBA in an epoxy system can be replaced by phosphorus compounds that are built into the
backbone of the resin. Unfortunately it is very difficult to obtain the same laminate characteristics
by this approach, hence the addition approach of red phosphorus.
It is known that with halogenated systems the higher the laminate glass transition temperature (Tg)
the lower the halogen content required to achieve V-0 performance. So to achieve FR properties the
resin Tg is increased, making the laminate more difficult to drill and rout. The cost also rises.
The advantage of the phosphorus-based system is that its tracking/arcing performance is
significantly improved, but other key parameters tend to suffer. The water absorption is high and
likely to cause problems with plated-through holes that may trap moisture and so cause blistering
when later heated, either during soldering or in service.
Epoxy systems incorporating ATH show an endothermic reaction and this is important in absorbing
heat produced in a fire and matches well with the decomposition of the TBBA based epoxy.
CEM3 laminates made with non-woven as well as woven glass in epoxy plus ATH (but no other
FR additives) give V-0 characteristics. Because of the lack of thermal stability of standard ATH,
the laminate can blister under certain processing conditions, such as reflow soldering. This problem
has been addressed by the development of modified forms of ATH with much improved stability
whilst retaining the FR effectiveness. These have been successfully used in CEM3 laminates to
produce a material that on combustion gives off mainly CO2 and some NO2, so toxicity is very low.
One such thermally stable (TS) material is Martinal TS610 from Martinswerk. This is added at at
least 200 pphr to achieve V-0 at 1.6 mm thickness, prior to incorporation into the non-woven glass
layer.
In woven glass cloth layers it is not possible to incorporate TS610 at these loadings. In CEM3
laminates TS ATH can be combined with phosphorus since in certain instances this can simplify
the manufacturing process. Unfortunately this raises the materials cost and can generate the
problems described above for P-containing systems. In processing Martinal-containing systems,
sedimentation of the filler must not take place and the company recommend a combination of
TS610 and TS601 with a suitable resin circulation method to minimise the potential problem.
Woven glass FR4 laminates have been available for a long time using standard ATH and lower
levels of bromine within the resin system. Above 60 phr of ATH, copper adhesion can be reduced
and above 80 phr mechanical properties can be adversely affected.
By incorporating TS ATH into the epoxy resin system, the level of phosphorus in the backbone of
the resin can be reduced. The use of an ATH filler will also reduce the laminate cost. The addition
of Martinal TS 601 to the phosphorus-based resin improves the flammability and allows a lower Tg
resin system to be used. Other laminate properties are not affected.
CEM3 laminates, incorporating Martinal TS, can be produced with very low potential toxicity. This
low toxicity should accelerate the use of this type of material worldwide.
FR4 laminates cannot at present incorporate the high levels of Martinal TS to achieve UL94 V-0
rating without other FR materials present. The combination of Martinal (TS601) with phosphorus
in the backbone of the resin would appear to be the best compromise currently available.
However, resins containing TBBA are very cost-competitive and continue to provide great efficacy
of flame retardant protection. Those who call for a halogen-free PCB system often tend to be
referring just to the flame retardant package employed, and perhaps forget to check on the halogen
status of the complete installed PCB package.
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7.4 Electronics Products

Significant changes are taking place in resins selected for moulding of housings and enclosures for
electronics products. A survey of the US market has indicators (Table 7.1).
A major influence on the choice of material is now being played by downsizing and, more
importantly, thin-wall moulding technology, bringing more demanding requirements for properties.
The main materials in the computer and business machine sector are ABS, PC/ABS alloys and high
impact PS, with some use of PVC and polycarbonate. In consumer electronics, however, HIPS is
almost exclusively used, and little change is expected up to 2003.
In the business machine sector, monitors are expected to account for nearly 30% of material
consumption and, in the consumer sector, stationary TV sets will make up 33%.
Table 7.1 Resin demand for electronics housings in the US, 1998-2003 (000 tonnes)
Average growth
1998
2003
(%)
Computers/business machines
413.1
465.9
2.4
Consumer electronics
325.0
401.8
4.3
Total
738.1
867.7
3.3
Source: Business Communications Co. Inc.
Technologies that will influence the use of materials in the future are (as well as thin-walling) EMI
shielding and the changes in flame retardant additives, under pressure from the need to comply
with environmental regulations in various countries.
Marketing is driven largely by the short product life cycles of computers and business machines,
and also tumbling retail prices. Logistical considerations have led to huge volumes of business
machines, including computers, being made in Asia, plus a move of US resin production and
conversion operations to Mexico.
Brominated flame retardants have been one of the cornerstones contributing to the safe and
spectacular development of computers, business machines and other electronic apparatus. This
market is consuming vast qualities of styrenic copolymers to produce the housings of this
equipment. Good standards of flame retardancy have been developed and applied in the US, and to
a lesser extent in Europe, and they can be achieved thanks to brominated flame retardants.
Recent developments call for styrenic materials with better moulding properties to produce lighter,
thinner and more complex parts with good impact properties. In some cases UV and light stability
is also requested. New flame retardants are now on offer to address these needs. They have been
developed by their suppliers from chemistry that is not based on that of diphenyl ethers, and so
offer an alternative solution to those sectors of the market that are reluctant to use deca- and
octobromodiphenyl ether.
The surge in new electronic products led by small computer-based devices has resulted in
significant changes in resin choices for enclosures. Downsizing and more importantly, the rush to
thin-wall constructions have led to a change in resin selection for enclosures.
The computer and business machine sector uses very few resins of consequence. ABS, PC/ABS
and HIPS followed by those of much less importance such as PVC and polycarbonate. On the other
hand the consumer product enclosure market is exclusively made up of HIPS with little change
foreseen over the immediate future.
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The computer/business sector enclosures should grow at 2.4% annually, with monitors taking
almost 30% of total resin consumption. The total in 1998 was 188,000 tonnes.
Growth on the consumer side is expected to be over 4%, from 138,000 tonnes to reach 182,000
tonnes in 2003. Stationary TVs will account for 33% of total resin, with audio/video and CDs
taking a further 35%.
In resin competition, PC/ABS will erode a significant portion of ABSs share, while HIPS will hold
its own along with PVC. Polycarbonates are expected to increase greatly, yet remain a minor resin
in this market. HIPS competes directly with ABS but not with PC/ABS.
Moves to restrict the use of halogenated flame retardants are starting to have a dramatic impact on
the way in which plastics are used in electronic equipment and the ability of electronic
manufacturers to provide the consumer with higher levels of fire safety. Certain plastics may no
longer be able to be used and, more importantly, the high levels of fire safety (such as UL94 5V
and above) may no longer be readily achieved without additional material cost.
The move to recover ever-increasing volumes of end-of-life equipment is certainly a challenge to
the electronic equipment industry and all those in its upstream supply chain.
Various labelling schemes operating in Europe that confirm the absence of brominated FRs from
the products so marked include an EC one, Germanys Blue Angel plus the TCO and White Swan
systems in Scandinavia.
In addition, a draft of the proposed EC Directive on waste electrical and electronic equipment
would ban some brominated compounds from 2004 (written in 1999). These are polybrominated
biphenyls and polybrominated diphenyl ethers. The directive would also require all halogenated
flame retardants to be removed from components in any waste equipment that is separately
collected.
As a result some computer manufacturers, such as Hewlett-Packard, have shifted to phosphorusbased FRs in housings for computer monitors. Siemens has developed a phosphorus-based
alternative to the TBBA used in the epoxy resin laminates that are the basis of all circuit boards.
Electronics giant NEC of Japan has entered the fray with a polycarbonate containing a silicone FR.
The company has licensed Sumitomo Dow to be the manufacturers of this special polycarbonate.
Sold as NuCycle, the new material is used to make NECs liquid crystal display monitors and
battery packs for portable computers. It is also applied for other polycarbonate applications,
covering projectors and plasma flat screens.
NEC has a target to stop using halogenated FRs by 2011 and has been shifting, generally, to
phosphorus compounds.
For all branches of E&E products, the call now is for flame retardant systems that do not rely on
halogens or phosphorus and the leading suppliers are all steadily improving their additives; despite
the considerable argument about the merits of different materials; not to mention the scientific
reasoning behind some legislation.
For E&E products in general, however, the real pressure is foreshadowed in the European WEEE
recycling legislation. Annex III of the draft requires that any plastics parts containing halogenated
flame retardants must be separated before recycling, so imposing additional costs, and militates
against the use of bromine-containing compounds.
This flies in the face of preliminary conclusions under the EUs own risk assessment programme
that indicate that there is no need for risk reduction from the two types, decabromo diphenylether
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(decaBDE) and octobromo diphenylether (octoBDE), mainly used in electrical and electronics
equipment. It also appears to be at odds with other studies on the effectiveness of these flame
retardants and recycling them. Fundamentally, there is also a growing feeling that the fairest way of
assessing flame retardants (and other additives) is a complete life-cycle assessment (LCA) on their
environmental impact.
The proposal has been attacked from several sides, not least the German Environment Ministry,
whose Deputy Director-General has been quoted as believing that there is no need for binding
recycling targets, and opposes substance bans such as those proposed for lead or the PBDE and
PBB flame retardants. In addition both the German Environment and Economic Affairs Ministries
were concerned at the excessively prescriptive and restrictive system being proposed for E&E
waste by the ECs Environment Directorate-General.
German studies have shown that polystyrene compounds flame retarded with decaBDE, as widely
used for housings, meet the stringent requirements of the German Chemicals Banning Ordinance.
They also indicated that no detectable amounts of brominated dioxins/furans were formed during
recycling. There was no debromination of the additive and exposure of workers to dioxins/furans
was below German workplace limits by some two orders of magnitude.
Fears have also been expressed that the material bans contained in the draft WEEE Directive would
infringe international trade agreements.
Practical confirmation of the effectiveness of brominated flame retardants also comes from recent
Japanese work, by copiers makers Ricoh and Fuji-Xerox. Setting up a practical recycling loop for
moulded copier components, and comparing recycling of an ABS compound flame retarded with a
brominated epoxy oligomer with that of eight other compounds retarded with organic phosphate
esters, it found that the recycled brominated ABS met the highest levels of fire safety, as
represented by the classification UL5V, which is the test with which most manufacturers of office
copiers comply. As a result, Japanese manufacturers of copiers are now specifying that new lines
must have 25-30% content of recycled material, containing brominated flame retardants.
Another source of confirmation of the overall benefits of flame retardants in general and of the
brominated species in particular is a LCA study from Sweden. This concludes that from an
environmental viewpoint there is little basis for a general prohibition on all halogenated flame
retardants. Looking specifically at the bromines, the environmental consultancy that conducted the
work, Orango AB, concludes that there are some 70 different types used in industry, with very
different properties. Bromine is a natural substance and is not an environmental toxin, it is even
used in cough medicine, but in some individual cases bromine may be included in synthetic
molecules that are stable and bioaccumulate, so giving at some point negative effects on health or
the environment.
Because fires themselves are a major source of polycyclic aromatic hydrocarbons (PAHs), a class
of carcinogenic substance found in combustion smoke together with dibenzodioxins and furans, the
use of flame retardant additives significantly decreases environmental emissions of this type. The
Swedish study compared US and European TV sets and showed that those manufactured to the
European standard gave off far higher emissions of PAHs.
US sets, containing brominated flame retardants, produced fewer emissions to the environment. US
makers must produce sets to meet the V-0 standard of the UL94 fire test but, in Europe, the
moulded plastic enclosure of a TV set needs only to pass a Horizontal Burn (HB) test. The US
manufacturers use the brominated flame retardant decaBDE to meet their specification, but in
Europe manufacturers have removed all flame retardants from their enclosures.
The final statement from the Swedish study concludes, In the case of key emission species
(polycyclic aromatic hydrocarbons, and dibenzodioxins and furans), there is a markedly higher
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total emission over the whole life cycle from the non flame-retarded TV than from the flameretarded TV.
The BSEF concurs that the concept of producer responsibility for collection and recycling of
equipment is agreed by the industry sectors affected by WEEE, but it will be difficult to achieve the
proposed targets. Moreover, if certain brominated compounds are one of the best solutions for
recycling (as found by the Japanese), the EC, with its mandatory separation of all plastics
containing halogenated species, is requiring the industry to perform a difficult task and trying to
pull in two directions simultaneously.
7.4.1 Telecommunications
Fire safety for plastics in telecommunications depends on the type of components under
consideration, and their location, as much as the specific polymer material from which they are
made. The products vary from small consumer items to high voltage cables. Therefore, the safety
requirements for a range of applications must be set quite differently, although the expected
lifetime conditions for a component may not always be clearly known or forecast.
In the case of small switches or connectors, the key parameter is ignitibility. If a loose connection
causes increased thermal exposure to the plastic of a component, then the problems will be
minimised if ignition to flame can be prevented. At present the plastics utilised are often
characterised by their performance in tests with small impinging flames, but we may ask what may
be such a small flame source in a real-life scenario?
The next step in achieving safety would be to limit the potential of fire spread from the ignited
component to the surroundings. This may be controlled through the burning characteristic such as
heat release rate or formation of flaming polymer droplets, but equally the manufacturer may
design those surroundings in such a way that small flames would not cause any harm.
The fire safety of equipment enclosed in cabinets could be controlled by consideration of the
components and cables inside or by designing the cabinet in an appropriate way. In some cases
active measures like detectors or water mist systems might be included.
Often the fire behaviour of cables is considered the main factor in a telecommunications system. In
addition to the cables themselves, the performance resulting from any passage through walls must
be considered. Sealing of power cables as they enter a building is usually carried out, but there is
often little control of the open holes created when installing cables within a building.
One issue when rating cables is what to take as the scaling denominator? Test rigs with equal areas
or equal numbers of cables have been used when comparing the behaviour of different products.
All data generated should be freely available for fire safety engineers to use when assessing the
potential consequences of fire in a cable bundle.
It is unfortunate that old cable runs, with possibly poorer fire behaviour, may be left in conduits
and so perhaps nullify the benefit achieved by employing new improved modern cables. It is
common now to set higher requirements for products intended to perform under higher
temperatures under normal use than in the past.
Current trends are for ever more control over fire safety of products due, in part, to the
globalisation of trade and the increased desire to adopt more rational performance-related standards
for products rather than piece-meal consideration of the elements in a component or system.
In Europe, some telecomm products such as cables will be considered as construction products and
so subject to the Construction Products Directive (89/106/EEC of 21/12/98). However,
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implementation after many years is still not settled, due to the wait for harmonised tests and
standards to invoke them.
A key issue is the development and resolution of the so-called Single Burning Item test. Other
European projects are covering the general testing of cables, FIPEC; and one for advanced methods
for the determination of fire effluent composition.
One aspect of a, reasonable, common market is the acceptance of test results from one laboratory
everywhere in the market area. On the other hand it appears that the rules governing the test and
certification procedures will become more stringent in order to guarantee the acceptance of the
results. It would not, therefore, be a surprise if the cost of a single series of tests and related product
certification increased so causing potential problems for manufacturers in small markets, albeit
great benefits for companies in international markets.
7.4.2 Consumer, Brown Goods

Studies in the US in the past, mainly through the auspices of the National Institute of Standards &
Technology (and its predecessor, National Bureau of Standards), have shown that the overall costs,
in terms of damage, health and environmental considerations, of non-flame retarded TV cabinets,
and other consumer items, that are involved in fires is much higher than those associated with a
properly formulated and flame retarded material used for the same purposes.
Testing by the Swedish national testing and environmental authorities on the same types of
products made use of a general life cycle analysis (LCA) model that has been modified to contain
the likelihood of fire occurrence and the consequences.
Both chlorinated and brominated dioxins are emitted in greater quantities from non-FR TVs with
just a Horizontal Burn (HB) rating compared to the TVs containing brominated flame-retardants to
a V0 rating level. Polycyclic aromatic hydrocarbons (PAH) are also given off in far greater
quantities by the non-FR TVs than the protected ones.
It is worth noting that the emission levels of both the brominated and chlorinated dioxin
equivalents from both the FR and non-FR TV life-cycles are low compared to other sources.
Figures indicate that such emissions from one million TVs during their 10-year life-cycle is at most
around 10 mg, or 1 mg/year. In the Netherlands, the annual emissions of dioxins from all known
sources are just short of 1,000 g. If we take a figure of 11 million TV sets in that country this would
equate to a total dioxin emission from TVs of roughly 11 mg/year or only 0.001% of the overall
national total emissions.
It should be noted that the production of PAH is many times higher than the production of all types
of dioxins and furans. It would be reasonable to conclude that PAH emissions represent a much
greater risk to health and the environment than the dioxin-equivalent emissions.
In addition, at least 16 people die each year in Europe, based on UK and European statistics. These
are known to be conservative due to the cautious estimate of the frequency of TV fires, based on
the HB rated sets in Europe. It is conjectured that there may be up to 10 times this number. In the
US, however, there is no record of any deaths from fires related to the V0 rated sets in that country.
Thus, the risk to human life must not be ignored in any overall assessment of the risk from flame
retardant additives.
This has been confirmed by work in Germany by the Fire & Environmental Protection Service.
The occurrence of TV fires in the US is more than an order of magnitude lower than in Europe (13
compared to 265 fires per million TVs). This dramatic difference provides compelling evidence
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that the higher fire safety classification of enclosure materials typically used in the manufacture of
TV sets sold in the USA does have a significant and beneficial effect on fire safety.
After dropping for several years, the number of TV set fires in Europe has stopped decreasing, and
in countries such as the UK, Sweden and the Netherlands where detailed statistics are kept there is
direct evidence that the figures are rising.
The European CE mark requires compliance to the local equivalent of IEC65, which allows HB
classified materials for enclosures. HB materials are much more easily ignited than those with the
stringent V0 classification, and are therefore much more susceptible to fires resulting from design
errors, manufacturing defects, misuse, external causes or the effect of ageing and general
deterioration.
Enclosures made from HB materials may not provide enough protection to consumers, especially
children and the elderly, or to their property.
Other countries such as the USA or Japan require higher safety ratings than Europe. The
technology to achieve that higher fire safety has been a normal commercial practice for many
years. Implicit in the studies on fire statistics and the LCA from Sweden, a return to the use of
materials with high levels of fire safety may be necessary to provide adequate protection to
European consumers.
It is in the interests of society, due to loss of life and property, to take measures to lower the
incidence of fire by analysing and acting upon the elements that contribute to fire safety, i.e.,
materials fire performance, design and consumer education. So, making materials less fire-safe is
obviously not a move in the right direction.
7.5 Electrical Cables
Cables used in mining, railways, shipbuilding and heavy industrial equipment have to be resistant
to fire, oils, abrasion and other hazards, yet remain flexible across a wide temperature range from
sub-zero to tropical and desert conditions.
25 years ago, this property spectrum could only be met by materials based on chlorinated rubbers
such as chloroprene and Hypalon, which on the whole served their purpose well. However, by the
end of the 70s, it was recognised by various cable users, especially the Ministry of Defence (MoD)
and the London Underground (LUL) that should cables covered with these materials become
involved in a fire, sufficiently strong that they themselves combusted then there was a potential
hazard. The combustion products generate much black smoke and acidic gases. The former
prevents evacuation by obscuring visibility and the latter is an irritant and corrosive agent. These
conditions become particularly hazardous in areas of restricted access and exit such as underground
rail systems and military vehicles. Other problem areas are those of high population density and
those containing capital-intensive plant and machinery.
The smoke evolved by chlorinated compounds is a consequence of the chemical structure of the
polymeric material and compounding ingredients. Acidic gases result from dehydrochlorination of
the polymer.
BICC began R&D for the MoD and LUL to develop halogen-free materials that would,
nevertheless, have the properties of inherent flame retardancy, fluid resistance and flexibility at
both high and low temperatures, yet have much reduced smoke and gas emissions. The programme
gained ever more urgency after the Falklands conflict of 1982 and the Kings Cross fire of 1988.
At that time the choice was limited to EP rubbers, EVA, ethylene methyl acrylate (EMA), and
nitrile formulations. None of these polymers are inherently flame retardant and only NBR
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possesses an adequate level of fluid resistance. Early work was centred on this group of materials,
either alone or in blends with each other or with plastics such as the polyester or polyamide
thermoplastic elastomers. The early offerings were EVA or EMA polymer systems plus large
amounts of hydrated fillers. These materials had poor processibility and had a poor level of
physical and mechanical properties.
The materials have evolved since the 1980s as new polymers and additives have come on the
market. Now, halogen-free compounds are available that have equivalent flame retardancy and
fluid resistance to the old chlorinated traditional materials, plus low smoke and acid gas properties.
High performance grades fully meet the Naval Engineering Standard NES 518, now known as DEF
Stan 61-12 (Part 31) and represent the ultimate in fluid resistant, flame resistant, halogen-free
rubber technology. Today, BICC Compounds offers a wide array of halogen-free elastomers as
solutions for applications not only in shipbuilding, but construction, petrochemical, railway and
automotive engineering. In addition to their fire performance, halogen-free materials now also offer
environmental and life expectancy advantages over traditional materials. They do not contain any
heavy metals, nor plasticisers or sulfur-based vulcanising agents; and can now be predicted to last
for around five times longer than traditional chlorinated elastomers under the same conditions.
Teknor Apex has various halogen-free insulation and jacketing compounds which provide
characteristics to allow communications and data cables, for both copper and fibre optic, to meet
European, IEC, requirements for minimal smoke toxicity. The Fireguard LSZH series offer good
productivity for cable extrusion, due to low die drool. The 1000 series grades, with Shore D
hardness from 43 to 56, give LOI levels from 35 to 53%. There are five 2000 grades with
hardnesses from 38 to 53 and LOI from 35 to 52%. In IEC 332-3C tests, cables with jackets and
buffers made from LSZH compound exhibit maximum char lengths of no more than 89 cm; the
permissible maximum is 250 cm.
European regulations governing cable sheathing flammability are slowly moving closer to the
tougher regulations now operating in the US. The European standard for plenum wiring, IEC 3323C, is about as demanding as the US standard for risers, UL 1666. The US plenum wiring standard,
UL910, is much tougher. A new European requirement, closer to UL 910 is believed imminent.
In simulated fire situations, while wiring meeting UL910 hardly burns at all, wiring meeting the
IEC requirements burns extremely quickly, creating extremely high temperatures that lead to
flashovers. Zero-halogen cable takes longer to burn than halogenated cable, but once ignited, it
spreads more rapidly.
Another company making moves in this field is MA Hanna, the US-based compounder now part of
PolyOne. Cable compounds became their first market-oriented product group, following an
expansion of their German-based unit Melos Carl Bsch in Melle. This increased production of
ECCOH brand of low smoke and zero halogen (LSOH) compounds was first made at Enviro Cable
Compounds based in Oslo, Norway, another subsidiary. The company is possibly the leader in wire
and cable compounds, after the in-house compounding of the cable makers themselves.
The LSOH materials, based on polyolefins, are designed to reduce risks of black corrosive smoke
from cable fires and are aimed at low- and medium-voltage uses. While the material is at least
twice the cost of PVC, it is not a major factor in total cable costs, depending on the type and size of
cable. On a big cable, the jacket will only be around 3% of the total cost, rising for a small cable to
20%. Market growth was seen as 10% pa with demand around 60-70 ktpa. The total demand for
PVC cable compounds is around 1000 ktpa, of which special flame retardant types take 20%.
BICC Compounds, a subsidiary of BICC Cables part of General Cable, have been at the forefront
of low smoke and fume technology. One area has been low smoke and zero halogen compounds to
meet the new Harmonisation Document for the insulation of single core unsheathed electrical
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cables. These types are designed for low-voltage point-to-point wiring between machinery and
light sources in factories, where they directly replace the PVC-based 6491X cable range. Such
cables are usually installed in areas where there are large numbers of people present, particularly
where there are restricted means of escape.
European Harmonisation document HD 22.9, from CENELEC, is specified in British Standard
BS7211 and calls for low smoke, zero halogen materials that maintain the levels of flame
retardancy, cost and processing speed experienced with PVC, while reducing the potential risk of
combustion products.
BICC has developed a range of crosslinkable compounds for this demanding application, which are
suitable for different manufacturing routes. Large amounts of hydrated mineral fillers are employed
in new polymers that permit high loadings, plus additional chemical additives that stabilise the
fillers in the polymer matrices and improve the characteristics of ageing and processibility.
The ability to crosslink the compounds gives improved physical properties, better chemical
resistance and shape retention at temperatures significantly above the melting point of the polymer
resin itself. This prolongs the life of the compound and its integrity in the event of a fire. One of
three methods can be utilised in the cable industry: peroxide, silane (either Monosil or Sioplas
techniques) and electron beam; each requiring a different compound to achieve the right properties.
Each has positive points and drawbacks.
For peroxide crosslinking, the compound has been selected to maximise the speed of the line by
providing maximum scorch safety time during extrusion, while giving maximum residence time in
the continuous vulcanisation tube. The version for silane processing has been formulated to
minimise silane dosages and avoid side reactions with the curing system, while the compound for
electron beam curing contains special promoters to maximise crosslink density.
Cable racks fall into three overall categories; ladders, open trays and closed trays. Their influence
on fire performance is considerable and can be measured in a version of the 3 m cube room smoke
test under IEC 61034. Unexpectedly, a closed tray does not afford complete fire protection since a
chimney effect can cause rapid fire propagation along the length of the sample.
Belgian cable company Kabelwerk Eupen has introduced a commercial application for polymerclay composites to make flame retardant cables. EVA-based cable jackets are combined with the
clay materials in what is called a one-pot synthesis extrusion technique. 5% of the nanoclay
improves the fire performance of the EVA compound by promoting char formation and delaying
degradation. In addition, it prevents dripping of any burning polymer material.
The maker of the nanoclay is Sd-Chemie, who believe that the nanocomposites could be used as
an alternative to PVC coatings and resins containing brominated FRs.
Kabelwerk Eupen have explored combining nanocomposites with other FRs. These include ATH in
EVA. The two companies have applied for a patent for this technology and claim that less ATH is
needed in a nanocomposite than in a standard compound, thereby leading to increased extrusion
speeds and improved elasticity.
To achieve typical flame retardancy for cables required by the most important international cable
fire test (IEC 60332-3-24, Tests on electrical cables under fire conditions Part 3-24: Test for
vertical flame spread of vertically-mounted bunched wires or cables) demands a high loading of a
mineral FR filler such as ATH. 65wt% of ATH with 35% of a suitable polymer like EVA must
often be used for cable jackets. A similar compound of EVA (with 28% VA content) with ATH and
5% of a nanocomposite can pass the same test. It was found that the ATH could be reduced to only
45% of the composition. The reduction in the total amount of the fillers results in improved
mechanical and rheological properties of typical EVA-based cable compounds. The char formed is
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very rigid with only very few small cracks and is believed to be the cause of a much reduced peak
rate of heat release when combusted.
A range of halogen-free low smoke compounds for cable insulation and sheathing are available
from AEI Compounds Ltd., in Gravesend, England. These come under the Catapyrric trade name.
Some, such as SX545:CM540U are silane crosslinkable; whereas others are moisture curable or
entirely thermoplastic.
7.6 Building and Construction
The introduction of flammable pentane as a blowing agent to replace HFCs and other potentially
ozone-depleting fluorocarbons in the manufacture of foam panels has brought with it the additional
factor of fire resistance.
The fire behaviour of pentane is such that in PU formulations, it is necessary for the pentane and
water components to be precisely coordinated with as little pentane as possible. In spite of this,
high quantities of flame retardant are required to pass the tests set in DIN 4102-B2. This creates a
more costly polyol component. By contrast, PIR formulations display different behaviour in fire
tests. Since the isocyanurate groups give the foam excellent flame retardant properties, PIR foams
fulfil the fire tests with much reduced levels of non-halogen flame retardants. In addition, higher
quantities of pentane may be utilised without impairing the FR properties of the foam to any great
extent.
Elastogran has developed pentane blown polyisocyanurate formulations with a much-reduced
content of halogen-free flame retardants. The company has developed new polyester polyols for the
package that contain isocyanurate. The new PIR systems also offer far better dimensional stability
for the resultant insulation panels.
Panels with paper or aluminium outer layers have been continuously produced in thicknesses from
20 mm to 140 mm. They are primarily used as roof insulation in the form of dimensionally stable
panels with flexible outer layers.
Another material that has become more widely recognised for its fire safety as an insulation
medium in construction is phenolic foam. Most products from the wide choice available today
provide good fire resistance and meet various relevant standards, either inherently or with the use
of flame retardants and facing materials. However, a significant difference arises with regard to the
level of smoke emissions. A surprising point is that Building Regulations do not set limits on
smoke emission by construction materials and components under fire conditions; even though it is
well accepted that smoke is often a serious hazard and may well be more life-threatening than the
fire itself.
Such safety considerations have led to an increase in the number of specifiers requiring phenolic
foam insulation. Although this is a cellular plastic, it has good fire performance, exhibits low flame
spread, extremely low smoke emission and is a very efficient thermal insulant.
The densely crosslinked structure of phenolic foam has an inherently low capability of smoke
generation, which is a result of the polymer being essentially a char forming material when heated
to ignition temperature. The char has a high carbon content that acts as good thermal insulation; it
burns slowly, without flaming or melting, and so avoids substantial coalescence of low molecular
weight organic species, which are known to be smoke producing.
Phenolic foam is unusual in that it combines the good thermal performance, moisture resistance
and structural strength of cellular materials with the fire performance of inorganic and fibrous
materials. The versatility of phenolic foam makes it ideal for a whole range of applications, from
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traditional heating and ventilation uses, structural applications such as roofing, cavity board, floors
and the like to composites panels for use in the food processing industry.
Awareness of phenolic foam is increasing all the time through such activities as the testing
protocols under the Euro-classification system and the European Phenolic Foam Association, that
highlight the excellent fire performance and low smoke and gas emissions of phenolic based
products. New preparation techniques in the 1980s have given rise to extensive usage of phenolic
foams for pipe and ducting insulation and to wider application in the flexible-face laminate market
for building insulation.
Such foams meet the requirements of most major fire tests relevant to the construction industry,
entirely unaided, while other organic insulants require the addition of flame retardants or facings
such as steel, aluminium or plasterboard.
An example is Kooltherm pipe and duct insulation from Kingspan Industrial Insulation that
achieves Class 0 rating as defined in the UK Building Regulations. This is a combination of
BS476: Part 6 for Fire propagation and Class1 Spread of Flame according to BS476: Part 7. These
tests demonstrate the excellent generic fire performance of phenolic materials without the aid of
additives or protective facings.
The Nord Test NT 036 is a full-scale test used by insurance authorities, where the ceiling of a room
is lined with 24 x 3.6 m lengths of insulated pipework. A 150kW burner is used and flame spread,
smoke and toxic gas emission are assessed. Phenolic foam gives negligible flame spread or smoke
and the quantities of CO and CO2 generated during the 15-minute test are small and toxicologically
insignificant. Also, under BS5111 the Kooltherm products register a smoke obscuration figure of
less than 5%, the same as mineral wool.
Phenolic foam pipe insulation has also been tested and approved by Factory Mutual for use as pipe
insulation, based on its low spread of flame.
A single European standard has been proposed for the construction industry based on a new test
currently called the Single Burning Item test, designated prEN SBI. In this, the reaction of
materials to fire is divided into Euro-classes (prEN 13501-1), see Chapter 8.
Flame retarded SMC parts have excellent resistance to fire in the SBI test. It is so good that it
achieved the highest classification for organic materials and the best smoke status.
The SBI test will succeed the following national standards, among others, in the construction
industry:
DIN 4102;
Epiradiateur NF-P-52-501/ NF-F-16101/2;
BS 476 Parts 6 & 7.
Unlike DIN 4102, in which some melting test specimens are rated as superior to non-melting
materials but exhibit totally different behaviour in a real fire, the SBI test offers the possibility of
testing the materials under more realistic fire conditions.
Because of this anomaly in DIN 4102, flame resistant thermoset materials are often rated as being
poorer performers than they actually are, especially in Germany. The SBI test is much more
realistic in this regard and does not disadvantage or advantage any material on account of its
peculiarities.
Highly filled formulations, with ATH, subjected to the SBI test gave rise to the results shown in
Table 7.2. The tests conducted by Michael Sommer (BYK-Chemie GmbH) on SMC panels reveal
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that the material passes all test specifications of the pertinent methods and can be modified to meet
all needs where necessary. Depending on section thickness, ATH content can be adjusted to allow a
component to achieve the appropriate specifications.
Table 7.2 Comparison of ATH-filled SMC compounds, and other materials, in the SBI test
FIGRA
THR
SMOGRA
Material tested
(W/s)
(MJ)
(m2/s)
Fire class B, smoke class S1
<120
<7.5
<30
UP, SMC, halogen-free FR
B
B
S1
Fire class B, smoke class S2
<120
<7.5
<180
PVC, FR
B
B
S2
Fire class C, Smoke class S1
<250
<7.5
<30
PF, phenolic foam
C
B
S1
<180
>7.5
<750
Fire class D, smoke class S2
S2
D
D
PP, pipes of 40 mm and 110 mm diameter
S2
D
D
PVC, cables with PVC jackets
>180
>7.5
>750
Fire class E or F, smoke class S3
S3
E/F
E/F
PC, FR, 3-coats
S3
E/F
E/F
PS, FR
S3
E/F
E/F
PU, FR foam
FIGRA = Fire Growth Rate; THR = Total Heat Release; SMOGRA = Smoke Growth Rate
Source: Michael Sommer, BYK-Chemie GmbH, reproduced with permission.
Products for outdoor use such as wall cladding, can be press moulded in many variants from SMC
or BMC. Pultruded profiles can also achieve B1 fire status if a resin such as DCPD or unsaturated
polyester/MMA is used with up to 250 phr of ATH as part of the additive package. The
classification of flame resistant GRP systems in the SBI test will be a great boost for the materials
enabling them to satisfy the fire protection rules of the future.
7.7 Upholstered Furniture and Textiles
The application of natural fibre based fabrics has increased in the furniture industry during recent
times after many years of decline, as synthetic materials were the favoured textiles and fillings. A
reappraisal of the fire properties of various materials in their proper context for coverings, barrier
layers and fillings has hastened this trend.
There is now the possibility of natural fibres having an increased resistance to ignition even in the
absence of flame retardants.
Cover fabrics, such as wool, cotton, flax, viscose and their blends, are often impregnated with
proprietary flame retardant systems such as Pyrowatex and Proban, which demonstrate fastness on
washing or cleaning. Wool has the advantage of a natural capacity to form intumescent
carbonaceous char with excellent thermoinsulating properties. Wool/cotton or wool/flax at 50/50
blends are most efficacious. Flax has the added property of protecting against moth infestation and
also prevents static build-up. Such blends pass the small ignition source test, e.g., the equivalent of
a lighted match, no ignition during a 20 second application, with the exposed fabric converted into
a char with no exposure of the underlying PU foam substrate.
Another way to protect the inner, support component of upholstery is the use of barrier materials in
the form of non-flammable interlayers placed between a covering fabric and the filling material.
Woven and non-woven fabrics as well as felt made from natural fibres (e.g., cotton, flax and hemp)
and their blends with flame retarded synthetic fibres, can be used.
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The Institute of Natural Fibres in Poznan, Poland has developed new barrier fabrics, both woven
and non-woven. The first was a cotton weave containing a small addition of polyester. The latter
was made of flame retardant flax and hemp fibres. The flame retardant and its application method
were developed by the institute. The flame retardant, called FOBOS M2T, was based on urea
polyborates and the sodium salt of alkyl-aryl sulfonic acid. The method of impregnation is cheap
and simple. It can be carried out on typical finishing equipment and increase manufacturing costs
by only 10-15%.
The use of a non-flammable barrier fabric has been shown not only to increase time to ignition but
also to reduce the maximum heat release rate. Various non-woven systems were found to offer
good fire prevention properties with differing fillings and the same linen/polyester covering, but the
best combination in a range of cone calorimetry tests was an impregnated flax/hemp non-woven.
This gave good times to ignition with all fillings, but the lowest figures for heat release, both in
total and for maximum and average rates of release was given with a PU foam filling.
The various projects at the institute reveal that natural barrier material treated with flame retardants
are an effective method for reducing flammability of upholstery systems. Barriers made from FR
treated nonwovens are much more effective than barriers made of difficult-to-ignite fabrics.
The move in the US to introduce regulations for the flammability of furniture fabrics has spurred
activity in the segment.
The US Consumer Product Safety Commission (CPSC) has found that the outer cover fabric is the
primary determinant of the initial growth of small open flame-ignited furniture fires. Injuries
caused by these fires are principally those of children playing with lighters and matches.
A study for the CPSC examined 16 flame retardant compounds and found eight immediately of
minimal risk.
The main three compounds already used in the UK for fabric protection appear to be on the
accepted list for the US standard. For cotton-based fabrics the major candidate is phosphonic acid
(3-[hydroxymethyl]amino)-3-oxypropyl dimethyl ester, sold as Pyrovatex. It is already used for
apparel and does not meet the definition of toxic under the Federal Hazardous Substances Act
(FHSA).
For synthetic fabrics, decaBDE and hexabromocyclododecane are the main candidates. Since these
compounds have large molecules they cannot be easily absorbed, although they require, typically a
synergist, usually antimony trioxide. The latter, however, has increasingly fallen under suspicion as
a possible carcinogen or at the very least an undesirable product to inhale as dust.
Zinc borate has continued to attract attention as a proven substitute, and is another not toxic
substance under the FHSA.
Meanwhile there is a fourth candidate, used for many decades in certain flame-resistant cotton
apparel fabrics. This is tetrakis hydroxymethyl phosphonium salts (THPS), with trade names such
as Proban.
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8 Fire Testing
8.1 Introduction
Depending on the particular polymer under consideration, the product type into which the polymer
is incorporated and the specific end-use application, many different fire retardant methods can be
used. The aim of all these modifications of a polymer product is to improve its fire performance to
pass the specified fire test(s) for the application concerned.
There are several ways to change the fire behaviour of a polymeric material especially at the
different phases of combustion. However, there is no single best way to improve the fire behaviour
of a certain polymer/polymer product because the needed performance depends on the
requirements in the intended end-use. Hence, the same product may need to be optimised in two or
more ways if it is to be used in different applications.
End-use applications of products can be grouped in many different ways depending on the purpose.
For fire safety, the essential points to bear in mind are regulatory requirements, and within those
the detailed end-use applications including exposure conditions, etc. Clearly identified application
areas are electrical and electronic equipment, textiles, furniture, cars, trains, ships, aeroplanes and
construction products. Within these groups the end-uses may vary considerably. The conditions of
the application, such as temperature, humidity, light exposure, etc., not only define the needs for
material properties but also reflect on the required fire performance. One example is fire-retarded
wood boards that can be used both indoors in reasonably stable conditions and outside under
varying exposures. In addition, specific applications in railways and a marine environment demand
different types and levels of performance.
The assessment of hazard in real fire situations requires the coupling of material and fire properties
with fire dynamics, and thus cannot be based only on small-scale laboratory tests measuring one or
a few parameters. Essential factors affecting the fire performance under real fire conditions cover
the following:
Material properties, such as thickness, density, heat absorption, heat capacity and strength as a
function of temperature;
Fire properties, such as heat release as a function of time, smoke and gas emission and charring
rate; and
Fire dynamics with properties such as vertical and horizontal flows.
The main features of real fire performance are the target for simulation or description in
classification tests that usually are small or intermediate scale in size. Even smaller scale and very
simple methods can be used in product development for cases where classifications tests have been
performed that are representative of the product family and type of concern. These tests may be
very helpful if the parameter(s) measured are relevant to the larger scale classification test and if a
proper correlation can or has been established between the two scales.
Key parameters to estimate fire behaviour of fire-retardant products, or indeed any product, are the
classic stages of ignitability, flame spread, heat release, smoke production, toxic or corrosive gas
emission; plus charring rate and mechanical properties (retention thereof) at elevated temperatures.
8.2 Specific Tests
Fire testing is a very complicated subject. To start with, fire performance is dictated by
requirements imposed by various, differing, bodies, such as:
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Governments in order to protect lives and property;

Insurance companies with a financial interest in minimising losses; and
Fire brigades wishing to minimise fire-fighting hazards.
In Europe, each country has its own fire test systems and requirements. North America also has
several different large- and small-scale tests.
However, one fact remains certain: no single test, whether large or small, can be used to predict the
performance of materials under actual fire conditions. Very simply, there are too many variables in
a real fire that are too complex to be incorporated into a single test.
Consequently, the interpretation of any fire test result and individual product material performance
is a complex matter. Any test is only an indication of performance under the conditions of that test.
No test can simulate real fire conditions. No test can predict the source of ignition, configuration of
construction, nor the involvement and potential contribution to the fire of other combustible
products.
It is generally recognised, however, that large-scale tests are more informative than small-scale
tests. They have also been shown to give repeatable results. Results from different large-scale tests
correlate closely and therefore give valuable information that may not be learned from small-scale
examination of materials or products.
In the UK, the late 90s saw strong influences from insurance companies who are demanding their
own standards be met before insurance is granted on a building. This work has been largely
directed by the Loss Prevention Council (LPC, an insurance industry grouping) and often utilises
US-style large-scale tests.
The large-scale tests, which are believed to be amongst the best of those available, are the Factory
Mutual Class 1 Calorimeter Test, the FM 25-foot Corner Test, and the so-called Mini-corner test.
Each offers drawbacks and benefits that need to be carefully evaluated.
The FM Calorimeter Test is primarily used for rating various metal deck roof constructions. It is
becoming internationally accepted as the most representative acceptance criterion for the roofing
and insurance industries. Class 1 can result in lower insurance rates for the whole building.
In this test the insulation board is topped with a conventional 3-ply built-up roof and the whole
assembly is heated by direct flame impingement from the underside for 30 minutes. Fuelcontribution rates are determined by direct fuel substitution and the time-temperature details are
recorded for the assembly. The results are cross-checked with the limits for Class 1 approval. FM
claims that in 100 ft x 20 ft (~30 m x 6 m) building tests, composite steel roof deck assemblies with
acceptable Class 1 ratings, would not lead to a rapid spread of fire if subjected to an interior fire.
The FM Corner Test is for measuring the propensity of materials to flashover or develop selfpropagating flame fronts in a structure designed to simulate a large-unoccupied factory or
warehouse. The test enclosure is 25 ft high (8 m) with one wall 50 ft long (over 15 m) and another
38 ft long (10.7 m). The test material is installed on the walls and/or ceiling, with or without
sprinkler protection, and is exposed to a fire generated by a 340 kg crib of wood. This crib
produces a temperature of up to 1000 C within 5 minutes. The material passes the test if flames do
not exceed the limits of the structure and if other criteria, such as degree of damage to the structure
are met.
This corner test has gained international acceptance when related to the use of cellular plastic
materials in buildings that are 25-30 ft high (7.69.1 m), as is typical of commercial and industrial
buildings.
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The third widely used test mentioned is the Mini-corner Test. This was especially designed to
replicate the behaviour of products in the FM 25-ft test on a smaller scale. It has been successfully
used for predicting results of the FM Corner Test (to find the propensity of flashover), except for
materials that melt at low temperatures.
The main points in favour of the corner test are listed as:
The ignition crib produces a realistic fire source with temperatures up to 1000 C. (Compare
this with, say, the B2 test in which the ignition source is a Bunsen flame on foam at ambient
temperatures in the laboratory.)
The test configuration is similar to a room and any interaction of the product under test with
other components can be observed.
The products under examination are usually full-size panels and so the application and fixing
details can be the same as normally used in a construction.
These conditions create an environment in which three practical characteristics can be observed:
How easily does the product ignite?
Does the flame spread lead to fire propagation and, if so, at what speed?
Will this propagation lead to flashover and total combustion of the product being tested?
For economic reasons, or for screening purposes, small-scale tests are still often used.
For a totally new product type, it is always important to ensure that the small-scale test(s) used are
representative (i.e., correlation known and differentiation possible) in relation to
large/classification-scale test(s) when choosing test methods for product development purposes.
Examples of test methods to measure the key parameters of ignitability, heat release, flame spread
plus smoke and gas production are:
The cone calorimeter (ISO 5660) [Rate of heat release from building products, 1993]
Single burning item (SBI) (prEN SBI) [Building products excluding floorings exposed to
thermal attack by a single burning item, 1999]
Room/corner test (ISO 9705) [Full scale room test for surface products, 1993]
Spread of flame/LIFT (IMO FTP Code, Part 5 and ISO 5658-2) [International Maritime
Organisation, Fire Test Procedures, test for surface flammability, 1998 and Lateral surface
spread of flame on building products with specimen in vertical configuration, 1995]
Fourier transform infrared (FTIR) gas analysis spectroscopy
In most cases the classification criteria for reaction to fire behaviour are based on the assumption
that early phase fire development causes the main hazard. This means that the key elements for
effective fire retardants are to delay ignition and to reduce heat release and smoke production, at
least during the early part of exposure.
8.3 Comparing Test Results
The major and enduring problems in fire science and technology are trying to compare results from
different test methods and scales of test. The following are some of the points to be borne in mind:
1. The parameters used do not correlate. Examples can be found of attempted correlation in
which parameters of a different nature are compared, such as limiting oxygen index value and
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heat release under high irradiance or smoke production in well-ventilated and under-ventilated
conditions.
2. Different fire exposure levels. In small-scale tests, the fire exposure may be too unrealistically
low to be able to discriminate between different fire behaviours occurring on the larger (real)
scale. As an example, the new European SBI test uses a propane burner of 30 kW in a corner.
As a second guarding test a 20 mm small flame (prEN ISO 11925-2) is used. This small test
can be used only as a screening test to see whether there is not any chance of passing the SBI
test. This is seen for a range of wood products in Table 8.1, which shows that the small flame
test is not able to differentiate between the different classes of product performance. It is even
more difficult to compare small flame test results with those from experiments that generate
flash-over from the exposure of a surface panel to severe enough fire conditions.
Table 8.1 Comparison between results of SBI and small flame test
Product
SBI class
Small flame class
FR particle board
_
_
Intumescent coat on particle board
_
_
Melamine faced particle board
D
_
Particle board
D
_
Birch plywood
D
_
Medium density fibre board
D
_
Low density fibre board
E
_
3. Different types of exposure. Whether the exposure is radiative or convective/conductive (or
various combinations thereof) may cause major errors in the interpretation of comparative
results; small flame ignition time data may rank materials differently compared with ignition
times under purely radiative conditions.
4. Limitations of applicability. In some tests, the overall behaviour is dependent on the possible
spread of fire within the specimen area. An example is the SBI test in which heat release data
are quite comparable with cone calorimetry if those from the product tested are such that it will
not spread fire much beyond the area of highest exposure behind the flame in the SBI corner.
However, this simple correlation is most probably not valid anymore for a product that will
spread fire under the SBI method.
5. Behaviour of joints and fixings. In small-scale tests, effects arising from the joints and fixing
techniques are not possible to measure and thus intermediate or even full-scale tests are needed
to demonstrate those effects.
Even though there have been many improvements in the harmonisation of fire testing, there are still
many different testing and classification requirements to be defined for a number of products
depending on the area of application, such as marine applications where IMO fire testing is one of
the few global systems, construction products where Construction Product Directive-related
harmonisation is at last to take place in Europe, aircraft, railways, cables, etc.
It is the actual geometry of a final product in combination with the energy input of the flame
retardant test or fire that determines what the degree of flame retardancy will be. The laws of mass
and heat transport dictate that when the geometry changes, mass and heat transfer will change in a
strong non-linear way. As a consequence, actual fire behaviour can be vastly different on end
products compared to FR tests on small-scale test specimens of the materials out of which these
products are made.
This poses a dilemma for designing FR materials, as on the one hand one tries to develop new FR
compositions using small-scale screening techniques while in reality many products will be
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subjected to flame or fire retardant tests which do not display any appreciable correlation with
small-scale tests.
Cable manufacturers have used the LOI test as a screening tool in the development of FR materials.
Many are moving away from this approach and the general contemporary consensus is that UL94
VB tests offer a better indication of actual large-scale cable test performance, although the
correlation is still weak. Recent changes in FR standards concern the large-scale cable flame
retardant IEC332-2 test and intermediate tests such as the SBI. These new tests could require
reformulation of existing products to obtain a lower rate of heat release, to reduce smoke evolution
or to eliminate burning drips. It is likely that such reformulation efforts of FR materials will be
screened initially by determining the rate of heat release in a cone calorimeter or in the final
product test rather than by FR tests such as LOI or UL94 VB.
This discussion does not imply that small-scale tests should be ignored. The importance of having
ignition resistant and effective FR materials at low enthalpy input is a significant contribution to
fire safety. The ultimate goal of the FR product manufacturer is, of course, to develop flame
retardant products that are as safe as possible. This requires a balanced approach to develop
materials with the appropriate levels of flame retardancy over a range of practically relevant smallscale and larger scale FR tests.
8.4 Tests for Building Materials
The process of harmonisation for the testing of the reaction of building materials to fire has been
going for over a decade. The culmination of all the effort over the years has emerged as a panEuropean testing and classification system that divides such materials into classes A1, A2, B, C, D,
E and F. The test methods to be followed are:
Table 8.2 Harmonisation tests and standards
Test Method
Standard
Non-combustibility
Pr EN ISO 1182
Calorific value (PCS)
Pr EN ISO 1716
Single burning item (SBI)
Pr EN 13823
Small burner test
Pr EN ISO 11925-2
Flooring radiant panel
Pr EN ISO 9239-1
Classification
Pr EN ISO 13501-1
Although some of the test methods are new, most are established techniques with slight
modifications.
Floor coverings are tested by the radiant panel method, which is already in use in most European
countries. The test methods for determining the calorific value and to confirm the nature of noncombustible materials (currently Class A building materials in Germany) are also well established
and have been modified only slightly for the European classification system.
A class E ranking, that means minimal demands on reaction to fire (e.g., currently class B2 in
Germany, denoting normal flammability), is awarded on the basis of results from the small burner
test, which is used in similar form in many European countries, such as Austria, Italy and
Germany).
For classifying combustible building materials in classes B to D, the single burning item test (SBI)
has been produced. It was developed using flat building elements for wall and ceiling linings, then
subjected to a round-robin test and finally verified in a room corner test (ISO 9705). The
specimens, of 1 m x 1.5 m and 1.5 m x 0.5 m, are arranged orthogonally, flat against the walls of
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the room corner with the largest dimension vertical, and exposed to a diffusion flame of 30 kW.
The heat release is determined by the oxygen consumption method, where the consumption of
oxygen is proportional to the heat released when an organic material burns.
An important characteristic is the fire growth rate (FIGRA), which is calculated by dividing the
heat released when the product burns by the time at which a specific rate of heat release is reached.
It should correlate to the time to flashover in the room corner test.
An additional criterion for ranking products in the SBI test is the total heat release (THR) in the
first 10 minutes of the test. Also determined are the smoke emission and the presence, or otherwise,
of burning drops or particles.
Unlike the previous tests that it supersedes, the SBI test involves exposing a relatively large area of
the specimen to a flame. The fire scenario in the SBI test also ignores the early stages of the fire
and any smouldering that may occur after the burner is removed. This may lead to different, often
worse, classifications as regards reaction to fire than was previously the case for any individual
material.
In particular, melting thermoplastic materials are often classified less favourably in the SBI test
because, first, a large amount of melted material may accumulate near the burner and be ignited by
the persistent heating, and, second, the poorly reproducible melting gives rise to relatively
extensive scatter of the test results.
The SBI test also classifies smoke. One criterion employed is the smoke growth rate (SMOGRA).
This is the maximum quotient of smoke emission divided by the respective point in time. There is
controversy about the relevance of such a value as regards risk posed by smoke emission in the
event of a real fire.
Owing to the relatively large amount of material that is decomposed in the vicinity of the burner,
many plastics end up with an unfavourable classification. By contrast, wooden materials, which
only evolve large quantities of smoke when they smoulder, receive a relatively good classification.
It is feared that the very existence of a smoke classification in the new Euro system, no matter how
inappropriate, may lead legislators to impose demands that were absent from previous building
regulations.
The SBI test was designed for two-dimensional products and it has still not been established how to
adapt or apply such a test for non-planar parts such as pipes, cables and linear seals. Indeed, the
cable industry is moving towards total unacceptance of the new system, and is proposing its own
system that would feature completely different test methods.
It remains to be seen how building products that cannot be tested by the SBI method will
eventually be tested, whether in a large-scale room-type test or another scenario; and also how
these various tests, under the new European classification system, are incorporated, as they
eventually must be, into national building regulations.
In the Single Burning Item test, the reaction of materials to fire is divided into Euro-classes (prEN
13501-1), see Table 8.3.
The SBI test will succeed the following national standards, among others, in the construction
industry:
110
DIN 4102;
Epiradiateur NF-P-52-501/NF-F-16101/2;
BS 476 Parts 6 & 7.
Table 8.3 Proposed European standards for the construction sector

Specification
Applied standard
No contribution to fire
ISO 1182 + ISO 1716

prEN SBI
prEN SBI
prEN SBI
prEN SBI
DIN 4102-1
DIN 4102-1
Hardly any contribution to fire

Little contribution to fire
Acceptable contribution to fire
Acceptable reaction to fire
No classification for fire
Euroclass
A1
A2
B
C
D
E
F
DIN 4102
Category
A1
A2
B1
B1
B2
B2
B3
Unlike DIN 4102, in which some melting test specimens are rated as superior to non-melting
materials but exhibit totally different behaviour in a real fire, the SBI test offers the possibility of
testing the materials under more realistic fire conditions.
The so-called Euro classification system for fire performance of building products will be in the
form of a tool kit of criteria, based on a common test procedure, from which individual Member
States will be able to select the requirements for their own specific standards.
This approach should separate detailed test standards from product classification and result in a
reduction of the amount of testing required. Only the SBI test will be needed and is expected to
give all the basic data required for the classification system. As a consequence, product standards
throughout the EU will refer only to classification standards; and appeals against standards set by
any individual country will only be allowed in reference to the classification.
An appeals procedure and the use of a large-scale room-corner reference test could be invoked in
cases where it can be argued that the SBI test might not give a true reflection of the reaction to fire
performance in a given end use. Such appeals can be requested by Member States or industry
federations and CEN, the European standards authority.
A transition period of some 8 to 10 years will probably pass before the relevant legislation and
standards have been adopted in each country. Even then, the individual Member States will be able
to set the level of fire performance they require in any particular circumstance, and products will
have to meet that level in order to sell for that purpose in that country.
8.5 Cable Testing
An EC funded project has been examining the various test methods that are used to evaluate
electric cables and their fire performance. This was funded by DG XII of the Commission and is
designated as Fire Performance of Electric Cables (FIPEC). Various levels of testing have emerged
from the project ranging from a small-scale, cone calorimeter test procedure especially developed
for cables and their constituent materials, a full scale procedure based on IEC 60332-3, but utilising
heat rate release and smoke production rate (SPR) measurements, and a real scale test for mock
cable installations.
Companies involved came from the cable manufacturing sector, cable users, material suppliers and
research bodies.
8.6 Mattress Tests
In the US, the federal government considered rejecting proposals to label PU mattresses with fire
hazard information. The Consumer Product Safety Commission was responding to a petition from
the Childrens Coalition for Fire Safe Mattresses, but the CPSC wishes to adopt fire standards that
111
would consider how an entire mattress behaves in a fire, not just the filling material. It is
recommending the development of complete standards for mattress flammability from open-flame
ignitions.
8.7 Clothing Tests
The protection of clothing, specifically nightwear, is only regulated in the UK and Ireland. Various
committees under the Consumer Policy and Health Protection Directorate (DG XXIV) of the
European Commission and the European Standards Body (CEN) have in recent years been
considering the introduction of a requirement for nationally enforceable specifications under the
umbrella of the General Products Safety Directive (92/59/EEC). A feasibility study mandated by
the European Commission on CEN was handled by Technical Committee CEN TC248 for Textiles,
Subcommittee 1 on burning behaviour.
This Study Mandate M/263 of December 1997 found that EN 1103:1995, a standard for the
burning behaviour of apparel fabrics should be the basis of a nightwear standard and that further
protocols were needed to consider any toxicological and dermatological risks from any treatments
used on such fabrics to meet any subsequent standards. The feasibility study identified a set of
parameters, which determined the fire resistance of nightwear and these must be taken into account
by the proposed standard. The two main parameters were rate of flame spread and flame surface
flash. Test methods capable of measuring these parameters must be determined. Factors such as
care maintenance, the ageing of nightwear by washing and drying must also be addressed. Any
flame retardants employed on the textiles should not be prohibited or be assessed as unacceptable
risks by the EC under any regulations or Directives.
These conclusions from the Study Mandate have resulted in a Standardisation Mandate for the
preparation of a draft standard. Mandate M/304 for such work was accepted and approved by CEN
in December 2001 and passed to the same committee, TC248.
The development of the requisite technical standard(s) is now underway. Once the necessary
mandated technical standards have been agreed, sleepwear sold throughout the EU will have to
comply with the agreed performance requirements. Thus the future should offer an enhanced level
of fire safety for nightwear, and protection for the most vulnerable, such as the very young and the
elderly.
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9 Environmental and Regulatory Matters

The saga of the effects, benign or malignant, of brominated diphenyl ethers continues, with hope
that a more scientific approach has at last been seen as the route forward. Waste directives relevant
to flame retardants have now been promulgated by the EU and the general attitude to halogenated
species also continues to attract attention in the chemical community.
This chapter covers some comments and information relating to fire safety, recycling and
environmental issues.
9.1 Fire Safety
Fire safety is an integral part of fire precautions, which aim to minimise the number of fires and the
damage from them. These measures hinder the initiation of fires, limit their propagation and, if
possible, exclude flashover. Preventing fires or delaying them makes escape possible over a longer
period of time. As a result, life, health and property are efficiently protected.
A fire always follows the same basic pattern of initiation, development to a full fire and then its
decrease. Fire precautions for combustible materials only apply to the early stage of a fire, i.e., the
initiating fire phase by preventing ignition and by influencing the parameters of fire propagation
and heat release.
The influence of new legislation is essential for increasing the fire safety level in many fields. One
striking example is the introduction of the UK regulations for flame retarded upholstered furniture
in 1988. It shows a drop of fires and a dramatic fall in deaths caused by such furniture. Compare
the figures for 1988 of 4818 recorded fires and 247 deaths to 1993 when there were 3746 fires and
146 deaths.
The fire safety of electrical and electronic equipment is promulgated by rules and regulations for
product safety laid down mainly by bodies such as Underwriters Laboratories (UL) in the USA,
and used all over the world. Standards organisations like the International Electrical Commission
(IEC) have fire safety requirements that may sometimes be based on those in UL standards.
Plastics used in E&E equipment have to meet both materials and finished components fire safety
requirements. They are part of product safety standards like UL 1950, CSA 22.2, IEC 950 and EN
60950 for business machines and UL 1410, UL 746, IEC 65 and EN 60065 for the safety of
consumer electronic items (see Table 9.1).
The flammability of the plastics materials covered by various UL safety standards are covered by
the ubiquitous UL94; Tests for flammability of plastics materials for parts in devices and
appliances and its counterpart IEC 707, to evaluate their performance with respect to resistance to
ignition and flame propagation. Depending on the requirements, materials have to meet horizontal
burning tests, UL94 HB or the more stringent vertical burning tests, Class UL94 V-2, V-1, V-0 OR
5V. These tests simulate ignition sources of lower energy that may occur in E&E equipment and
impinge on plastics parts in electrical components.
Materials meeting the highest levels of these Bunsen burner tests, V-0 or 5V, have proved most
effective in conferring a high level of safety to E&E equipment against both internal and external
sources of low energy ignition. Contrary to the USA, where UL94 V-0 classification is nearly
always required for plastics materials used in office and consumer electronics; in Europe, according
to IEC 65, besides plastics used as fire enclosures, major plastics parts like TV-set back plates and
housings only have to fulfil the horizontal classification, HB.
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Table 9.1 Product safety standards

Business Equipment
UL 1950
Underwriters Laboratories. Information technology equipment including
electrical business equipment.
CSA 22.2
Canadian Standards Association. Safety of information technology equipment,
including electrical business equipment.
IEC 950
International Electrotechnical Commission. Safety of information technology
equipment, including electrical business equipment.
EN 60950 / European Standard. Safety of information technology equipment, including
A2
electrical business equipment.
Consumer Equipment
UL 1410
Underwriters Laboratories. Television receivers and high-voltage video products.
Underwriters Laboratories. Polymeric materials
UL 746
Short term property evaluations
A
Long term property evaluations
B
Use in electrical equipment evaluations
C
Fabricated parts
D
Industrial laminates, filament wound tubing, vulcanised fibre, and materials used
E
in printed wiring boards
IEC 65
International Electrotechnical Commission. Safety requirements for mains
operated electronic and related apparatus for household and similar general use.
EN 60065
European Standard. Safety requirements for mains operated electronic and related
apparatus for household and similar general use.
In a Draft for the revision of IEC 65 issued in the late 90s, basically no more flammability
requirements at all are foreseen if the plastics materials exceed a certain distance from potential
ignition sources with open circuit voltage. The same is true if potential ignition sources are
protected by a fire enclosure; the other materials in a TV will require no safety classification. The
new IEC 65 draft would thus allow the use of TV backplates and housings without any fire safety
classification, because it relies on the technical design of the TV rather than on the safety level of
the materials used.
In the past, in Europe, plastics used for backplates and housings in office and consumer electronics
virtually all complied with the high specifications of V-0 and V-1 classifications. This guaranteed a
high level of fire safety of materials against internal fire sources plus external ones like candles.
For TV sets, this was done on a voluntary basis, as, in principle, only the low levels of fire safety
requirements for materials in IEC 65 had to be met.
9.1.1 European Standards for Television Sets

Starting in Germany in 1993, requirements that excluded the use of halogenated flame-retardants
and plastics for copiers, PCs and printers were introduced. These were given eco-labels (Blue
Angel Eco-label). TVs that did contain them were deprecated in consumer magazines.
As a consequence, the majority of TVs available in Europe now no longer contain flame retardants
at all in backplates and housings.
Backplates and housings make up the majority of plastics used in TVs. The use of materials with
lower safety levels in such appreciable amounts could affect the overall fire safety level of E&E
equipment with, as a consequence, a lower degree of protection for life or property. In addition, as
more fires would result, the environment would also become affected. Therefore, fire safety should
be included as an environmentally relevant criterion in the requirements for eco-labels and
consumer magazines.
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Introducing fire safety, as an environmental criterion, would further fit into the attempts worldwide
to hold and extend the existing high level of fire precautions. The international harmonisation of
fire regulations in building, transportation and electrical engineering and electronics will eventually
create global requirements for combustible materials and finished parts where high levels of fire
safety will have to be achieved.
Work in the US at the end of the 1980s by the then National Bureau of Standards (now the National
Institute of Standards and Technology) had conclusively shown that housings containing flame
retardants and so meeting higher fire safety requirements better resisted ignition and delayed flame
propagation and subsequent involvement of the whole apparatus in the fire than non-flame retarded
products (NBS Special Publication 749, 1988). It was shown that the total quantity of toxic
combustion products released by the flame-retarded plastics (expressed as carbon monoxide
equivalents) was one-third that of non-flame retarded plastics. An extensive, more recent, study by
an independent fire consultancy in Germany has confirmed such findings for TVs and PC monitors
and has warned against ignoring fire safety in any push for chemical correctness and protection of
the environment. Findings from this work include:
The materials flammability tests carried out showed that sufficiently flame retarded plastics
meet the high requirements of vertical tests, UL95 V. The low flame retardancy of non-flame
retarded plastics only met the lower horizontal tests, UL94 HB.
The tests with external ignition sources of increasing intensity showed that flame retarded
UL94 V plastics generally do not burn, whereas HB-rated plastics readily ignite when exposed
to the lowest energy ignition source, typical of a short-circuit or to accidental contact with an
open flame.
Older model European TVs and backplates generally have higher safety levels than new sets
currently available in Germany.
New TV sets and backplates purchased in Germany can in most cases be ignited by the lowest
energy ignition source.
TVs bought in Japan and the USA have high to very high fire safety levels.
New PC monitors have high fire safety levels. They do not burn when exposed to the different
ignition sources.
In two simulated real life fire tests in a fully furnished room, a new TV purchased in
Germany when ignited by the lowest level of heat source, led to flashover in the room after just
about 7 minutes. A TV form the USA did not ignite and did not burn at all, even when exposed
to the highest intensity ignition sources.
There is therefore a need to use plastics parts with a higher level of fire safety meeting the
requirements of UL94 Vertical tests so as to ensure adequate consumer protection. External fire
sources, inadequate design, manufacturing faults or defects due to simple wear and tear, plus
consumer misuse may lead to flashover and fully developed fires in a very short time if housings
and backplates are not flame retarded to meet the vertical test criteria.
To optimise fire safety for TVs in Europe, housings and backplates should be made resistant to
external ignition sources at the lower end such as candles. This could be achieved by harmonising
fire safety standards for consumer electronics with the North American requirements by upgrading
the IEC 65 Standard used in Europe.
Fire safety plays a key role in society, because it helps to reduce fire hazard and so prevent fires. It
contributes to the saving of human lives, to protect property and, indirectly the environment.
Therefore, the objective of all should be to hold and improve fire safety levels in all fire and
environmental regulations and technical standards.
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A leading European fire expert, Jurgen Troitzsch, has spoken out about the weakness of the
European standard of flame retardancy for TV sets.
As fire safety standards have been relaxed in Sweden, fires attributed to E&E increased by >30%
during 5 years to 2000.
9.1.2 Brominated Flame Retardants

The Brominated Flame Retardant Industry Panel, the US industry trade association within the
Chemical Manufacturers Association commissioned work to quantify the benefit derived from
BFRs in the USA. The basis of this analysis is US fire data from the National Fire Protection
Association (NFPA). This study concluded that within US experience, the total number of lives
saved as a result of the use of brominated flame retardants in the analysed products ranges from
630 to nearly 1000 a year (Table 9.2).
Table 9.2 Estimated lives saved by brominated flame retardants annually in the USA
Product flame
Total lives saved
Maximum
Total lives
Total lives
retarded by
from secondary
potential lives
saved from
saved
brominated
ignition
saved
direct ignition
additives
Television and
90
100
190
510
appliances
Electrical wiring
> 80
> 80
> 80
Fabric back-coating
144
160
Cushioning
216
216
Total
> 630
> 960
Source: The Contribution of Brominated Flame Retardants to Life Safety in the United States,
Benjamin/Clark Associates, Inc., reproduced with permission from Speciality Chemicals Magazine.
There have been ongoing discussions about emissions from the incineration of plastics that have
been flame-retarded. On this issue the WHOs International Program for Chemical Safety has
stated of PBDEs that properly controlled incineration, i.e., according to current European
regulations, does not lead to the emission of significant quantities of dioxins or furans.
There has also been some discussion about what happens when products made with BFRs burn in
accidental fires, such as the catastrophic fire at Dsseldorf Airport in 1996. However, the official
report on the fire stated that dioxins and furans were either not detected or were found at levels well
under the limit values considered today.
The Fire and Environmental Protection Service, a highly respected organisation in German and
European fire safety circles, has shown by the scrupulous analysis of the outcome of fires involving
plastics materials, and two well documented German fire disasters that the cancer risk from PAH is
up to 500 times higher than that of polyhalogenated dioxins and furans. The Dsseldorf airport and
Lengerich fires gave rise to wild speculation about the chemical species that caused and
represented the most danger. As with all fires it was shown that carbon monoxide contributes
overwhelmingly to the toxic hazards generated and causes over 90% of fatalities in fires.
Decomposition products from flame retardants, like HBr, HCl and HCN, do not play a role in the
acute toxicity of fire gases, which is driven by carbon monoxide. This is also true for the formation
of dioxins and furans. PAHs are found in high amounts in all fires involving any natural and
synthetic carbon-based materials (i.e., almost any non-metallic material) and include carcinogens.
Polyhalogenated dibenzodioxins (PHDD) and furans are generated from organic or inorganic
116
compounds in fires at usually 3 orders of magnitude lower amounts, and then only when halogencontaining materials are present.
The impact of PAHs and PHDD and furans in the two major fires mentioned showed that the
cancer risk from PHDD/Fs is substantially lower than that of PAHs. Both pollutants are strongly
bound to soot and they are of low bioavailability. This explains why no chronic toxicity effects
from these pollutants were reported, not only by persons accidentally exposed to fire gases during
one exposure, but also from frequently exposed professionals such as fire fighters and sanitation
personnel.
The findings of these two fires indicate that the chronic toxicity potential from dioxins and furans is
highly overestimated and that the contribution of polybrominated dioxins and furans released by
the flame-retarded plastics is negligible.
Regarding the end use and also recycling and incineration aspects, more and more studies have
been conducted on smoke and the products of decomposition.
In 1996, the well-respected German testing centre Forschungszentrum Karlsruhe ran combustion
trials at its TAMARA pilot incinerator. Results indicate that, even under extreme conditions,
electrical and electronic (E&E) plastic waste can safely undergo co-combustion with municipal
solids.
The work carried out at Karlsruhe has given further proof that municipal solid waste combustion
is an ecologically acceptable and economically sound disposal route for typical amounts of
electrical and electronic waste containing brominated flame retardants. Some of the main
conclusions of this work are:
The high amounts of E&E plastic waste material added has a positive influence on the
combustion process (i.e., cleaner and more complete combustion) and the burnout of the
bottom ashes has improved.
The dioxin and furan levels remained within the range typically found in such incineration
plants the addition of the extra E&E waste did not increase these levels.
Reflecting on the emissions throughout the production, use and disposal of TV sets, the latest
LCA studies conclude that there is significantly higher emission of polycyclic aromatic
hydrocarbons (PAH) and halogenated dibenzodioxins/furans for non-flame retardant TVs.
The positive contribution of brominated flame retardants as a life saver is a proven fact and
European manufacturers of electronic goods should not jeopardise fire safety in an attempt to gain
market acceptability.
As fire safety standards have been relaxed in Sweden, fires attributed to EEE increased by >30%
during 5 years to 2000.
E&E enclosures made from flame-retarded resins are effective in preventing the ignition and
spread of fire, in turn saving lives and the destruction of property. Numerous studies and a broad
base of fire experience have demonstrated the value of flame retardants. Some of the conclusions
that these studies point out are that, compared to plastics with no flame retardants, FR plastics:
Provide up to 15 times more escape time.

Release only one-third the amount of toxic gases (CO equivalents).
Generate essentially the same amount of smoke.
117
In the US, the estimated annual saving of life by the use of BFRs in E&E is 190, with a maximum
figure of 510 souls. European statistics have been analysed and show that at least 16 lives are lost
each year as a direct result of TV fires, with the true figure perhaps up to ten times higher.
Such data reaffirm the need for FR plastics of the highest safety standards to ensure appropriate
consumer protection.
9.2 Brominated Flame Retardants
Brominated flame retardants (BFRs) are often the most effective when both performance and cost
are considered. While these FRs are of positive benefit, used to protect the polymers that make up
television sets, personal computers, soft furnishings, etc., they are now an issue related to
environmental pollution and, in some quarters, deemed toxic. Some studies indicating the presence
of polybrominated diphenylethers (PBDEs) in marine life and breast milk have added fuel to the
environmental lobbys calls to have these products banned or their use severely restricted.
Manufacture of BFRs requires specific handling and expertise and, for this reason, they are
produced in a few specialised facilities around the world. In response to concerns about their
products and to focus their efforts in research, the major producers have established an organisation
to steer the work. The Bromine Science and Environmental Forum (BSEF), which comprises
Albemarle, Dead Sea Bromine, Great Lakes Chemical, Elf Atochem (as was) and Tosoh, was
established in 1997 to conduct scientific research and to provide scientific data to support the safe
use of bromine-containing products.
The BSEF admitted that brominated compounds and halogenated materials in general have had a
bad press. But the industry has for some time sought to look at the issues surrounding BFRs and
their use by addressing environmental exposure and looking at product composition. Industrys
commitment does not propose a ban or phaseout of BFRs.
Brominated flame retardants can be divided into three main groups: polybrominated diphenyl
ethers (PBDE), hexabromocyclododecane (HBCD) and tetrabromobisphenol-A (TBBPA), which is
by far the most widely produced and used of all the brominated flame retardants.
Of the PBDE group, decabromodiphenyl ether (decaBDE) is the most widely used and, according
to studies, no trace of decaBDE has been found in the environment. What is more, current research
has shown that this compound cannot be broken down into the shorter chain compounds. TBBPA
and HBCD, used in a wide range of products, have not been found in the environment either,
according to this current research.
Meanwhile the shorter chain PBDEs have been found widely, particularly in the marine
environment. However, the chairman of the BSEF has commented that the flame retardant industry
has not and does not produce or use these shorter chain compounds in any large quantity. In fact
recent studies show that pentabromodiphenyl ether (pentaBDE) was widely used by the mining and
drilling industry in the 1980s and early 1990s as a hydraulic fluid, yet no one looks into these
industries to explain the presence of these compounds in marine life.
These latter industries seemed unwilling, at the time, to contribute to the debate or the research. It
must be remembered that the flame retardant industry is a relatively young one, established in the
early 1970s, and the BSEF highlights a report published in 1992, which provides evidence of
PBDEs in sediment dating back to the 1940s.
So what are the other possible sources of these compounds? Apart from the historic uses already
mentioned, it is known that many organobromine compounds, including chemical precursors of
brominated flame retardants are naturally present in marine life.
118
There has always been a school of thought that anything naturally occurring, part of the
environment, would be dealt with by nature, being easily broken down. This theory may need
reappraisal after a study at Carlton University. This claims (in Environmental Science and
Technology, an ACS publication) to have found a naturally occurring substance that is similar in
chemical structure to PCBs, an industrial chemical banned because of damage it caused to the
reproductive systems of wildlife, particularly birds, that had eaten fish from polluted waters. These
pollutants contain chlorine and bromine and the work appears to have identified a naturally
occurring substance that is as persistent as any man-made pollutant. If the findings are proven, it
could mean a radical rethink not only by the many environmental groups lobbying to ban halogencontaining compounds, but also a radical look at the policy making business.
Of course, the flame retardants industry cannot rule out misuse by itself or its customers, and to this
end producers set up a programme of product stewardship in order to educate all those using
brominated flame retardants as to best practice. BFR loading in polymers is illustrated in Table 9.3.
Table 9.3 Examples of brominated flame retardant loadings in polymers (V-0 classified)
Loading of BFR
Loading of Sb2O3
Base Polymer Brominated flame retardant
(%)
(%)
23
8
Polypropylene Decabromophenyl ether
27
8
Ethylene
bis(tetrabromophthalimide)
Polystyrene
Decabromodiphenyl ether
12
4
Tetrabromobisphenol-A
15
4
ABS
Octobromodiphenyl ether
20
6
Tetrabromobisphenol-A
20
4
4
12
PET
Decabromodiphenyl ether
4
17
Pentabromobenzyl acrylate
4
18
TBBPA carbonate oligomer
Source: R Borms, European Chemical News.
To facilitate a better understanding of the issues surrounding BFRs, the BSEF set up a research
programme, which was carried out by independent researchers at the Netherlands Fisheries
Institute. The research has been broken down into several main areas:
Food chain residues will look at how the shorter chain PBDEs have entered the marine life, the aim
being to trace the route and follow it right back to its source.
Sediment core studies will also be carried out, whereby sediment from the ocean will be taken,
dated and analysed. This will put a timescale to the presence of these brominated compounds. The
results will be looked at in relation to the existence of the flame retardant industry and any possible
use prior to the development of BFRs.
The programme is expected to last two years, with summaries of progress published on a regular
basis. Other issues that the BSEF will address are recycling and life cycle analysis (LCA).
Consumer safety is an ever-growing issue. With consumer purchasing power rising and the number
of personal computers and other electronic equipment in the home increasing, politicians and those
in a position to make policy, will have to weigh up some very serious issues. Manufacturers of
electrical products, particularly those aimed at the European market, may have to look at the
possibility of consumers laying the blame squarely at their door, when it is realised that a serious
incident could, perhaps, have been prevented if adequate levels of BFRs had been used.
A report commissioned by the UK Department of Trade and Industry has indicated the benefits
from BFRs outweigh the possible hazard risks to the environment and human health. The report
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entitled Risks and Benefits in the Use of Flame Retardants in Consumer Products describes the
work carried out at the Polymer Research Centre of Surrey University, England.
It concludes that there are many benefits from using flame retardants. An example is the reduction
of the risk of death or injury from a fire involving consumer products, such as upholstered
furniture, by between 30-90% when flame retardants are used. The UK government accepted the
report as an important contribution to the debate on the use of FRs in consumer products and is also
supportive of the risk assessment work commissioned by the EU, underway in the mid 1990s.
There have been, however, concerns about the safety of brominated flame retardants. Although in
1995 the World Health Organisation (WHO) found that the risk to the general population from
TBBA was insignificant, more recent research has cast doubt on this conclusion. Concern arose in
Sweden following revelations that brominated FRs caused irreversible brain damage and disrupted
thyroid systems of newborn mice. Also, levels of polybrominated diphenyl ether have been found
in the breast milk of Swedish women over the last 25 years. With claims that TBBA has hormonedisrupting effects, the Swedish Chemicals Inspectorate recommended that two groups of
brominated flame retardants be phased out within five years.
A further safety concern was that combustion of brominated flame retardants might lead to the
formation of bromodioxins. The possibility of combustion is perhaps less of a worry because the
dioxins are produced at around 600 C higher than processing temperatures but lower than fire
temperatures. And old computers and televisions are usually dumped in landfill sites rather than
burned. Furthermore, manufacturers are now developing brominated FRs that do not produce
dioxins on combustion, and others that char rather than burn so that the bromine is retained in the
residue.
Nonetheless, the WHO recommended that brominated flame retardants should not be used where
suitable replacements are available. Plastics containing no flame retardants are now being used in
computer monitor housings. These have an internal fireproof metal layer, which also provides
electromagnetic shielding. Whether this is a satisfactory substitute for flame retardants is still very
uncertain.
Moves to legislate for the recycling of electrical products and the partial phase-out of some
brominated flame retardants has resulted in the WEEE and RoHS Directives (see Sections 9.3 and
9.4).
Results of the studies commissioned by the BSEF have given a strong signal of support for the
probity of BFRs. Findings from the highly regarded GfA laboratory at the University of Erlangen,
Germany say that BFRs do not hinder plastics from being recycled and can withstand at least five
recycles. This has important implications for the use of plastics in electronics since it was shown
that HIPS retarded with decaBDPE will meet the requirements of the German Chemicals Banning
Ordinance, which is regarded as one of the strictest regulations in existence.
The findings provide strong support for the BFRs known to be among the most efficacious of flame
retardants for plastics, especially engineering ones. Three separate elements within the test
programme provided the following results:
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Formation of dioxins/furans: A compound containing standard loadings of decaBDPE was

injection moulded and reground to simulate recycling. After five cycles the material was
analysed for brominated dioxins and furans. The compound showed no detectable amounts and
the recycled forms showed levels below the limit of the German Dioxin Decree by a factor of
about 40.
Debromination: The same compound was analysed for possible degradation of the FR additive.
Comparison of concentrations before and after recycling showed no change, indicating that no
decomposition (i.e., debromination) had occurred.
Workplace exposure: A flame retarded PS was subjected to two successive simulated recycling
cycles and workplace exposure to PBDD/F was monitored during processing. At all stages,
exposure to dioxins/furans was below the German workplace limits by about two orders of
magnitude.
The BSEF said that recycling was the key to future environmental sustainability of many industrial
processes and it was necessary for additives manufacturers also to help users of plastics (e.g.,
makers of electronic equipment) to close the loop.
Another study, at a recycling plant in Sweden, showed that the workers were being exposed to
diphenyl ethers. BSEF is collaborating with the company to develop the best practice for its
processes.
In September 2001, the European Parliament took the unprecedented step of voting to ban two
chemicals for which risk assessments were still ongoing. Octabromodiphenyl ether (octaBDE) and
decabromodiphenyl ether (decaBDE) were lumped in with pentaBDE during a debate on the ECs
proposed ban on the latter chemical, which was based on an already completed risk assessment.
All three flame retardants would be banned by 2006 according to the parliament. OctaBDE should
be banned by mid-2003 and the deca- version three years later. However the decaBDE ban would
be repealed if the completed risk assessment shows it to be harmless.
Penta residues in other substances must not exceed 0.1%, according to the parliament vote, rather
than the 5% limit proposed by the EC.
These measures, heavily altered, reached final adoption in December 2002, as a formal
Amendment to the Use Ban Directive of 1976 that relates to restrictions imposed on the
marketing and use of certain substances deemed dangerous after suitable scientific investigation.
Parliament and Council have decided to exclude from this Directive decaBDE in view of its
importance for fire safety and due to an ongoing scientific risk assessment being due to be finalised
by the EU in 2003. The Directive will consequently prohibit only octaBDE and pentaBDE from the
EU market by mid-2004.
The risk assessment of decaBDE has so far found no significant risk and its completion in the
Summer of 2003 will be the basis for any future policy decision on decaBDE.
DecaBDE is widely used to protect furniture textiles from fire sources in accordance with UK and
Irish furniture fire safety legislation, which provides the consumer with the highest levels of fire
safety in the world. An estimated 3,160 lives have been saved by the UK legislation alone in the
period 1988-2000.
A new study carried out by Toronto University finds that, of the 3 PBDE flame retardants, neither
decaBDE nor octaBDE is likely to be transported in the environment over long distances. The
study clarifies recent reports from the Arctic Monitoring and Assessment Programme (AMAP)
which incorrectly stated that PBDEs had been found in the Arctic when this should only have
referred to the constituents of pentaBDE.
The potential for substances to be transported over long distances or as it is technically known, the
potential for long-range transport (LRT), is one of the four recognised criteria in assessing whether
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or not a substance might qualify as a persistent organic pollutant (POP). (The other three criteria
for defining a POP are persistence, bioaccumulation and toxicity.)
Researchers in the field of environmental modelling at Toronto University have studied the
potential for LRT of the constituents of the three PBDE flame retardants known as pentaBDE,
octaBDE and decaBDE. These products have different physico-chemical and also different
toxicological properties.
The recently completed study used the most advanced mathematical models to estimate whether or
not the investigated substances have a potential for LRT. The various models used all came to the
same conclusions:
PBDEs with a low degree of bromination such as those contained in commercial pentaBDE are
likely to undergo LRT
PBDEs with seven or more bromine substitutions, such as those which make up most of
commercial octaBDE and which make up the total content of decaBDE, are likely not to be
subject to LRT.
These conclusions are supported by recently published monitoring studies, which find the
constituents of pentaBDE at remote locations (Arctic, Siberia, etc.), but which do not find any
substances related to octaBDE or decaBDE at the same locations.
The Dutch Ministry of the Environment announced in February 2003 that the temporary ban of the
production, trade and use of the flame retardant FR-720 shall not be prolonged This means that
imports into the Netherlands of BDBPT and products containing BDBPT will not be restricted. FR720 is the bis(2,3 dibromo)propyl ether of TBBA.
The temporary ban proved unjustified as it lacked scientific evidence that BDBPT should be of any
concern with respect to acute toxicity. The product is not found in the environment and an initial
risk assessment in January 2002 commissioned by the industry for the Dutch Government showed
the substance was of no concern.
The EU Commission had opened an infringement procedure against the Dutch Government on the
basis of an unjustified barrier to trade. The ban would have also set a precedent whereby any EU
Member State could have banned any substance merely on the grounds of incomplete data and
ignoring the need for further science to be conducted.
Following the decision to lift the ban, further research is to be conducted on behalf of the Ministry
of Environment by RIVM, the Dutch National Institute for Public Health and the Environment with
publication by end of 2003.
9.3 EU Directives
The German Environment Ministry attacked European proposals to ban individual substances, such
as specific flame retardants in the draft regulations for the recycling of electrical and electronics
equipment. They were backed by the countrys Ministry of Economic Affairs. The Environment
Ministry saw no need for binding recycling targets and opposed substance bans such as those
proposed for lead and the PBDE and PBB flame retardants. Both Ministries were concerned at the
excessively prescriptive and restrictive system being proposed at that time (2000) for electrical and
electronic waste by the EU Commissions Environment Directorate-General.
They had planned to include a phase-out of PBDEs in the disposal of Waste Electrical and
Electronic Equipment (WEEE) Directive, in spite of the fact that preliminary conclusions under EU
risk assessments indicated that there was no need for risk reduction from the two types, decaBDE
and octaBDE, mainly used in such equipment.
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The German criticism is part of a growing call that substance restrictions should have no place in
waste legislation, but should be separately considered and be based on life-cycle risk assessments.
For example, German legislation on end-of-life IT equipment does not contain any substance
restrictions. Studies in Germany have effectively demonstrated that polystyrene compounds flame
retarded with decaBDE, which is widely used for housings of such equipment, meet the stringent
demands of the German Chemicals Banning Ordinance. The studies also indicated that no
detectable quantities of brominated dioxins or furans were formed during recycling, that there was
no debromination of the additive and that the exposure of workers to dioxins/furans was at least
two orders of magnitude below German workplace limits.
Another factor is the consideration that the material bans contained in the draft WEEE Directive
would infringe international trade agreements.
The surprise move by the EC in mid-2000 to make three separate pieces of legislation out of a
single original draft directive on waste electrical and electronic equipment (WEEE) served to
concentrate attention on brominated flame retardants (BFRs) in such applications.
Under the early draft, EU countries shall ensure that the use of lead, mercury, cadmium,
hexavalent chromium, PBB, and PBDEs (polybrominated biphenyls and polybrominated diphenyl
ethers) in electrical and electronic equipment is substituted on 1 January 2008. These have now
become the subject of the Restriction of Hazardous Substances directive (RoHS). Additionally the
Commission was proposing that all plastics containing BFRs be separated out from electrical and
electronic equipment before recycling or disposal.
This could have left the plastics industry trying to face two ways at the same time. Restrictions on
BFRs would rob companies of some of the most effective flame retardants available, at a time
when politicians and fire-fighters are pressing for increased levels of flame retardancy for plastics
in certain E&E applications.
The proposals on PBBs would not affect the plastics market, since their production had already
been discontinued and very few E&E makers use the substances. However, PBDEs are widely used
by the industry.
The legislation, although directed at equipment used in Europe, has international implications,
given the high levels of imports, especially from Asia, of products like personal computers and
small appliances. Indeed, the feeling at the influential US Association of State Fire Marshals is
such that it has complained to Brussels that moves to ban BFRs would compromise fire safety.
There are even indications that it could try to block importation of any E&E equipment whose fire
safety is reduced as a result of the WEEE proposals.
The draft directive showed that the commission was concerned about risks involved in landfilling,
incinerating, and recycling plastics that contain BFRs. For example, in one section on recycling the
draft states: Halogenated substances contained in WEEE, in particular BFRs, are also of concern
during the extrusion of plastics, which is part of the plastic recycling. This is due to the fact that
during recycling of plastics containing BFRs, brominated dibenzofurans and brominated dibenzop-dioxins may be formed. Various studies suggest that the risk of generation of dioxins is a reason
for the complete lack of recycling of plastics containing BFRs.
However, the industry-funded Bromine Science and Environmental Foundation (BSEF) in Brussels
says that the proposals would very likely be changed significantly, since they now have to be
considered by both the European Parliament and EU member states. According to the BSEF, indepth studies completed in Germany and discussed earlier in this chapter show that recycling of
PBDEs meets the strictest dioxin legislation in the world.
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Given the tough recycling targets set by the WEEE proposal (EU countries will be required to
collect at least 4 kg of waste E&E equipment per person per year), it seems difficult to imagine
enforced separation of all BFR plastics if this is going to impose additional costs for the very
plastics most suited to recycling.
For decaBDE, the risk assessment has so far found no significant risk and, following the
assessment's completion in the Summer of 2003, it will be possible for the EU to exempt decaBDE
from phase-out under the RoHS Directive. The importance of the 11 October WEEE agreement is
that the EU will base its decision for decaBDE on scientific risk assessment and individual EU
Member States will not be able to undermine this. Under the Council/Parliament agreement, each
EU Member State will have to wait until July 2006 to introduce the restrictions under the RoHS
Directive, thus maintaining the cohesion of the EU Single Market for electrical and electronic
products. The European Brominated Flame Retardant Industry Panel (EBFRIP) observed that The
Conciliation agreement means that the future EU regulatory status of decaBDE will be based on
scientific risk assessment. This is surely a welcome conclusion for decaBDE, a chemical substance
for which a significant risk has not been identified either for the environment or for human health
and which continues to save 1000s of lives through fire prevention.
In February 2003, the EU Directives on the management of electrical and electronic waste (WEEE)
and hazardous substances in E&E equipment (RoHS) were published in the EU official journal.
By 13 August 2004, EU Member States will have to transpose both laws onto their own national
legislation.
Under the WEEE Directive, manufacturers will then have another 2 years - until 31 December
2006 - to reach the recycling and recovery targets set up for the different categories of E&E
appliance. By this time, plastics containing brominated flame retardants (BFRs) will have to be
separated prior to recycling, energy recovery or disposal. The Directive's requirement to increase
mechanical recycling is an advantage for plastics containing BFRs as they offer high level of
stability during the recycling process. The separation requirement will in turn facilitate the
recycling and recovery of plastics containing BFRs for which there is a wide range of tested
recycling and recovery technologies.
Under the RoHS law, manufacturers will have to cease using PBB, pentaBDE, and octaBDE in
new E&E equipment from 1st July 2006.
9.4 Recycling Matters
The bromine industry became concerned in early 2000 about the formal proposal from the EC to
mandate increased levels of recycling for Waste Electrical and Electronic Equipment (WEEE). The
BSEF stated that the requirement to separate all WEEE containing halogenated flame retardants
would increase costs for collection and disposal. This is in complete contrast to Japanese copier
makers who were specifying the very same halogenated flame retardants on grounds of the relative
ease of recycling them.
Ricoh and Fuji-Xerox were specifying 30% and 25% recycled ABS for mass production during
2000. The Japanese copier industry established that recycled ABS can match the performance
requirements set down for virgin material. The brominated flame retardants used in the compounds
are said to be stable and have the advantage of not hydrolysing during the recycling process. In
addition, only brominated FRs can enable ABS to meet the fire safety test 5V, claimed to be the
highest level of safety.
A closed loop recycling technology for components that contain brominated flame retardants has
been specifically developed by Fuji Xerox, in conjunction with the resin manufacturer Ube Cycon,
by purchasing crushed and granulated waste components, decontaminating, re-compounding and
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shipping back a quality-assured compound. This encourages the equipment manufacturer to make
the effort of controlling the quality of the waste parts.
It also allows the recycled resin to be pigmented at the same time as it is reprocessed with the
addition of virgin material and additives. This is seen as an advantage over conventional processes,
in which the colouring is usually added after the recyclate has been pelletised. This, in turn,
required secondary melt processing, with possible further heat deterioration and additional costs.
The company sees the ABS system as a model for recycling other resins.
The top cover of the DocuCentre 550 copier is moulded in ABS, flame retarded with a brominebased additive to meet 5V UL94, having been compounded from virgin material plus reclaim from
the same part. Fuji Xerox has been recycling unretarded HB ABS since 1998 and has established
an upgrade recycling technique that raises the HB rating to 5V.
A similar system has been introduced by Ricoh, recycling 5V material for the exterior cover of its
copiers. Reclaim accounts for 3-5% of all resin and the technology was introduced on 8 new
models. The trend is expected to increase, both in the number of models and the quantity of
material recycled in each.
The mouldings for recycling are chopped into pieces between 4 and 15 mm in size. After cleaning
the chips are sent to the resin manufacturer for re-compounding. Addition rates of reclaimed
material in subsequent mouldings range from 25 to 75% at Fuji and 30-70% at Ricoh. As the
recycled resin shows some drop in properties, and is recycled on average two or three times, the
amount of virgin resin must be increased.
The cost of reclaimed material is higher than the equivalent virgin compound but Fuji Xerox
expects that, long-term, closed-loop recycling will reduce procurement cost of raw materials and
fully cover the cost of reclaiming.
A Japanese study in 2000 by Techno Polymer, a leading plastics manufacturer in Japan suggests
that key plastics that are retarded with brominated additives are, in fact, easier to recycle.
The company compared various ABS compounds, some containing a brominated epoxy oligomer
and others various organic phosphate esters. It was concluded that among the commercially
available plastics suitable for business machines, only FR-ABS retarded by the brominated
compound shows flawless recyclability in terms of keeping the original performance after the
thermal history and accelerated hydrolysis testing. The company also found that the recycled
brominated ABS met the highest levels of fire safety, as represented by the UL94 5V classification,
which is the test with which most copier makers comply.
With regard to incineration, the European Brominated Flame Retardant Industry Panel (EBFRIP)
has supported a programme at the TAMARA pilot incinerator of the Forschungszentrum Karlsruhe
(the Karlsruhe Research Centre). The conclusion of this project (to be found at www.firesafety.org)
is that, even under extreme conditions, E&E plastic waste rich in plastics containing BFRs can
safely undergo co-combustion with municipal solid waste and it is an ecologically acceptable and
economically sound disposal route for normal amounts of E&E waste containing brominated flame
retardants.
In addition, amounts of E&E plastic waste material added to municipal solid waste have a positive
influence on the combustion process, giving a cleaner and more complete combustion, and the
burnout of the bottom ashes is improved. The levels of dioxin and furan remained within the range
typically found in such incineration plants and the addition of extra E&E waste does not increase
these levels.
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Most municipal waste incinerators today add active carbon to the combustion procedures, as this
effectively helps decrease the already-low concentrations of dioxins to near-zero levels. This stateof-the-art dioxin abatement technology guarantees compliance with air emission regulations, even
if dioxin and furan levels were significantly higher than those found during the co-combustion test
performed at Forschungszentrum Karlsruhe.
Plastics that are flame retardant to the more stringent UL94 V-0 standard have been shown to
reduce emissions to the environment compared to plastics flame retarded to the less stringent
IEC65 horizontal burning (HB) standard, which has been more prevalent in Europe in recent times.
The Swedish National Testing and Research Institute has developed a total life-cycle assessment
(LCA) model directed at determining the cost of measures taken to attain a high level of fire safety.
The first full application of that method was for TV sets that were V-0 or HB rated. The LCA
concluded that the loading on the environment was less for the TV containing the brominated FR
than for the TV set without FR. The main reason for this is the greater number of fires and the
resultant environmental emissions associated with the TVs made from HB material.
As the volumes of E&E items have increased it is now seen that there must be adequate treatment
options to replace landfill. Plastics, on average, represent 20% by weight of current E&E products,
with the share estimated to rise in the future. With end-of-life recovery being an integral part of the
life cycle of plastics, appropriate measures must be taken to ensure the maximum value is obtained
from the plastics after their first life in E&E equipment.
The proposed WEEE directive imposes a collection target of 4kg per person in the EU by 2006. It
also establishes recovery targets of 60-80% and reuse/recycle targets of 50 to 75% depending on
the type of item involved.
Plastics containing BFRs enjoy a wide range of options at end of life and fit into the accepted
mantra of reduce, reuse, recycle. On the reduce level, flame retardants contribute due to fires
prevented and the resulting reduction in the need to replace fire-damaged goods that would contain
fresh material. Plastics containing BFRs can be reused in the same application as shown by the
recycling (refill and reuse) of copier toner cartridges.
Some of the considerations when choosing recycling options include:
The cost and complexity of disassembling the different types of E&E,

Identifying the different components and compositions of the disassembled parts,
Separating and sorting the various materials, such as metal coatings, paints,
The ease of recycling the various materials obtained, and
The value of the materials resulting from the recycle operation.
Contrary to the proposed WEEE directive many believe that a form of recycling is energy
generation from plastic waste with bromine recovery as a form of recycle.
Recycle should cover mechanical recycle in the originally intended application or in a downgraded
application, or feedstock recovery with or without bromine recovery, or energy generation with at
least the bromine recovered.
Some think that energy recovery without any bromine should be classified as disposal, alongside
landfill or incineration with no energy output at all.
To take the mechanical recycling route, several steps such as sorting and dismantling are almost
certainly involved, plus comminuting of larger pieces now present. Mechanical recycling can result
in compounds for use in an original or lesser application, depending on the thoroughness of all the
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intermediate stages that may be necessary. It certainly offers the highest value for end of life E&E
FR plastics.
This method may be feasible for large plastic parts such as TV back covers and some copier, and
other, enclosures where the cost of disassembly and sorting may be offset by the extra value
obtained from such recycling compared to other options.
A technique that could have application in a broader range of end-of-life E&E FR plastics is
feedstock recycling. The EBFRIP in cooperation with the BSEF has carried out a feasibility study
on bromine recovery from waste E&E. Plastics from the waste E&E are co-fed with municipal
solid waste (MSW) either to a pyrolysis unit or to an incineration unit for syngas generation or
energy recovery, respectively. The flue gas is scrubbed and bromine salts are recovered which can
then be converted back to bromine, so closing the loop on the use of bromine in BFRs. Depending
on the nature of the resultant waste ash it may be recovered for secondary materials, such as basalt,
metal or cement. The conclusions of the feasibility study are that it is economically and
ecologically feasible to perform feedstock recycling, or bromine recovery.
The project could reduce the emission of so-called greenhouse gases and also provide bromine
producers with the opportunity of recycling a minimum of 10,000 tonnes a year of bromine in
Europe.
The waste to energy recovery route covers energy via incineration or as a fuel source in smelters,
cement kilns or chalk ovens as is often the case with plastic waste today. Past problems with
standards of operation at incinerators, such as operating temperature, residence times and
emissions, led to concerns over the incineration of plastics waste in the past. However, since that
time more stringent requirements for operation have been introduced, such as a minimum of 850 C
in the combustion chamber, minimum of 2 sec residence time for the resulting flue gases at 850 C,
in the presence of at least 6% oxygen.
The Association of Plastics manufacturers in Europe (APME) has issued a definitive report on the
Karlsruhe Trials at the TAMARA facility already mentioned above. This is entitled Recycling of
bromine from plastics containing brominated flame retardants in state-of-the-art combustion
facilities. This has demonstrated that in modern plants with suitable wet scrubbing equipment,
recycling of bromine in plastics waste containing BFRs is technically feasible. The expectation is
that mechanical recycling of plastics from WEEE will often not be efficient, so implementation of
the EU directive on the management of such wastes will mean that such materials will be
increasingly available for bromine recycling in such facilities.
APME estimates that WEEE plastics comprise just over 3% of the 19 million tonnes of collectible
post-consumer plastics in Europe. This quantity, of around 733,000 tonnes is projected to rise
significantly in the future. EEE is defined by the directive as all appliances dependant on electric
currents or EM fields in order to work, and which use AC up to 1000V or DC up to 1500V. This,
of course, covers, business machines, telecommunications equipment, brown and white goods,
small hand-held domestic appliances plus medical and other equipment such as sewing machines
and household leisure and garden goods.
The waste plastics become available for dedicated recovery after either a manual dismantling and
separation process, or after mechanical shredding and refining.
On average, around 30% of the plastics in E&E contain flame retardants of one type or another. In
2000, of the plastics with FRs used in E&E goods, 59% used non-halogenated types and the rest
were halogenated.
The major location of the BFRs is in business, data processing and telecomms equipment at 53% of
EEE using BFRs. Brown goods have 22%, industrial items a further 7%, household ones just 2%
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with the remaining 16% spread over others. Interestingly, just one BFR represents over 50% of
the total BFR market. This is tetrabromobisphenol-A.
The incineration programme was designed for bromine levels in a mix of WEEE and ordinary
MSW to be between 0.5 and 1.0 wt%. This is more than 100 times the typical concentration in
MSW. Depending on the mix and type of WEEE the bromine could be found in the bottom ash, fly
ash and/or the gas phase in varying proportions.
Bromine was expected to promote volatility of metals, since metal bromides tend to have low
boiling points. This was indeed observed as metal transfer to the fly ash increased for copper, lead,
zinc and others present in the generality of the MSW. There was no significant correlation between
increased bromine levels and the overall level of halogenated dioxins and furans; and the
brominated dioxins and furans that were present were almost totally destroyed or removed.
Bromine can be recovered from various species that reach the gas phase.
APME estimate that up to 8000 tonnes of bromine a year is available for recovery from such
facilities. Up to 2-3% of WEEE FR plastics can be safely added to the fuel mix in combustion
facilities, well exceeding the amount that is ever likely to be produced. They also suggest a
dedicated or multipurpose pyrolysis/gasification facility as a route for bromine recycling from
WEEE plastics. More information is available on the APME website at www.apme.org.
A further study, recently completed by TNO (the Dutch engineering, testing and scientific
organisation) has concluded that the presence of bromine in plastics (as a flame retardant) does not
adversely affect energy recovery equipment for household waste treatment. Levels of bromine in
the plastic waste going to energy recovery can be easily increased by a factor of 9-10 times before
any additional adverse effect could occur in the equipment.
Like several materials found in the household waste stream, bromine has the potential of corrosive
properties, which could by definition adversely affect the energy recovery equipment. However,
given the presence in household waste of other potential corrosive materials like hydrochloric acid
and the comparatively low levels of bromine (up to 100 times lower than chlorine), it was
important to find out up to what level of plastics containing BFRs could be added to a feedstock
recycling or an energy recovery facility without causing additional equipment corrosion. Currently,
plastics containing BFRs form on average only 0.35% of the total waste going to household waste
treatment.
Levels of BFR containing plastics in the household waste are unlikely to exceed even 3% under the
new EU Directive on Waste Electrical and Electronic Equipment (WEEE). Hence, BFR plastics are
compatible with WEEE solutions such as feedstock and energy recovery.
The study was funded by the European Brominated Flame Retardant Industry Panel (EBFRIP) and
can be found at http://www.ebfrip.org.
9.5 Postscript
Recent and current regulatory programmes and pronouncements, in Europe and nationally, about
brominated flame retardants are but part of a political concept called Sustainability.
Since the EU and its Market is a huge size, arguably second only to the USA, any legislation
coming out of Europe that potentially affects trade in some way or another, is noted across the
world.
The generally accepted definition of sustainable development is development that meets the needs
of the present without compromising the ability of future generations to meet their own needs. This
implies that mankinds collective effort to improve the quality of life on Earth will be sustainable
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if, and only if, the resulting perturbation is not allowed to exceed the capacity of our planets
ecological support systems.
This presupposes that the earths natural product cycles are by definition sustainable.
In 1998, the United Nations Commission on Sustainable Development (UNCSD) recognised that
business and industry would play a crucial role in the global quest for sustainable development and,
on that occasion, UNCSD made reference to the OECD Risk Assessment Programme on
brominated flame retardants as a model example of a global, voluntary chemical industry initiative.
By contrast, the 2nd Integrated Product Policy (IPP) Conference in early 2001 explicitly
acknowledged the hurdles barring the way to sustainable development and justified the exclusively
green focus of the proposed policy initiative on the grounds of political pragmatism. It set 3 key
pre-conditions of success for IPP:
The prices of green products must be competitive;

Green product design must be encouraged;
The market demand for green products must be stimulated.
In June 2001, the EU Committee of the Regions emphasised the need for IPP to be framed on the
basis of the fundamental principles underpinning EU environmental policy. They are:
a) the Precautionary Principle, and
b) the Substitution Principle.
The precautionary principle states that where there are threats of serious or irreversible damage,
lack of scientific certainty shall not be used as a reason for postponing cost-effective measures to
prevent environmental degradation. In its Communication of 2/2/00 the European Commission
emphasised that regulatory measures that invoke the Precautionary Principle should start from a
scientific evaluation. This should be as complete as possible and should identify at each stage the
degree of scientific uncertainty. The European Council endorsed the Precautionary Principle at the
Nice Summit in December 2000, and recalled measures should be periodically reviewed and
amended as necessary.
In September 2001, the Danish EPA recommended that Danish enterprises, importers and retailers
of electronic equipment should voluntarily reject products containing brominated FRs. This
initiative came one month after the publication of the updated Danish EPA Action Plan on
Brominated Flame Retardants. Its objective was the international phase-out of the use of the most
problematic BFRs, the short-term focus being on the PBBs and PBDEs. A further objective of this
Action Plan was to assess flame retardants that are potentially less harmful to the environment and
health so as to facilitate substitution, thereby helping to promote the development of greener
products.
There has been much debate in the last four to five years around the sources of organohalogens
found in apparently threatened species (including man). There has been a school of thought that
believes such chemicals can have only anthropogenic origins, but this has been increasingly
challenged by the results of various studies.
Back in 1999, the general scientific view tended to be that all organohalogens accumulating in
wildlife came from industrial sources or other human activities. This included a report by a joint
US/Canadian body, the International Joint Commission (IJC) responsible for environmental
monitoring of the Great Lakes, which stated that there is something non-biological about
fluorinated, chlorinated and brominated organics.
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Other statements claimed that some types of synthetic compounds are not found in nature,
including halogenated hydrocarbons such as PCBs, although the IJC shifted slightly later to say
that the presence of BDPEs, chlorinated paraffins and naphthalenes in the tissue of a range of
species was a mystery.
Next, the first recorded instance of a naturally produced organohalogen accumulating in the eggs of
wild birds and marine species was identified as 1,1-dimethyltetrabromodichloro-2,2-bipyrrole.
As a result the investigators expressed the opinion that a better understanding of the natural sources
of organohalogens was essential when regulations concerning anthropogenic organohalogens were
being prepared. Subsequently, there were reports of a previously unknown natural organochlorine
contaminant in the blubber of marine mammals and in birds, and the bioaccumulation of
halogenated dimethylbipyrroles in the Arctic marine food chain.
Since the first naturally occurring compound mentioned above, much work continues to be reported
on organohalogens such as hexahalogenated dimethylbipyrroles (HDBPs) that are produced
naturally by many types of algae and marine organisms and can accumulate in animals higher up
the food chain. Natural brominated compounds have been detected in blubber extracts from marine
animals. Other naturally occurring compounds such as methoxy tetrabromo diphenyl ether isomers
have been reported and may be misinterpreted as methoxylated metabolites of tetrabromodiphenyl
ether.
Other interesting facts cover the generation of chlorine and bromine themselves. The natural
production of chlorine occurs by the injection of sea-salt aerosol generated by wind stress into the
air over ocean surfaces and is the major global source of atmospheric chlorine. The production rate
for this natural phenomenon is estimated to be 50 times greater than the estimated anthropogenic
production capacity of around 40 megatonnes. Turning the same model to calculating the bromine
in sea salt aerosol, then the corresponding oceanic production rate is about 7 megatonnes, with the
man-made figure being not much over one-half a megatonne.
All this information suggests a reappraisal of the basis for much of the regulatory effort at both EU
and national levels on BFRs. Although there is legitimate concern over some halogenated manmade chemicals, there has been an apparent distortion of perspective on the relative toxicity impact
potentials (TIP) of anthropogenic versus naturally occurring organohalogens.
The lack of adequate TIP data on alternatives to BFRs should give pause for thought, not to speak
of the relative flame-retardant efficiency and design adequacy of the candidate substitutes.
The politics of plastics additives and complex chemical species in general seem to be at variance
with scientific findings and their interpretation. One global trend that has been gathering pace is
utilising science to confirm the key reason for using FR technology in the first place namely, that
these products save lives and property.
Sweden has been generally credited with being most strongly against FR additives, with its
Chemical Inspectorate providing the leading critical voice. Yet, in April 2001, the Inspectorate
criticised as inconclusive some research by environmental activists in their case against
brominated FRs. Just because a fire retardant contains bromine does not make it dangerous.
Nevertheless, the Nordic countries are still looking closely at FR products. Important questions
have been raised in Scandinavia about antimony, phosphate, and bromine-based FRs. But, again,
the prevailing view highlights the role of these products in saving lives and property as the prime
considerations.
Much time in 2001 was spent in the EU Commission and the Parliament looking at brominated FRs
in the context of the WEEE and hazardous substance ban (RoHS) directives. At one point the
130
Commission considered banning all brominated FRs. Instead the Parliament passed a law that will
ban rarely-used PBBs and PBDEs for E&E equipment.
Risk assessments on two important additives, the decabromo and octabromo types, show that these
chemicals are environmentally acceptable.
In Tokyo, the Japan Environment Association changed its ecolabel criteria for copiers, printers and
PCs. The change withdraws the exclusion of all BFRS to just PBBs and PBDEs, products that have
little impact on the marketplace. Pressure for this change had filtered up from Japanese OEMs, who
recognise the superior recyclability of BFR plastics and also the consumer demand for greater fire
safety.
In recent years, the National Academy of Sciences in the US has examined the effects on human
health of 16 FR chemicals used to meet new furniture fire safety standards. The studies produced
enough data for the Academy to definitely evaluate eight of these products. It concluded that there
were no significant environmental or health concerns related to their use.
131
132
European Suppliers of Flame Retardants

Company Names and Addresses
A Schulman
Pedro Colomalaan 25
B-2880 Bornem
Belgium
Tel: +32 38 944211
Fax: +32 38 897110
A Schulman GmbH
Huettenstrasse 211
50170 Kerpen-Sindorf
Germany
Tel: +49 2273 5610
Fax: +49 2273 561350
E-mail: aschulman@de.aschulman.com
http://www.aschulman.com
Akzo Nobel Functional Chemicals BV
PO Box 247
3800 AE Amersfoort
Netherlands
Tel: +31 3346 76767
Fax: +31 3346 76100
E-mail: webmaster@functionalchemicals.com
http://www.functionalchemicals.com
Alcan Chemicals Europe
135 Aberdour Road
Burntisland
Fife
Scotland
KY3 0EP
United Kingdom
Tel: +44 (0) 1592 411000
Fax: +44 (0) 1592 411111
E-mail: nicola.carlyle@alcan.com
http://www.alcanchemicals.com
Americhem Europe Limited
Cawdor Street
Eccles
Manchester
M30 0QF
United Kingdom
Tel: +44 (0) 1617 897832
Fax: +44 (0) 1617 877832
E-mail: dbooth@americhem.com
http://www.americhem.com
133
Aquaspersions Limited
Beacon Hill Road
Halifax
West Yorkshire
HX3 6AQ
United Kingdom
Tel: +44 (0) 1422 386200
Fax: +44 (0) 1422 386239
E-mail: info@aquaspersions.co.uk
http://www.aquaspersions.co.uk
Areton International Plastics Limited
Unit 47/48 Clywedog Road North
Wrexham Industrial Estate
Wrexham
LL13 9XN
United Kingdom
Tel: +44 (0) 1978 664646
Fax: +44 (0) 1978 664647
E-mail: contact@areton.com
http://www.areton.com
Arto Chemicals Limited
Arto House
London Road
Binfield
Bracknell, Berkshire
RG42 4BU
United Kingdom
Tel: +44 (0) 1344 860737
Fax: +44 (0) 1344 860820
E-mail: sales@artochemicals.com
Biesterfeld Plastic Benelux BV
Oude Bosscheweg 15
5301 LAZaltbommel
Netherlands
Tel: +31 418 572315
Fax: +31 418 572370
E-mail: m.cobelens@biesterfeld.com
http://www.biesterfeld-plastic.com
Blagden Specialty Chemicals Limited
Osprey House
Black Eagle Square
Westerham
Kent
TN16 1PA
United Kingdom
Tel: +44 (0) 1959 560805
Fax: +44 (0) 1959 565656
E-mail: jwebb@blagdenspecchem.co.uk
134
Borax Europe Limited

1A Guildford Business Park
Guildford
Surrey
GU2 8XG
United Kingdom
Tel: +44 (0) 1483 242000
Fax: +44 (0) 1483 242001
E-mail: borax_europe@borax.com
http://www.borax.com
Bromine & Chemicals Limited
201 Haverstock Hill
London
NW3 4QG
United Kingdom
Tel: +44 (0) 2074 317707
Fax: +44 (0) 2074 317797
Broste AB
Kryptongatan 9B
431 53 Molndal
Sweden
Tel: +46 3174 64440
Fax: +46 3177 69676
E-mail: janh@broste.com
http://www.broste.com
Cairn International Limited
Cairn House
Elgiva Lane
Chesham
HP5 2JD
United Kingdom
Tel: +44 (0) 1494 786066
Fax: +44 (0) 1494 791816
E-mail: cairn.int@lineone.net
http://www.cairninternational.co.uk
Caldic Belgium
Terlochtweg 1
Hemiksem
2620
Belgium
Tel: +32 3 8704811
Fax: +32 3 8704859
http://www.caldic.com
135
Campine SA
Nijverheidsstraat 2
Beerse
Antwerp
2340
Belgium
Tel: +32 1460 1511
Fax: +32 1460 1577
http://www.campine.be
Capital Rubber & Plastics Limited
Units 9/11
Deans Factory Estate
Lambs Lane
Rainham Essex
RM13 8XL
United Kingdom
Tel: +44 (0) 17085 52214
Fax: +44 (0) 17085 24004
http://www.capitalrubber.uk.com
Ceepree Products Limited
Springfield House
Lower Eccleshill Road
Darwen, Blackburn
Lancashire
BB3 0RP
United Kingdom
Tel: +44 1254 702800
Fax: +44 1254 873009
E-mail: ceepreesales@ceepree.com
http://www.ceepree.com
CH Erbsloeh KG
Duesseldorfer Strasse 103
47809 Krefeld
Germany
Tel: +49 2151 52500
Fax: +49 2151 525100
E-mail: info@che-kg.de
http://www.cherbsloeh.de
Charlotte Chemical Inc
2500 Wilcrest
Suite 334
Houston
Texas 77042
USA
Tel: +1 52 5 203 6226
Fax: +1 52 5 203 6434
E-mail: charlot1@inetcorp.net.mx
http://www.charlotte.com
136
Clariant (Italia) SpA - Masterbatches Division

Via Lainate 26
20010 Pogliano Milanese (MI)
Italy
Tel: +390 2 99187558
Fax: +390 2 99187552
http://www.clariant.masterbatches.com
Collinda Limited
Collinda House
25 Ottways Lane
Ashtead
Surrey
KT21 2PL
United Kingdom
Tel: +44 (0) 1372 278416
Fax: +44 (0) 1372 278559
E-mail: info@collinda.co.uk
http://www.collinda.co.uk
Colortek Farbsysteme GmbH
Ringstrasse
Gerwerbegebeit 1
19357 Karstadt
Germany
Tel: +49 38797 760
Fax: +49 38797 76200
E-mail: info@colortek.de
http://www.colortek.de
DSBG Eurobrom BV
PO Box 158
2280 AD Rijswijk
Netherlands
Tel: +31 7034 08438
Fax: +31 7039 99035
E-mail: wilmerr@eurobrom.dsbg.com
http://www.dsbgfr.com
Duslo AS
PO Box 33
927 03 al'a
Slovakia (Slovak Republic)
Tel: +421 31 7753388
Fax: +421 31 7753018
E-mail: duslo@duslo.sk
http://www.duslo.sk
137
Dyna-Grout Inc
24B Skidmore Road
Deer Park
NY 11729-7217
USA
Tel: +1 631 242 3366
E-mail: dynagrout@hotmail.com
http://www.dynagrout.com
E & E Limited
Bramley Road
Milton Keynes
MK1 1PT
United Kingdom
Tel: +44 (0) 1908 271511
Fax: +44 (0) 1908 375611
E-mail: rcook@vopak.com
E. Wood Limited
Standard Way
Northallerton
North Yorkshire
DL6 2XA
United Kingdom
Tel: +44 (0) 1609 780170
Fax: +44 (0) 1609 780438
E-mail: grant@ewood.co.uk
Ferro Chemicals SA
Etang de la Gafette
BP 28
13521 Port-de-Bouc
France
Tel: +33 04 42 40 73 00
Fax: +33 04 42 40 73 33
http://www.ferro.com
Gabriel-Chemie GmbH
Industriestrasse 1
2352 Gumpoldskirchen
Austria
Tel: +43 2252 636300
Fax: +43 2252 63660
E-mail: office@gabriel-chemie.com
http://www.gabriel-chemie.com
Gedriplastics NV
Industriezone Peerderbaan 1419
B-3960 Bree
Belgium
Tel: +32 89 469760
Fax: +32 89 469766
E-mail: info@gedriplastics.com
http://www.gedriplastics.com
138
Great Lakes Chemical Corporation

Tenax Road
Trafford Park
Manchester
M17 1WT
United Kingdom
Tel: +44 (0) 1618 722323
Fax: +44 (0) 1618 753177
E-mail: kgreen@glcc.com
http://www.pa.greatlakes.com
Hardie Polymers Limited
53 Stockiemuir Avenue
Bearsden
Glasgow
Scotland
G61 3JJ
United Kingdom
Tel: +44 (0) 1419 423330
Fax: +44 (0) 1419 424001
E-mail: sales@hardie-polymers.co.uk
http://www.hardie-polymers.co.uk
Intermag Company Limited
Bath Road
Felling Industrial Estate
Gateshead
NE10 0LG
United Kingdom
Tel: +44 (0) 1914 382030
Fax: +44 (0) 1914 384717
E-mail: sales@intermag.co.uk
Internatio BV
Wilhelminaplein 32
3008 Rotterdam (AV)
Netherlands
Tel: +31 10 2908600
Fax: +31 10 2908611
E-mail: info@internatio.com
http://www.internatio.nl
Internatio NV
Blarenberglaan 21
Industrieterrein Noord A
2800 Mechelen
Belgium
Tel: +32 1529 4950
Fax: +32 1529 4952
E-mail: f.meeremans@internatio.be
http://www.internatio.com
139
Italmatch Chemicals SpA

Via Pietro Chiesa 7/13
Torri Piane - San Benigno
16149 Genova
Italy
Tel: +390 10 642081
Fax: +390 10 4695296
E-mail: n.gatti@italmatch.it
http://www.italmatch.it
Joseph Storey & Company Limited
Heron Chemical Works
Moor Lane
Lancaster
Lancashire
LA1 1QQ
United Kingdom
Tel: +44 (0) 1524 63252
Fax: +44 (0) 1524 381805
E-mail: info@josephstorey.co.uk
http://www.josephstorey.co.uk
KMZ Chemicals Limited
48 Station Road
Stoke D'Abernon
Cobham
Surrey
KT11 3BN
United Kingdom
Tel: +44 (0) 1932 866426
Fax: +44 (0) 1932 867099
E-mail: info@kmzchemicals.ltd.uk
Krahn Chemie GmbH
Grimm 10
20457 Hamburg
Germany
Tel: +49 4032 092-0
Fax: +49 4032 092-297
E-mail: c.schur@krahn.de
http://www.krahn.de
Laminopol Sp zoo
Ul. Szczecinska 58 B
76200 S&#322 upsk
Poland
Tel: +48 59 8453463
Fax: +48 59 8452959
E-mail: office@laminopol.com
http://www.laminopol.com
140
Martinswerk GmbH
Kolner Strasse 110
50127 Bergheim
Germany
Tel: +49 2271 9020
Fax: +49 2271 902557
E-mail: manfred.weber@albemarle.com
http://www.martinswerk.de
Microfine Minerals Limited
Raynesway
Derby
DE21 7BE
United Kingdom
Tel: +44 (0) 1332 673131
Fax: +44 (0) 1332 677590
E-mail: minerals@microfine.co.uk
http://www.microfine.co.uk
National Chemical Company
NCC House
42 Lower Leeson Street
Dublin 2
Ireland
Tel: +353 1 6131400
Fax: +353 1 6616676
E-mail: avlooney@ncc.ie
http://www.ncc.ie
Nexans CSPL UK Limited
Tandy House
Felixstowe Road
Abbey Wood
London
SE2 9AA
United Kingdom
Tel: +44 (0) 2085 573481
Fax: +44 (0) 2085 573535
Nordmann, Rassmann GmbH
Kajen 2
20459 Hamburg
Germany
Tel: +49 4036 870
Fax: +49 4036 87249
E-mail: info@nrc.de
http://www.nrc.de
Omnia Chemie GmbH
Gorsenkothen 45
D-40882 Ratingen
Germany
Tel: +49 2102 81431
Fax: +49 2102 841253
141
Omya Sas
35 Quai Andre Citroen
75015 Paris
France
Tel: +33 1 4058 4482
Fax: +33 1 4058 4469
http://www.omya.com
Polyadd Limited
53A Denby Lane
Codnor
Ripley
Derbyshire
DE5 9SP
United Kingdom
Tel: +44 (0) 1773 570994
Fax: +44 (0) 1773 570994
E-mail: peter@polyadd.co.uk
http://www.polyadd.co.uk
Produits Chimiques de Lucette
ZI de la Vallee Verte
53940 Le Genest Saint Isle
France
Tel: +33 2 4301 2310
Fax: +33 2 4302 4906
http://www.pcdlucette.com
PVC Technical Services
P.O. Box 1377
Silver City
New Mexico 88062
USA
Tel: +1 505 534 9098
E-mail: 2beeps@roadrunner.com
http://www.plasticsnet.com
Rakem Limited
Wellington Street
Bury
Manchester
BL8 2BD
United Kingdom
Tel: +44 (0) 1617 620044
Fax: +44 (0) 1617 620033
E-mail: sales@rakem.co.uk
http://www.rakem.co.uk
142
Rhodia Consumer Specialties Limited

PO Box 3
210-222 Hagley Road West
Oldbury
West Midlands
B68 0NN
United Kingdom
Tel: +44 (0) 121 429 4942
Fax: +44 (0) 121 420 5151
http://www.albright-wilson.com
Salmon & Cia Lda
Rua Da Cova Da Moura 2-6
1399-033 Lisboa
Portugal
Tel: +351 21 3920130
Fax: +351 21 3920189
E-mail: salmon@salmon.pt
Schill & Seilacher "Struktol"
Aktiengesellschaft
Moorfleeter Strasse 28
D-22113 Hamburg
Germany
Tel: +49 40 733620
Fax: +49 40 73362194
E-mail: info@struktol.de
http://www.struktol.de
Solvay Fluor und Derivate GmbH
PO Box 220
30002 Hannover
Germany
Tel: +49 511 8572162
Fax: +49 511 817338
E-mail: joachim.rieger@solvay.com
http://www.solvay-fluor.com
Synergistic Polymer Systems
PO Box 2116
Bellaire
Texas 77402 -2116
USA
Tel: +1 713 780 8888
Fax: +1 713 780 8887
E-mail: synpoly@bigfoot.com
Tolson Polymers BV
Westblaak 194
3012 KN Rotterdam
Netherlands
Tel: +31 10 2141 918
Fax: +31 10 2420 800
E-mail: info@tolson.nl
143
Tropag GmbH
Bundesstrasse 4
20146 Hamburg
Germany
Tel: +49 4041 4013-0
Fax: +49 4041 4013-20
E-mail: info@tropag.com
http://www.tropag.com
VAMP Srl
Viale S. Boezio, 4-6
20145 Milano
Italy
Tel: +39 02 3492281 / 3490518
Fax: +39 02 33103681
E-mail: vampv@tiscalinet.it
http://www.paginegialle.it/vampsrl
Vamp Tech SpA
Viale delle Industrie 10/12
20040 Busnago (MI)
Italy
Tel: +390 39 6957821
Fax: +390 39 6820563
E-mail: info@vamptech.it
http://www.vamptech.com
West & Senior Limited
Milltown Street
Radcliffe
Manchester
M26 1WE
United Kingdom
Tel: +44 (0) 1617 247131
Fax: +44 (0) 1617 249519
E-mail: stesenior@westsenior.co.uk
http://www.westsenior.co.uk
Wilfrid Smith Limited
Elm House
Medlicott Close
Corby
Northamptonshire
NN18 9NF
United Kingdom
Tel: +44 (0) 1536 460020
Fax: +44 (0) 1536 462400
E-mail: info@wilfrid-smith.co.uk
http://www.wilfrid-smith.co.uk
144
Abbreviations and Acronyms

ABS
AMAP
AOM
APC
APME
APP
ATH
ATO
BAPP
BCC
BDBPT
BDP
BDPE
BEO
BET
BFR
BHPP
BMI
BPADP
BSEF
CFR
CMHR
CPSC
CPVC
CR
CTI
DAHP
DCPD
decaBDE
DEEP
DEMMP
DKS
DPE
DSBG
DTI
E&E
EBFRIP
EBT
EBTBP
EEA
EG
EM
EMA
EPB
EPDM
EPS
ETP
EVA
FHSA
FIGRA
FIPEC
FMVSS
acrylonitrile-butadiene-styrene terpolymer
Arctic Monitoring and Assessment Programme
ammonium octamolybdate
Arab Potash Company
Association of Polymer Manufacturers in Europe
ammonium polyphosphate
alumina trihydrate
antimony trioxide
bis(4-aminophenyl) phenyl phosphate
Business Communications Corporation
bis(2,3-dibromo)propyl ether of TBBA
bisphenol A bis(diphenyl phosphate)
bromodiphenyl ether
brominated epoxy oligomer
specific surface area, Brunauer-Emmett-Teller method
brominated flame retardant
bis(3-dihydroxyphenyl) phenyl phosphate
bismaleimide
bisphenol A diphenylphosphate
Bromine Science & Educational Forum
chlorinated fire retardant
combustion modified heat resistance
Consumer Product Safety Commission
chlorinated PVC
chloroprene
Comparative Tracking Index
diammonium hydrogen phosphate
dicyclopentadienol
decabromo diphenylether
diethyl ethyl phosphonate
diethyl(methacryloxymethyl) phosphonate
Dai-Ichi Kogyo Seiyaku
diphenyl ether
Dead Sea Bromine Group
Department of Trade and Industry
electrical and electronics
European Brominated Flame Retardant Industry Panel
ethylene bis(tetrabromophthalimide)
ethylene bis(tetrabromophthalimide)
ethylene-ethyl acrylate copolymer
expandable graphite
electromagnetic
ethylene methyl acrylate
ethane 1,2 bis (pentabromophenyl)
ethylene-propylene-diene terpolymer
expanded polystyrene
engineering thermoplastic
ethylene-vinyl acetate copolymer
Federal Hazardous Substances Act
fire growth rate
Fire Performance of Electric Cables
Federal Motor Vehicle Safety Standard
145
FR
FST
FTIR
GMA
GRP
GWFT
HALS
HB
HBCD
HDBP
HDT
HET
HIPS
HRR
IEC
IPP
Jodico
JV
LCA
LDPE
LIFT
LOI
LPC
LRT
LSOH
LUL
MBEO
MC
MDH
MFI
MHC
MMT
MoD
m-PPO
MSW
NBS
NFPA
NOR
OBSi
octaBDE
ODOPB
OI
PA
PAH
PBB
PBDE
PBI
PBO
PBT
pbw
PC
PCB
PCB
PE
PEEK
146
flame retardant
fire-smoke toxicity
Fourier transform infrared
glycidyl methacrylate
glass reinforced plastic
Glow Wire Flammability Test
hindered amine light stabiliser
horizontal burning
hexabromocyclododecane
hexahalogenated dimethylbipyrroles
heat deflection temperature
hexachloroendomethylenetetrahydrophthalic
high impact polystyrene
heat release rate
International Electrical Commission
Integrated Product Policy
Jordan Dead Sea Industries
joint venture
life-cycle assessment
low density polyethylene
lateral ignition flame spread test
limiting oxygen index
Loss Prevention Council
long-range transport
low smoke zero halogen
London Underground
modified brominated epoxy oligomer
melamine cyanurate
magnesium hydroxide
melt flow index
magnesium hydroxycarbonate
montmorillonite clay
Ministry of Defence
modified polyphenylene oxide
municipal solid waste
National Bureau of Standards
National Fire Protection Association
N-alkoxy hindered amines
organoboroxo-siloxane
octabromo diphenylether
2-(6-oxido-6H-dibenzo(c,e)(1,2)oxaphosphorin-6-yl)-1,4-benzenediol
oxygen index
polyamide
polycyclic aromatic hydrocarbon
polybrominated biphenyl
polybrominated diphenyl ether
polybenzimidazole
polybenzoazole
poly(butylene terephthalate)
parts by weight
polycarbonate
polychlorinated biphenol
printed circuit boards
polyethylene
polyetheretherketone
pentaDBE
PET
PHA
PHDD
PMMA
PON
POP
PP
PPO
PS
PU
PVA
PVC
R&D
RDP
RHR
RoHS
RTM
SAN
SBI
SBS
SEA
SG
SMC
SMOGRA
SPR
TBBA
TBBPA
TCPP
TDCP
TGPSO
THPS
THR
TIP
TMCPP
TPMP
TPP
TPU
TS
UL
UNCSD
UP
UV
WEEE
XPS
ZB
ZHS
pentabromo diphenylether
polyethylene terephthalate
polyhydroxyamide
polyhalogenated dibenzodioxins
polymethyl methacrylate
phosphorus oxynitride
persistent organic pollutant
polypropylene
polyphenylene oxide
polystyrene
polyurethane
polyvinyl alcohol
polyvinyl chloride
research & development
resorcinol diphenyl phosphate
rate of heat release
Restriction of Hazardous Substances
resin transfer moulding
styrene-acrylonitrile polymer
Single Burning Item
styrene-butadiene-styrene
specific effective area
specific gravity
sheet moulding compound
smoke growth rate
smoke production rate
tetrabromobisphenol A
tetrabromobisphenol A
trichloropropylphosphate
tris dichloropropyl phosphate
triglycidyl phenyl silane oxide
tetrakis hydroxymethyl phosphonium salts
total heat release
toxicity impact potential
tris monochloropropyl phosphate
cyclic diphosphonate ester
triphenyl phosphate
thermoplastic polyurethane
thermally stable
Underwriters Laboratories
United Nations Commission on Sustainable Development
unsaturated polyester
ultraviolet
Waste Electrical and Electronic Equipment Directive
extruded polystyrene
zinc borate
zinc hydroxystannate
147
148
ISBN: 1-85957-385-1
Rapra Technology Limited

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experience providing technology, information and
consultancy on all aspects of rubbers and plastics.
The company has extensive processing, analytical
and testing laboratory facilities and expertise,
and produces a range of engineering and data
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knowledge-based systems.
Rapra also publishes books, technical journals,
reports, technological and business surveys,
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These publishing activities are supported by an
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Market Report

Flame Retardants for Plastics

Dr. Peter W. Dufton

Rapra Technology Limited

2003, Rapra Technology Limited

Typeset, printed and bound by Rapra Technology Limited.

1.1 Background .............................................................................................................................. 1

3.1 General ................................................................................................................................... 11

4.1 Organic Halogen Containing Materials.................................................................................. 17

4.3.4.2 Commercial Products ............................................................................................... 38

6.1 General Comments ................................................................................................................. 77

7 End-User Market Sectors............................................................................................................ 89

8.1 Introduction .......................................................................................................................... 105

9.1 Fire Safety ............................................................................................................................ 113

Abbreviations and Acronyms..................................................................................................... 145

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Chapter 7 briefly examines some major end uses. These cover

Automotive; Other Transportation

Flame Retardants for Plastics Market Report

2 Summary and Conclusions

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Table 2.1 Examples of flame resistance standards

2.2.2 Electrical Appliances

2.2.3 Business Machines and Consumer Electronics

Flame Retardants for Plastics Market Report

2.2.4 Building and Construction

2.3.1 Testing and Environmental Factors

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

raising of the ignition temperature,

Flame Retardants for Plastics Market Report

3.2 Organic Halogen Compounds

3.3 Phosphorus Compounds

Flame Retardants for Plastics Market Report

3.4 Antimony Trioxide

Flame Retardants for Plastics Market Report

The advantages and disadvantages of antimony trioxide are summarised below.

3.5 Alumina Trihydrate

3.6 Magnesium Hydroxide

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

4 Products and their Markets

4.1.1 Bromine Compounds

4.1.1.1 Dead Sea Bromine Group

Flame Retardants for Plastics Market Report

Improvements have been made to FR-1806, a hexabromocyclododecane (HBCD), to provide better

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Improved flame retardation properties and antimony trioxide-free systems,

Flame Retardants for Plastics Market Report

4.1.1.2 Great Lakes

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Flame Retardants for Plastics Market Report

Saytex HP-800 is tetrabromobisphenol A bis(2,3-dibromopropyl) ether and is also very efficient.

4.1.1.4 Ferro Corporation

4.1.1.5 Unitex Chemical Corporation