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FEATURE ARTICLE www.rsc.org/materials | Journal of Materials Chemistry

Fire retardant polymers: recent developments and opportunities

Serge Bourbigot and Sophie Duquesne
Received 16th February 2007, Accepted 21st March 2007
First published as an Advance Article on the web 18th April 2007
DOI: 10.1039/b702511d
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In this Feature Article, we discuss recent developments of flame retardant polymers. Three
approaches are considered: (i) inherently flame retardant polymers, (ii) chemically modified
polymers and (iii) flame retardants as additives for polymers. We have tried to show the new
directions and concepts emerging in the field of flame retardancy. We have mainly focused our
comments on flame retardants, nanofillers and surface treatment because very promising concepts
appeared recently in the published literature. Synergistic aspects are also fully discussed.

1. Introduction (global demand for flame retardant is forecast to increase by

The development of science and technology provides the
availability of sophisticated products but concurrently
increases the use of combustible materials.1 Polymeric
materials are commonly used in everyday day life increasing
fire hazards and so flame retardants are very often incorpo-
rated into them to limit their flammability. As an example, in
2004, there were 508 fire-related deaths in the UK, compared
with 593 in 2003.2 The highest number recorded was 1 096
deaths in 1979. Through the 1980s and 1990s there was a
general downward trend in fire-related deaths. This trend can
be linked to the toughening of the legislation in terms of fire
hazards combined with the growing use of flame retardants
Laboratoire des Procedes dElaboration des Revetements Fonctionnels
(PERF), LSPES UMR-CNRS 8008, Ecole Nationale Superieure de
Chimie de Lille (ENSCL), BP 90108, 59652 Villeneuve dAscq Cedex,
France. E-mail: serge.bourbigot@ensc-lille.fr; Fax: +33 (0)3 20 43 65 84;
Tel: +33 (0)3 20 43 48 88
4.8% per year to 2.2 million metric tons in 2009).3
The flammability behavior of polymers is defined on the
basis of several processes and/or parameters, such as burning
rates (solid degradation rate and heat release rate), spread
rates (flame, pyrolysis, burn-out, smolder), ignition charac-
teristics (delay time, ignition temperature, critical heat flux for
ignition), product distribution (in particular, toxic species
emissions),4 smoke production, etc. Our goal is then to inhibit
or even suppress the combustion process acting chemically
and/or physically in the solid, liquid or gas phase. We can
interfere with combustion during a particular stage of this
process, e.g. during heating, decomposition, ignition or flame
spread. Three approaches can then be considered to reduce the
flammability of polymers: (i) to use inherently flame retarded
polymers (e.g. poly(tetrafluoroethylene), polyoxazoles, poly-
(ether-ether ketone) or polyimides);5 (ii) to chemically modify
existing polymers (e.g. copolymerisation of flame-retardant
monomer into PET chains6 or organic/inorganic hybrid

Serge Bourbigot was born on textiles, the simulation of heat

7 April 1964 in Paris.
Graduating from Ecole
Nationale Supe rieu re de
Chimie (ENSCL) of Lille,
Prof. Bourbigot passed his
PhD in 1993. He joined
ENSCL as a lecturer in 1993
and he passed his Habilitation
a Diriger des Recherches in
chemical engineering at the
University of Lille in 1998.
He got the position of
Professor in chemical engineer-
Serge Bourbigot ing at ENSAIT (Ecole
Nationale Superieure des Arts
et Industries Textiles) in 1999. In 2002, Prof. Bourbigot left his
laboratory to go to NIST (National Institute of Standard and
Technology at Gaithersburg, MD, USA) on sabbatical leave for
a year. In 2003 at the end of his sabbatical leave at NIST,
ENSCL offered him the position of Professor in flame
retardancy. His research interests include the development of
new flame retardant formulations for polymeric materials and
transfer in intumescent coat-
ings, and NMR methods for
characterizing (nano)filled
polymers and chars.
Sophie Duquesne, born in
1975, received her French
Ingenieur degree in chemical
engineering from Ecole
Nationale de Chimie de Lille
(ENSCL) in 1998 and her
PhD in spectrochemistry from
the University of Lille in 2001.
Sophie Duquesne She joined ENSCL as a lecturer
in 2001. Her research interests
include the processing of new flame retardant coatings and the
comprehension of the mechanism of intumescence from both
chemical and physical aspects. She also studies the modelling of
heat transfer in intumescent coatings during the combustion of
the materials. Her area of interest has further broadened to
include the processing, thermal degradation and fire retardancy
of polymer nanocomposites.

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polymers such as epoxy resin prepared from silsesquioxanes);7 a. Inherently flame retardant polymers
(iii) to incorporate flame retardants into polymers via
Before exploring details of the high performance polymers, it is
usual procedures.1 These three approaches will be further
important to define their parameters. For this discussion,
commented upon in the first section of this Feature Article
they are classified as polymers with a continuous operating
to provide the reader with the basic understanding of the
temperature ranging from 180 uC to 300 uC (or higher) and
mechanism of action leading to flame retardancy.
a degradation temperature higher than 350 uC. The flame
After commenting on the basics of flame retardancy in the
retardant ability of the polymer is defined using usual fire
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first part of this paper, we will emphasize recent developments

in the field of flame retardant (FR) polymers. Our article is
not an encyclopedic review of the literature associated with
polymer-based flame retardants; instead, we have tried to show
the new directions and concepts emerging in this field of
science. The following section will be devoted to the concept of
intumescence. It is a relatively older concept since the first
comprehensive paper was published in the early 1970s8 and the
first patent came out in 1938,9 but a brief review of the
literature shows that intumescence is largely employed to make
FR polymers or FR paints and that some recent developments
are very promising. More recently, it has been reported that
the presence of nanodispersed particles (e.g. montmorillonite
(MMT) clay, carbon nanotubes (CNT), polyhedral silses-
quioxanes (POSS)) in polymeric matrices produces a sub-
stantial improvement in fire performance (see ref. 10 and
references therein). In the following part, we will comment
critically upon the opportunity of using nanoparticles as flame
retardants taking into account the aspect of dispersion and
discussing the benefits of making polymer nanocomposites as
FR polymers. The next section of the paper will report the
aspects of synergy in FR systems. Finally, the last part will
investigate a very novel route for making polymers with low
flammability. The goal is to modify the polymeric surface
laying down a thin film on the polymer using plasma assisted
polymerization techniques. In addition to the reduction of
the flammability of the material, this approach offers
opportunities for designing multifunctional materials.
2. Basics of flame retardancy
Various methods can be used to protect materials more effec-
tively against attack by fire. Inherently FR polymers or high
performance polymers can be used but this implies the use of
specific materials which might not have the required properties
(e.g. aging, cost, etc.). Nevertheless, they exhibit very low
flammability and are very efficient. The second method is to
chemically modify the existing polymer to synthesize a FR
polymer. In this case, specific production processes are required
and very often the new FR polymer remains only synthesized
at the laboratory scale. The last method is to use flame
retardants and/or particles (micro- or nanodispersed) directly
incorporated in the materials (e.g. thermoplastics or thermo-
sets) or in a coating covering their surface (e.g. structural steel
or textiles).8 This approach is often preferred to provide low
flammability to polymeric materials because it is an acceptable
compromise between cost and properties and because it brings
great flexibility to design materials with multifunctional
properties. The first two approaches will be briefly described
in the following sections based on recent works and the last
one will be fully described in terms of mechanism of action in
order to introduce the other sections of this article.
testing methods (e.g., limiting oxygen index (LOI),11 cone
calorimetry,12 UL-94,13 etc.).
Development of high performance polymers started at the
end of the 1950s with the event of space travel, and continued
with military research. Polyimides (PI), for example, cannot
be ignited and incandesce in the presence of a flame. They
represent an important class of heterocyclic polymers and are
used in the most diverse applications. On the other hand,
several polymers among the so-called rigid-rod polymersa
relatively new class of heat resistant polymeric materialhave
been developed by the US Air Force Ordered Polymer
Program (polyoxazole or polythiadiazole). These polymers
are relatively difficult to manufacture and process, leading
to high production costs, but they exhibit remarkably low
flammability.14 The tendency to char of the organic inherently
FR polymers increases with their degree of linking: the forma-
tion of gaseous decomposition products and the tendency to
burn with an open flame diminish consequently.
Recently, a new family of p-phenylene-heterocyclic rigid-rod
and extended chain polymers including poly(p-phenylene-
2,6-benzobisthiazole) (PBZT) and poly(p-phenylene-2,6-
benzobisoxazole) (PBO) has attracted attention (Fig. 1).15,16
It was demonstrated that these two polymers exhibit excellent
mechanical properties and outstanding heat and flame
resistance. Their long-term mechanical tensile performance at
high temperatures was found to be critically associated with
the stability of the CO or CS linkage at the heterocyclic rings
on these polymers backbones. PBO polymers with the CO
linkages displayed substantially higher thermal stability
compared to PBZT containing CS linkages.
The development of these rigid-rod polymers has also
recently led to a novel polymer called poly(2,6-diimida-
zole[4,5-b:49,59-e]pyridinylene-1,4(2,5-dihydroxy)phenylene or
PIPD, also known as M5 during the development stage
(Fig. 2).17 PIPD exhibits extremely high fire resistance
properties like the other rigid-rod polymers.
Inorganic polymers are a broad class of polymers with
backbones consisting of alternating different atoms including
carbon, silica, phosphorus, nitrogen, boron, etc. Some of them
Fig. 1 Repeat units of PBZT (a) and PBO (b).

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Fig. 2 Repeat unit of PIPD.
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are not flammable (e.g. potassium aluminosilicate, or poly-
(sialate-siloxo) or geopolymer)18 and they do not need any
flame retardants or any flame retardancy treatment but
others exhibit poor flame retardancy needing FR treatment.
Nevertheless, pure inorganic polymers (compared with
inorganicorganic polymers) are non-flammable which is
why they were not studied in terms of reaction to fire in the
literature. A particular type of inorganic polymer attracted
attention in the late 1990s, the so-called geopolymers, as
potential low flammable materials for aircraft. Geopolymers
are linear poly(metasilicate)s with four-coordinate aluminate
crosslinks. The fire response of geopolymers exhibits promis-
ing performance compared to other organic polymers.19
The organic polymers reach the time to flashover (sudden
transition to a state of total surface involvement in a fire of
combustible materials within a compartment causing an
extremely rapid temperature rise) within 20 min (except
engineering plastics at 25 s but they release a lot of smoke)
while geopolymers never ignite. Another study confirms the
good fire resistance of geopolymers in the case of granulated
blast furnace.20
Many other polymers exhibit high fire and heat resistance
but their inclusion would be beyond the scope of this paper.
Here only the most recent developments have been given.
b. Chemically modified polymers
The incorporation of FR additives might require relatively
high loadings to be effective (typically 1040 wt% except for
the case of nanoparticles) and may result in adverse changes to
the physical and mechanical properties of the polymer (see
discussion in the following sections). An alternative approach
is to incorporate FR species via copolymerization or some
other type of chemical modification (e.g. grafting). The
relatively low loadings required to achieve sufficient flame
retardancy and the appropriate selection of the comonomer or
other modifying group may keep detrimental changes to the
physical and mechanical properties of the polymer to an
acceptable minimum (e.g., FR in the polymeric chain including
epoxy resins,21,22polyesters23 and polyurethanes).24 Recent
developments in the chemistry of halogen-free flame retardant
polymers involve polymers or reactive monomers that are
inherently flame retarding such as those containing P, Si, B, N
and other miscellaneous elements.25
Recent works report the incorporation of phosphorus into
polymeric materials as part of the polymeric chain in particular
in epoxy resins. Cured epoxy resins have a high concentration
of hydroxyl groups and therefore, P-containing flame
retardant compounds are particularly effective because P
tends to react with OH groups.26 Based on this approach,
Hergenrother et al.27 synthesized epoxies and their curing
agents (aromatic diamines) containing phosphorus to prepare
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FR epoxy formulations. Phosphorus was incorporated within
the backbone of the epoxy resin. The diamines included both
phosphonate and phosphine oxide structures while the epoxide
compounds included phosphates, phosphites, phosphonates.
They found that flame resistance is observed at a P
concentration of 1.5% by weight and fire resistance is observed
at P concentration of about 3% by weight. Flammability
reduction was attributed to the promotion of charring by P in
the condensed phase. Phosphorus appears to act as a catalyst
for char formation, i.e. P promotes char but is not consumed
in the chemical reactions that form char.
Marosi et al.28 used a similar approach synthesizing a
phosphorus-containing reactive amine, which can be used
both as a crosslinking agent in epoxy resins and as a flame
retardant. They showed that the synthesized amine can
substitute the traditional epoxy resin curing agents providing
excellent flame retardancy. The incorporation of nanoclay into
these systems improves the thermal stability as well as the
flame retardancy. More recently, Hoffman et al.29 reported the
feasibility of introducing phosphorus-containing groups into
the chemical backbone of thermoplastics, leading to the
successful synthesis of a novel halogen-free flame retardant
poly(sulfone) with a glass transition temperature exceeding
200 uC and of a poly(ether-ether ketone) with improved
thermal stability. The incorporation of these novel modifiers
into an amine-cured epoxy system showed promising flame
retardancy. Based on those results, Perez et al.30 further
evaluated the potential of such a phosphorus-modified
poly(sulfone) (P-PSu) as a flame retardant (Fig. 3). They
found a significant improvement of flame retardancy for the
epoxy resin modified by P-PSu. The suggested mechanism
involves char enhancement in the conditions of fire forming a
protective barrier. They also noticed an additional effect in the
gas phase depending on the concentration of phosphorus in
the material.
Silicon compounds are other molecules to be incorporated
in polymeric chains to provide flame retardancy to the
material. The flame retardant effect arises partly from the
property that silicon compounds have in diluting the more
combustible organic components and partly from the
barrier that silicaceous residues can form.31 The use of silicon
compounds as reactive components in flame-retardant systems
seems to have been little explored, despite their relatively low
combustibility, although interest has recently been shown in
the use of POSS as both additives and reactive components
in thermoplastics and thermosets.7,32 POSS have a notable
mechanical reinforcing effect upon polymers in which they are
incorporated, even at quite low loadings, and they improve
thermal stability and flame retardancy.
Fig. 3 Phosphorus modified PSu synthesized in ref. 30.
J. Mater. Chem., 2007, 17, 22832300 | 2285

Very few papers were published in the recent literature on
Si-containing polymers. Ebdon et al.33 investigated flame
retardancy of poly(methyl methacrylate) (PMMA) and poly-
styrene (PS) copolymerized with Si-containing acrylate mono-
mers. It was shown that introduction of Si-containing groups
resulted in a marginal increase in flame retardancy in both
styrene and methyl methacrylate copolymers. They suggested
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that the flame retardancy mechanism depends on the nature of
the Si-containing comonomer and arises mainly from a vapor
phase mechanism except in the case of copolymers with
monomers containing oligodimethylsiloxane side chains in
which case significant char yields suggest also a condensed
phase component.
The flame retardant action of the boron-containing com-
pounds on polymeric materials is mainly in the condensed
phase. It was found that these boron compounds promote char
formation in the burning process. The mechanism involving
the formation of the char is clearly related to the thermal
action of boric acid with alcohol moieties.34 Glass coatings can
be also formed at the surface which contribute to a barrier
effect, because they exclude oxygen and prevent further
propagation of combustion. Martin et al.35 investigated the
effectiveness of boron-containing monomers as flame retar-
dant components in chain reaction polymers in styrenics. Two
novel difunctional styrenic monomers2,2-bis(4-vinylbenzyl)
propane-1,3-diol and 5,5-bis(4 vinylbenzyl)-2-phenyl[1,3,2]
dioxaborinanewere synthesized and copolymerized. They
reported a significant improvement of flame retardancy via a
mechanism involving the formation of a protective barrier of
boron oxide, which prevents the degradation of the polymer.
This brief overview of recent works shows that good
performance can be achieved using FR reactive monomers
to synthesize polymers with acceptable low flammability. The
mechanism of action involves mainly a condensed phase
mechanism with the formation of a protective barrier
composed of char and oxides. Gas phase involvement is
also suggested in specific cases. All these mechanisms will
be detailed in the next sections where flame retardants as
additives will be considered.
c. Polymers containing flame retardants
Depending on their nature, flame retardants can act chemically
and/or physically in the solid, liquid or gas phase. Some of the
mechanisms described below have been already suggested in
the previous sections. Our intention here is to provide the
reader with the general principles of the mode of action of
flame retardants. Based on those principles, the recent
developments will be then overviewed in parts 3 to 6.
Flame retardants interfere with combustion during a
particular stage of this process, e.g. during heating, decom-
position, ignition or flame spread. The various ways in which
a flame retardant can act are described in the following
paragraphs. They do not occur singly but should be considered
as complex processes in which many individual stages occur
simultaneously with one dominating (e.g., using hydroxides
exhibits an endothermic decomposition cooling the substrate
and diluting the ignitable gas mixture due to the formation of
inert gases associated with the formation of an oxide protective
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barrier). There are several ways in which the combustion
process can be retarded by physical action:
(i) By formation of a protective layer. The additives can form
under an external heat flux a shield with a low thermal conduc-
tivity which can reduce the heat transfer from the heat source
to the material. It then reduces the degradation rate of the
polymer and decreases the fuel flow (pyrolysis gases issuing
from the degradation of the material) able to feed the flame in
flammable molecules. It is the principle of the intumescence
phenomenon (see section 3 of this paper).8,36 Phosphorus
additives may act in a similar manner. Their pyrolysis leads to
thermally stable pyro- or polyphosphoric species which form
a protective vitreous barrier. The same mechanism can be
observed using boric acid based additives, inorganic borates,
silicon compounds or low melting glasses.34,37
(ii) By cooling. The degradation reactions of the additive
can play a part in the energy balance of combustion. The
additive can degrade endothermally which cools down the
substrate to a temperature below that requires for sustaining
the combustion process. Aluminium trihydroxide (ATH) acts
partially under this principle and its efficiency depends on the
amount incorporated in the polymer (generally 60 wt.-% in
thermoplastics).38
(iii) By dilution. The incorporation of inert substances (e.g.
fillers such as talc or chalk) and additives which evolve inert
gases on decomposition dilutes the fuel in the solid and
gaseous phases so that the lower ignition limit of the gas
mixture is not exceeded.39
The most significant chemical reactions interfering with the
combustion process take place in the condensed and gas
phases:
(i) Reaction in condensed phase. Here two types of reaction
can take place. Firstly, breakdown of the polymer can be
accelerated by the flame retardant causing pronounced flow of
the polymer and, hence, its withdrawal from the sphere of
influence of the flame which breaks away. Secondly, the flame
retardant can cause a layer of carbon (charring), a ceramic-like
structure and/or a glass to be formed on the polymer surface.40
(ii) Reaction in gas phase. The radical mechanism of the
combustion process which takes place in the gas phase is
interrupted by the flame retardant or their degradation pro-
ducts. The exothermic processes which occur in the flame are
thus stopped, the system cools, and the supply of flammable
gases is reduced and eventually completely suppressed. In
particular, metallic oxides can act as flame inhibitors.
Note that fire retardant additive systems may be used alone
or in association with other systems (sometimes using small
amounts of the last system) in polymeric materials to obtain a
synergistic effect, i.e. the protective effect is higher than that
assumed from addition of the separate effects of each system
(see the fifth section of this paper).41,42
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Fig. 4 Number of references dealing with intumescence (database
Chemical Abstract Plus).
3. Intumescence: an older concept for recent
developments
Even though intumescent systems have been reported in the
literature since 1938,9 they still appear as an attractive topic
and represent a wide and interesting area of research and
development as demonstrated by the number of papers or
patents dealing with this subject since the 1980s (Fig. 4). The
aim of this section is to comment upon the recent development
and applications for intumescents.
Intumescent systems were first reviewed in the 1970s by
Vandersall8 and were mainly applied to paint. It was the
pioneering comprehensive work of Camino et al. which
permitted the development of this concept to polymers.43,44
Now it is well established that they are mainly composed of
an inorganic acid or a material yielding acidic species at
temperature between 100 and 250 uC, of a char former and of a
component that decomposes at the right temperature and at
the right time to enable the blowing of the system. Typical
examples of components used in intumescent systems are
reported in Table 1.
The following sequences of events was proposed to occur in
the development of the intumescent phenomena:
1. the inorganic acid is released between 150 and 215 uC
depending on its source and other components
Table 1 Examples of components of intumescent systems
(a) Inorganic acid source
Phosphoric
Sulfuric
Boric
Ammonium salts
Phosphates, polyphosphates
Borates, polyborates
Sulfates
Halides
Phosphates of amine or amide
Products of reaction of urea or guanidyl urea with phosphoric acids
Melamine phosphate
Product of reaction of ammonia with P2O5
Organophosphorus compounds
Tricresyl phosphate
Alkyl phosphates
Haloalkyl phosphates
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Fig. 5 Intumescent coating (from ref. 48).
2. the acid esterifies the carbon rich components at
temperatures slightly above the acid release temperature
3. the mixture of materials melts prior to or during
esterification
4. the ester decomposes via dehydration resulting in the
formation of a carboninorganic residue
5. released gases from the above reactions and degradation
products cause the carbonizing material to foam
6. as the reaction nears completion, gelation and finally
solidification occur. This solid is in the form of multicellular
foam (Fig. 5).
A typical example is the case of polypropylene (PP)
ammonium polyphosphate (APP)/pentaerythritol (PER) sys-
tem.36,4345 The reaction of the acidic species (APP and its
degradation products into orthophosphates and phosphoric
acid) with the char former agent (PER) takes place in a first
stage (T , 280 uC) with formation of ester mixtures. The
carbonisation process then takes place at about 280 uC (via the
formation of double bonds followed by DielsAlder reaction
and a free radical process increasing the size of the poly-
aromatic structure).46 In a second step, the blowing agent
decomposes to yield gaseous products (i.e., evolved ammonia
from the decomposition of APP) which cause the char to swell
(280 T 350 uC). The intumescent material decomposes
then at higher temperatures and loses its foamed character at
about 430 uC.45 Concurrently, the heat conductivity of the
(b) Polyhydric compounds
Starch
Dextrins
Sorbitol, mannitol
Pentaerythritol, monomer, dimer, trimer
Phenol-formaldehyde resins
Methylol melamine
Char former polymers (PA-6, PA-6/clay nanocomposite PU, PC, etc.)
(c) Blowing agents
Urea
Urea-formaldehyde resins
Dicyandiamide
Melamine
Polyamides
J. Mater. Chem., 2007, 17, 22832300 | 2287

char decreases between 280 uC and 430 uC and the insulation
of the substrate is enhanced.47
The foam layer acts as a heat insulator, limiting the heat
transfer from the heat source to the polymer and the mass
transfer from the polymer to the flame resulting in improved
fire retardant performances. When designing an intumescent
system, it is important to take into account the chemistry of
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the system. As an example, the carbon containing ingredient
must decompose in such a manner that a carbon residue
is formed in the presence of the inorganic acid. However,
chemistry is not the whole story of the intumescence
phenomenon. The efficiency of the system is also driven by
the plasticity of the coating at the temperature corresponding
to the expansion of the material. First measurements have
recently been carried out regarding this topic.49 It was
shown that the rheological and mechanical properties of the
intumescent protective charred layers developed by several
materials could be correlated with their fire retardant
performance.50,51 The growing bubbles in the corresponding
temperature field will be affected by those parameters and this
effect can not be neglected in terms of temperature gradients
and heat transfer in intumescent systems.52
The intumescent systems were firstly designed as fire
protective coatings for metallic structures and the need for
such coatings is still increasing. Intumescent materials are
classified as either thick or thin film intumescent coatings.
Intumescent thick films are usually based on epoxy resins and
contain agents that intumesce when exposed to heat (typical
commercial systems under the brand names Nullfire from
Tremco or Chartek from Akzo Nobel). They are available as
solvent free systems that allow application of up to 810 mm
per coat. These films are particularly efficient in the case of
hydrocarbon and jet fires. Thin intumescent films were
introduced as early as the 1930s and are used for protection
from cellulosic type fires. They are generally available as
solvent or water based systems, and applied by spray or
brush-roller in thin film coats up to 3 mm thick. They typically
use thermoplastic acrylic based resin systems, and they
respond rapidly and intumesce quickly when exposed to a
cellulosic type fire environment. Although the patent literature
is abundant, research papers dealing with the mechanism of
action of the different ingredients regarding the fire protection
of intumescent coating are relatively recent. The mechanism of
action of a highly efficient epoxy-amine based intumescent
system designed to protect steel in the case of hydrocarbon fire
has been recently investigated.34,53 It was shown that the
combination of ammonium polyphosphate derivatives and
boric acid leads to a high efficiency coating. It is suggested
that the formation of borophosphate is responsible for the
development of a hard intumescent char: the borates provide a
hard and mechanically resistant char, while the presence of
phosphorus allows good adhesion of the char to the steel plate.
The role of the binder resin in the development of thin film
intumescent coatings has also been recently investigated.54,55
The effect of the nature of the monomers, which compose the
binder, on the chemical reactivity between the binder and the
intumescent additives was examined. In this study, special
attention was devoted to the expansion rate and to the
dynamic viscosity of the molten intumescent system within the
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expansion steps. It was found that the thermal insulation
is greatly improved when using a mixture of linear and
crosslinked copolymers as the binder in intumescent coatings
particularly when these copolymers are prepared from mono-
mers showing good reactivity with ammonium polyphosphate.
Earlier in the 1980s, intumescent systems were used to flame
retard polymer and in particular thermoplastics.5658 However,
such systems present some drawbacks (water solubility,
migration of the additives throughout the polymer) that
can be prevented by synthesizing novel phosphorus- and/or
nitrogen-containing systems. As an example, APP based
systems can not be used in high temperature processing
polymers (such as poly(ethylene terephthalate), PET) because
it begins to loose ammonia and water from 250280 uC45 and
PET is usually processed in this range of temperature. In such
a case, the synthesis of phosphorus-containing copolymers
(see section 2) is one efficient way to address the issue of
flame-retardation of polymers using the intumescence concept.
Moreover, the copolymerization could fix the fire retardant
monomer completely and thus dissolution or extraction cannot
take place when the materials are used leading to permanent
fire retardant properties. In this field, Ma et al.59 reported the
synthesis of phosphatepolyester copolymers from spirocyclic
pentaerythritol di(phosphate acid monochloride)s (1). It was
shown that the LOI of the copolymer increases with increasing
phosphate content to reach a maximum of 30 vol%. Wang
et al.23 reported the synthesis of a novel intumescent flame
retardant, poly(2,2-dimethylpropylene spirocyclic pentaery-
thritol bisphosphonate) (2) to yield PET with both excellent
flame retardancy and anti-dripping properties.
Another drawback of the APP-based systems is their high
water solubility. The encapsulation and the coating tech-
nologies are potential ways of investigation to go beyond this
limitation. The use of microcapsules of di-ammonium hydro-
gen phosphate (DAHP) with a polyether-polyurethane shell
and a polyester-polyurethane shell were reported as intumes-
cent flame retardants (FR) in a commercial polyurea coating
for textiles.60 The expected advantages of this new concept of
encapsulated FR agent are to be compatible with a polymeric
matrix in order to give a permanent FR effect and to be itself
an efficient FR intumescent formulation for many materials.
Both types of DAHP microcapsule present in the polyurea
coatings on cotton fabric give an efficient FR effect, although
the char developed with microcapsules is a little less heat
resistant than that developed with the pure DAHP.
The development of new environmentally friendly synthesis
pathways to flame retardant systems also appears as an
interesting way of investigation. Recently, Liu and Wang61
This journal is The Royal Society of Chemistry 2007

have proposed to use the catalytic action of phosphotungstic
acid in the synthesis of melamine salts of pentaerythritol
phosphate (MPP) (3) in order to solve the problems of
conventional preparation methods (the use of the poisonous
reactant POCl3; the high temperature of the reaction and thus
the high energy consumption, etc.). It was showed that this
acid can remarkably enhance the conversion degree of the
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reaction and make the reaction temperature decrease by 20 uC
while keeping a satisfactory conversion, thus greatly control-
ling the energy-consumption in the preparation process
of MPP. The results also indicated that as compared to
non-catalyzed MPP, the phosphotungstic acid-catalyzed
MPP flame retardant system remarkably improved the
flame retardant properties by effectively consolidating and
stabilizing the char layer, while maintaining good mechanical
properties.
The synthesis of PEPA (1-oxo-4-hydroxymethyl-2,6,7-
trioxa-l-phosphabicyclo[2.2.2]octane) (4) and bis(PEPA)phos-
phate-melamine salt derivatives prepared by a novel and safe
protocol was also reported.62 These new salts were incorpo-
rated into polypropylene (PP) and exhibit good fire retardant
performance via an intumescence mechanism.
The use of polyols such as pentaerythritol, mannitol or
sorbitol as char formers in intumescent formulations for
thermoplastics is associated with exudation and water solubi-
lity problems. Moreover, these additives are often not
compatible with the polymeric matrix, and the mechanical
properties of the formulations are then very poor. Fire
retardant intumescent polyolefin-based formulations using
charring polymers (thermoplastic polyurethane and poly-
amide-6) as carbonization agents have been developed. These
formulated blends have improved mechanical properties in
comparison with polymers loaded with classical FR formula-
tions, and they avoid the problems of exudation and water
solubility.6368
The organic intumescent systems represent a large part of
the studies dealing with intumescence while the processing of
intumescent mineral systems is even older.69 Mineral intumes-
cent systems may be based on alkali silicates. The swelling of
the material on heating or on contact with a flame is due to
an endothermic process and is associated with the emission of
water vapor that is ionically hydrated in the silicate system.70
This journal is The Royal Society of Chemistry 2007
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The solid foam formed is rigid and consists of hydrated silica.
The structure remains solid until it reaches its glass-softening
point. Since only water vapor is released, toxic fumes that
may be released from organic-based systems are eliminated.
Intumescent alkalis have serious limitations, in particular
they are sensitive to carbon dioxide which is present in the
atmosphere causing the silicate coating to gradually lose its
intumescence, to become brittle, and to lose its adhesion.
Coatings based on a system of sodium silicate, potassium
silicate, and lithium silicate that provides exceptional environ-
mental stability and a high degree of intumescence, have
been recently developed.70 This coating was proposed to be
used for the fire protection of glass reinforced plastics for
naval applications.
Expandable graphite represents another class of inorganic
intumescent systems. Expandable graphite (EG) is a graphite
intercalation compound (GIC). It appeared in the literature in
1841.71 It is a layered crystal consisting of sheets of carbon
atoms tightly bound to each other. Chemicals (such as sulfuric
acid) may be inserted between the carbon layers. When
exposed to heat, EG expands and generates a voluminous
insulating layer thus providing fire performance of interest to
the polymeric matrix. EG has been used advantageously in
polyurethane coatings to develop fire protective coatings for
polymeric substrates.72
4. Polymer nanocomposites as fire retardant
polymers: myth or reality
Gilman et al. reported that the presence of nanodispersed
montmorillonite (MMT) clay in polymeric matrices produces
a substantial improvement in fire performance.7375
Gilman and other groups subscribed to this approach and
developed hybrid polymeric materials including organo-
modified clays,7679 nanoparticles of TiO2,80 nanoparticles of
silica,81 layered double hydroxides (LDH),82,83 carbon nano-
tubes (CNT)84,85 or polyhedral silsesquioxanes (POSS) .8688
All these materials exhibit low flammability in terms of heat
release rate (HRR) associated with other properties such as
enhanced mechanical properties. Typically, the peak of HRR
is decreased by 5070% in a cone calorimeter experiment.
However, the UL-94 and LOI results of polymer nanocompo-
sites are poor. As an example, the peak of HRR of polyamide-
6 (PA-6)/clay nanocomposites is decreased by 63% compared
to virgin PA-6 at 35 kW m22 while the UL-94 test is failed (no
rating) and the LOI is only 23 vol%.89 Typical fire behavior of
polymer nanocomposite during UL-94 or LOI testing does not
exhibit dripping and the formation of a char layer can be
observed at the surface of the material. Nevertheless, the
carbonaceous layer is not effective enough to stop the flame
and the material continues to burn slowly failing the test.
According to recent published works, our aim in this section
is to discuss critically if polymer nanocomposites are (or
might be) real flame retardant polymers. The first point to be
considered is the nanodispersion (since the filler must be
nanodispersed to talk about nanocomposites) and its influence
on flame retardancy. The mechanism of action will be then
examined and critical aspects of nanocomposites as flame
retardant polymers will be finally discussed.
J. Mater. Chem., 2007, 17, 22832300 | 2289
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nanocomposite formation has not occurred. A quick overview

of the literature indicates that this is probably true.9093
Polymer clay nanocomposites can exhibit different morpho-
logies but from the discussion above no assumption may be
made about their role in the fire behavior. In general, polymer
clay composites are of three categories:94 (i) microcomposites:
the clay tactoids exist with no penetration of the polymer into
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the clay lamellae; (ii) exfoliated composites: the individual clay

Fig. 6 Comparison of the heat release rate (HRR) plots for pure
EVA, EVA-Na+ (microcomposite) and EVA-C30B (nanocomposite)
at 50 kW m22 heat flux with a mass fraction of 5% layered silicate.
a. Nanodispersion and flame retardancy
The obvious aspect of nanodispersion when investigating
flame retardancy is not always commented on in the literature
and it is often assumed when incorporating the so-called
nanoparticles that a polymer nanocomposite is formed. The
first question is then: what is the role of the nanodispersion?
To answer this question, we take as a representative example
poly(ethylene-co-vinyl acetate) (EVA) containing MMT clay
(numerous organomodified (OM) MMTs are widely used to
make polymer nanocomposites). MMT clays organomodified
by methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium
chloride (C30B) and raw MMT (Na+) were melt blended
with EVA (EVA containing 19% vinyl acetate) according to
a protocol described in ref. 90. EVA-C30B exhibits an
exfoliated/intercalated intermediate structure determined both
by X-ray diffraction and by transmission electronic micro-
scopy (TEM) while EVA-Na+ is a microcomposite. Cone
calorimetry experiments reveal that the peak of heat release
rate (HRR) is decreased by 25% for the microcomposite
(EVA-Na+) and by 50% for the nanocomposite (EVA-C30B)
compared to virgin EVA (Fig. 6). This result suggests that a
real nanodispersion should be achieved to achieve the lowest
flammability. Similar conclusions were also reported in other
published works.91,92 Zheng and Wilkie93 extended those
conclusions in a more general way suggesting based on
experience and on literature that no reduction or a slight
reduction in the HRR peak can be taken as an indication that
layers are dispersed as single platelets into a continuous
polymer matrix; (iii) intercalated composites: in an intercalated
composite the insertion of polymer into the clay structure
occurs so as to swell the spacing between platelets in a
regular fashion, regardless of the clay to polymer ratio.
Characterization and quantification of the nanomorphology
is not an easy task with the usual techniques (e.g. WXRD,
TEM) which is why we have developed at NIST a novel
method using solid state nuclear magnetic resonance (NMR)
of protons. It is able to quantify the degree of nanodispersion
of the layered silicate in the bulk polymer.95,96 From our
approach, we proposed 2 parameters relating to the dispersion.
The first parameter, f, is the fraction of the potentially
available clay surface which has been transformed into
polymer/clay interfaces. The second parameter, e, is a relative
measure of the homogeneity of the dispersion of these actual
polymer/clay interfaces. These parameters can be used to
quantitatively investigate the effect of the morphology of the
polymer nanocomposite on the fire properties. Zhu and Wilkie
synthesized different polystyrenes (PS) according to a protocol
described in reference 97 used as well calibrated samples
for our purpose. Cloisite Na+ was organomodified by three
different ammonium salts, namely, N,N-dimethyl-n-hexadecyl-
(4-hydroxymethylbenzyl)ammonium chloride, OH16, N,N-
dimethyl-n-hexadecyl(4-vinylbenzyl)ammonium chloride,
VB16, and n-hexadecyl triphenylphosphonium chloride,
P16.76 The preparation of the VB16, OH16 and P16
nanocomposites with styrene was then accomplished by the
bulk polymerization technique. The values of the fraction of
the interface polymer/clay available in PS, f, as well as the
associated degrees of homogeneity of the nanomixing, e, are
given in Table 2.
PS nanocomposites containing OH16, P16 and VB16 clays
have been evaluated by cone calorimetry. It is found that clay-
based nanocomposites have a lower heat release rate (HRR)
than does the virgin polymer (Fig. 7). The peak of HRR
(PHRR) of the virgin PS is 1025 kW m22 and those of PS-P16,

Table 2 Fraction of the interface polymer/clay, f, available in PS and estimation of the degree of homogeneity, e, in PS/MMT nanocomposites
Polymer Residuea (wt%) T1H/s fb e (%) TEM/XRD conclusions

PS 0 26 0
PS/P16 2.3 9.31 0.46 69 Nanodispersed, intercalated
PS/OH16 2.0 10.5 0.34 63 Nanodispersed, intercalated/exfoliated
PS/VB16 2.0 9.00 1.0 39 Exfoliated
a
Residue at 800 uC measured by TGA in air. b An exfoliated structure allows intimate contact between each MMT platelet and the polymer;
hence, maximal interfacial area will be exposed and f will be close to one. In the opposite case of a microcomposite structure, the dispersion of
MMT platelets is comparatively poor and the polymer/clay interfacial area is small (f will be close to zero). In the intermediate case
(intercalated structure or mixed intercalated/exfoliated), the measured relaxation rate at the shorter times will be controlled by the
nanodispersion of MMT, by the number and the size of tactoids and by the number of delaminated layers in the polymer (0 , f , 1). The
lower f value of PS/OH16 exhibiting a mixed intercalated/exfoliated morphology compared to PS/P16 exhibiting an intercalated structure
suggests the presence of larger tactoids for PS/OH16 than for PS/P16 (see ref. 96 for complete discussion).

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Fig. 7 Heat release rate (HRR) curves at 50 kW m22 of PS,

PS/OH16, PS/VB16 and PS/P16 versus time.

PS/VB16 and PS/OH16 fall to 590 kW m22, 520 kW m22 and

500 kW m22 respectively. The suggested mechanism by which
clay nanocomposites function involves the formation of a char
that serves as a barrier to both mass and energy transport. It
should also be noticed that PHRR is decreased by about 50% Fig. 8 TEM image of PS/MWNT (without IM) (on a part of the
for the three nanocomposites as expected for nanocomposites image the background was removed to perform image analysis).
exhibiting a reasonable dispersion. From Fig. 7, it can be seen
that there is not a large difference between the three nano- case of PS/MWNT-IM (Fig. 9) (similar compatibilization has
composites. According to NMR data, PS/OH16 and PS/P16 been found with MMT in epoxy resin103).
almost exhibit the same nanostructure (same f and e) but have To evaluate the influence of the nanodispersion, PS
90 kW m22 difference in PHRR. PHRR of PS/VB16 falls at an nanocomposites were evaluated using a radiative gasification
intermediate value between those of PS/OH16 and PS/P16 instrument similar to the cone calorimeter developed at
and its nanostructure is an exfoliated structure not very well NIST.104 The mass loss rate of the three samples recorded
distributed in the polymer (e = 39%). This observation suggests versus time is shown in Fig. 10. Reduction of mass loss rate of
that no definitive conclusion may be made regarding the PS nanocomposites is observed compared to the virgin PS but
morphology of nanomixing and fire performance relation-
ship. We need now to synthesize exfoliated PS nanocomposites
with a very good distribution of MMT platelets as a model to
determine and to quantify precisely the effect of exfoliation on
fire properties. This work is in progress in our laboratory and
will be published in a separate paper.
Carbon nanotubes (CNTs) can also be nanodispersed in
polymeric matrix and are of interest for flame retardancy.
Kashiwagi et al. reported the first study on the flammability of
polymer carbon nanotube nanocomposites.98 They showed
significant flame retardant effectiveness of polypropylene
(PP)/multi-walled carbon nanotube (MWNT) (1 and 2% by
mass) nanocomposites. According to the authors, CNTs were
reasonably well dispersed but no further compatibilization was
used and we suspect that some aggregates might remain.
Indeed nanotubes preferentially aggregate into bundles, where
adjacent tubes are held together by strong van der Waals
attractions.99 Further compatibilization can be achieved
through functionalization; such as through covalently bonding
organic groups directly to the CNT.100,101 We have prepared
well dispersed MWNT polystyrene (PS) nanocomposites via
melt extrusion using trialkylimidazolium tetrafluoroborate
(IM) compatibilized MWNT.102 TEM images combined with
image analysis reveal that agglomerates (#1 mm) of nanotubes
dominate in the case of the PS/MWNT without IM (Fig. 8) Fig. 9 TEM image of PS/MWNT-IM (on a part of the image the
while well dispersed single nanotubes can be observed in the background was removed to perform image analysis).

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Fig. 10 Mass loss rate of the virgin PS compared to PS nanocompo-
sites in a gasification experiment at 50 kW m22.
the mass loss rate of PS/MWNT-IN is significantly lower
than that of PS-MWNT. This indicates as in the case of MMT
that the highest nanodispersion is required to get the best
performance.
With the two typical examples presented above, we may
suggest that the quality of the particles nanodispersion is one
of the key parameters to get the highest performance in terms
of peak of HRR. Other works found in recent published
papers using different particles confirm our conclusions.
Costantino et al.105 synthesized new hydrotalcites organo-
modified with different anions which were melt-blended in
polyethylene (PE) to form PE nanocomposites. An exfoliated
morphology was reported and the peak of HRR was decreased
by 55% as expected when a real nanocomposite is formed.
Laachachi et al.106 used nanoparticles of Fe2O3 and TiO2 at
different loading to make poly(methyl methacrylate) (PMMA)
nanocomposites by melt-blending. They compared the nano-
composites with their microcomposites at the same loading
(15 wt%) but surprisingly, the peaks of HRR for those samples
(micro vs. nano) are similar. The peak of HRR is decreased by
30% for Fe2O3 and by 40% for TiO2. The explanation was
given by Wilkie et al.107 arguing the fact that PMMA/clay
nanocomposites do not exhibit any changes in the evolved
products upon incorporation of clay. They suggested that the
number of degradation pathways of the polymer is one of the
factors that can affect the fire retardancy of polymer/clay
nanocomposites. If the degradation occurs by only a single
pathway as in the case of PMMA, then more thermally stable
products are not produced and the fire retardancy is not
significantly improved in the presence of clay. The measured
performance can only be explained by the relatively high
loading diluting the fuel and by the formation of a potential
oxide barrier at the surface. Du et al.108 used halloysite
nanotubes (HNTs) with hollow nanotubular structures in
polypropylene (PP). A surface treatment of HNTs can make
them organophilic and enables the preparation of PP
nanocomposites. According to scanning electronic microscopy
(SEM) the authors suggested HNTs were dispersed in the PP
matrix evenly at the nanoscale. Cone calorimetry gives support
for this assumption since the peak of HRR is decreased by
55% while PP microcomposites prepared with unmodified
HNTs gives only 25% reduction.
2292 | J. Mater. Chem., 2007, 17, 22832300
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b. Mechanism of action
Polymer nanocomposites exhibit low flammability and this
section will discuss the recent understanding of the mechanism
of action. The mechanism of protection involves in each case
the formation of a char layer covering the entire sample
surface acting as insulating barrier and reducing volatiles
escaping to the flame. The formation of such a layer which
does not form cracks when burning is critical to obtain a low
heat release rate from nanocomposites.
Kashiwagi et al.109 first examined the mechanism of flame
retardancy of a PA-6 clay nanocomposite. Visually, they
observed the formation of a thin char layer on the top of the
samples during a cone calorimeter experiment. In the case of
the PA-6 nanocomposite, the char layer is tougher and grows
throughout the combustion yielding a rigid multicellular
char-brick. TEM of the combustion char layer of the nano-
composite reveals a multilayered silicate structure. The silicate
sheets forms a large array of fairly even layers. It was suggested
that this structure may act as an insulator and a mass transport
barrier, slowing the escape of volatile products generated as
PA-6 decomposes. This first important result provides two
pieces of information: (i) the accumulation of silicate platelets
at the surface and (ii) the favored carbonization to yield a
protective layer. The accumulation of aluminosilicate platelets
was evidenced by Wang et al.110 using X-ray photoelectron
spectroscopy (XPS) examining several polystyreneclay nano-
composites. The accumulation of oxygen, from the alumino-
silicate, on the surface of the polymer was observed, along with
the loss of carbon. This confirms that the formation of the
barrier comes from the clay. They noticed that there is no
difference depending upon the extent of exfoliation or
intercalation of the nanocomposite. This result suggests as
we mentioned above that the nanomorphology should not
significantly influence the fire behavior.
In a recent work, Kashiwagi et al.111 investigated step by
step the mechanism of the formation of the char layer in PA-6
clay nanocomposites (nanocomposites exhibit an exfoliated
morphology) collecting residues at various sample mass losses
prepared via a gasification process. The analysis of the
floccules of blackened residues showed that up to 80% by
mass of the residues consists of clay particles and the
remainder is thermally stable organic components with
possible graphitic structure. Furthermore, clay particles
were stacked in the carbonaceous floccule residues and the
d-spacing of the clay platelets is in the range of 1.31.4 nm as
compared to the well exfoliated original sample. It is then
suggested that the accumulation of the initially well-dispersed
clay particles in the sample on the burning/gasifying sample
surface is due to two possible mechanisms. One is recession of
the polymer resin from the surface by pyrolysis with the de-
wetted clay particles left behind. Another mechanism is the
transportation of clay particles pushed by numerous rising
bubbles of degradation products and the associated convection
flow in the melt from the interior of the sample toward the
sample surface. Kashiwagi et al. mentioned that numerous
rising bubbles may have another effect on the transport of clay
particles. Bursting of the bubbles at the sample surface pushes
the accumulated clay particles outward from the bursting area
This journal is The Royal Society of Chemistry 2007

and forms the island-like floccules instead of forming a
continuous net-like structure of clay filled protective layer.
Therefore, both PA6clay nanocomposite samples did not
produce sufficient amounts of protective floccules to cover the
entire sample surface and the protection is not completely
efficient. In a more recent work, Lewin112 completed the
fundamentals of the previous mechanism. He pointed out that
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the causes of the migration are: temperature and viscosity
gradients of the melt with regard to heat source; propelling the
organically layered silicate to the surface by gas bubbles
from the decomposing surfactant and polymer; and by the
difference in surface free energy between the polymer and the
polymerclay aggregate. He emphasizes that the structure of
the nanocomposite changes to a microcomposite when the
sample burns. The concentration of the surfactant decreases
and the polymer is removed from the clay, pristine clay is
formed, and aggregates to microcomposite particles, which do
not migrate to the surface in non-directional heating. Finally,
he postulated that the migration depends on (i) the amount
of exfoliated clay particles which are the reservoir for the
migration, (ii) the nature of the surfactant, and (iii) its rate
of decomposition.
Similar mechanisms were reported for polymer CNT nano-
composites and polymer POSS nanocomposites. Once again
Kashiwagi et al.113,114 investigated the mode of action of CNTs
(multi-wall and single-wall CNTs) as flame retardants as they
did in the case of polymer clay nanocomposites. They found
that the shape of carbon particles appear to be important for
effectively reducing the flammability (comparison carbon
black vs. MWNT) but they reported that the effects of residual
iron particles and of defects in the MWNTs on the HRR of the
nanocomposite were not significant. The flame retardant
performance is achieved through the formation of a relatively
uniform network-structured floccule layer covering the entire
sample surface without any cracks or gaps. In the particular
case of a PMMA/SWNT nanocomposite, they noticed when
the concentration of SWNT was low (0.2 wt%) the formation
of discrete islands assigned to the localized accumulation of the
nanotubes as a result of fluid convection accompanying bubble
formation and rise of the bubbles to the surface through the
molten sample layer and bursting of the bubbles at the surface.
These then formed a network layer acting as a heat shield to
slow the thermal degradation of the polymer. In a recent
comprehensive work,115 they demonstrated that the incorpora-
tion of CNTs as well as carbon nanofibers at a sufficient
loading (1 wt%) in a polymer matrix permitted upon heating
the formation of a jammed network structure such that the
material as a whole behaves rheologically like a gel. This
permits quickly the formation of a continuous network
protective layer much more efficient that the formation of
discrete islands aggregating as a function of time.
POSS is also a candidate for the design of polymer nano-
composites.116118 It reinforces polymer chains on a molecular
level analogous to the macroscopic reinforcement that fibers
provide in composite structures. Lichtenhan et al.119 showed
the efficiency of using POSS in commodity and engineering
polymers. As an example, the peak of heat release rate
(external heat flux = 35 kW m22) of a polyether block amide
polymer (PEBAX) is decreased by 77% when using POSS
This journal is The Royal Society of Chemistry 2007
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compared to virgin polymer.120 The suggested mechanism is
char formation at the surface of the material which can act as
an insulating barrier.121 It is similar to the mechanisms we
described above. The organic groups on POSS cages undergo
homolytic SiC bond cleavage at y300350 uC in air.
This process is immediately followed by fusion of POSS
cages to form a thermally insulating and oxidatively stable
silicon oxycarbide black glass surface char (SiOC
ceramified char).122
As a conclusion of this section, we have seen that polymer
nanocomposites exhibit similar mechanisms of flame
retardancy whatever the nanoparticles involves. The key point
is the formation of a protective charred layer lowering the heat
release rate and hindering the combustion of the polymer.
This then gives rise to the question: can we achieve real low
flammability with polymer nanocomposites?
c. Critical discussion
Polymer nanocomposites exhibit low flammability when
evaluated by cone calorimetry (sample in horizontal position)
but fail other tests, in particular those with samples in vertical
positions (e.g. LOI, UL-94). In a critical paper on the
flammability of layered silicate polymer nanocomposites,
Bartholmai and Schartel123 showed no relevant flame behavior
enhancement in LOI and UL-94 tests except for the dripping
which becomes limited. They proposed a mechanism of
protection similar to that described above but they suggested
the interesting feature that the influence of the barrier vanished
for small external heat flux (like in the cases of LOI and
UL-94). They also noticed that the fire behavior observed for
nanocomposites was different in terms of slower burning
velocity and hindered dripping. They postulated that viscosity
became the governing parameter. In addition to this, we
should notice that in a typical cone calorimetry evaluation,
nanocomposites tend to burn slowly and nearly completely. In
terms of total heat evolved, no relevant difference between
nanocomposites and reference material is generally detected
proving that the charred layer slows the escaping flammable
molecules and spreads out the time of combustion. Using
kinetic analysis, Bourbigot et al.124 suggested that the clay acts
as a char promoter slowing the degradation and providing a
transient protective barrier to the nanocomposite in combina-
tion with the aluminosilica barrier which arises from the clay.
The combination of these two effects is an important factor
lowering the HRR.
Nanocomposites need further improvements to increase the
ignition delay time which is usually less than that of the
neat polymer.114,125 The first convincing explanation of this
behavior was proposed by Kashiwagi et al.114 in the particular
case of PP/MWNT. The external heat flux is absorbed very
near the sample surface in the case of PP/MWNT. Therefore, a
narrow layer in the vicinity of the PP/MWNT sample surface is
rapidly heated and its temperature becomes high enough to
initiate thermal degradation of PP and to generate evolved
degradation products to initiate ignition. On the other hand,
the PP sample is heated over a greater depth and it thereby
takes a longer time to heat the sample to initiate degradation.
Very recently Dubois et al.126 reported that incorporating
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crushed MWNT in EVA permits surprisingly both the
reduction of the PHRR of EVA and the increase of the time
to ignition. They attributed this effect to a chemical effect
through the chemical reactivity of the radical species existing
at the surface of crushed MWNTs during combustion. The
demonstration is based on the slight increase of thermal
stability (15 uC) comparing EVA/MWNT and EVA/crushed
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MWNT during the first step of degradation. It is then assigned
to the modification of the thermooxidative pathway. This
explanation might be correct to explain the TG curve but it is
not sufficient for the fire behavior. The authors did not take
into account the potential modification of thermophysical
properties of the surface of the sample due to the incorpora-
tion of crushed MWNTs (see discussion above). This last effect
might be predominant and, in this particular case, beneficial.
We can suggest that the shorter length of crushed MWNTs
modifies the IR absorption as explained above in such a way
that the resulting effect increases the time to ignition. It was
confirmed by Delichatsios127 in the case of a PA6 clay
nanocomposite (such an effect can be also assumed for
MWNTs) who suggested that ignition occurs earlier because
the formation of the melt, which has higher conductivity than
the solid, is delayed in the nanocomposite. Because of the
lower conductivity of the solid, the time to reach the ignition
temperature at the surface decreases for the nanocomposites.
This provides evidence that the thermophysical properties are
the governing parameters for the time to ignition.
From this discussion, we can draw some conclusions about
the ability of polymer nanocomposites to be considered as
flame retarded polymers. When the dispersion of the filler is at
the nanoscale, the resulting nanocomposite has a relatively
limited contribution to fire associated with enhanced dripping
behavior but it is not self-extinguishing, the ignition time is
shorter and it does not reduce the flammability of the materials
(LOI, UL 94). Three parameters are then crucial: (i) the
nanodispersion state, (ii) the quality and the rate of formation
of the protective barrier, and (iii) the viscosity of the melt.
5. Synergy
How is synergy defined? The word is derived from the Greek
word synergos, meaning to work together or, literally, to co-
operate. Synergy is often associated with the cliche: the whole
is greater than the sum of its parts (which dates back to
Aristotle, in The Metaphysics). In the field of fire retardancy,
synergists are often required in order either to sharply improve
the performance of materials or to decrease the loading of
FR additives while maintaining the performance. Numerous
additives can provide synergistic effects in flame retardant
Table 3 Cone calorimeter data for PP/metal hydroxides composites and their nanocomposites (experiment carried out with incident heat flux of
50 kW m22)
PP content ATH content MDH content
(wt%) (wt%) (wt%)
100
80 20
60 40
77 20
70 20
2294 | J. Mater. Chem., 2007, 17, 22832300
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formulations, including halogenantimony, bromineammo-
nium, brominechlorine, brominephosphorus, etc.128131
It is not the aim of this section to give an exhaustive list
of the existing synergisms but to discuss the effects of
synergists with pertinent examples in metal hydroxides and
in intumescent systems.
Metal hydroxides are widely used to flame retard polymers
and in particular elastomers for cable applications. However,
one of the major drawbacks of this class of additives is the
high loading in the polymer to reach similar levels of flame
retardant behavior as conventional halogen based fire
retardants. The introduction of more than 60 wt% of additives
in the matrix leads to deleterious effects on melt viscosity and
mechanical properties of the materials (and in particular their
elasticity).132 That is the reason why researches dealing with
the development of synergistic agents for metal hydroxides are
the topic of numerous papers. As an example, the use of
polymer nanocomposites and in particular those based on
layered silicates133 and/or carbon nanotubes134 in combination
with metal hydroxides allow the total additives loading to
decrease while maintaining the performance of the system. To
maintain heat release rate as low as 200 kW m22, the content
of ATH in ethylene vinyl acetate (EVA) copolymer can be
decreased from 65% by weight to 45% by weight by the
incorporation of only 5% by weight nanofiller.133 Similarly, the
combination of metal hydroxides (aluminium or magnesium)
with organomodified clay has been studied as a potential fire
retardant system for polypropylene.135 The combination of
polypropylene with 5% inorganic clay and 20% of metal
hydroxide gives 80% reduction in the peak heat release rate,
which is similar to what is obtained when 40% of the hydroxide
is used alone (Table 3).
The mechanism of action of synergists in metal hydroxide
based systems is mainly attributed to physical effects in the
condensed phase. The reinforcement of the ceramic-like
structure resulting from the degradation of the polymer/metal
hydroxide blends should lead to inhibition of the heat and
mass transfer between the surface and the melting polymer and
thus to higher fire retardant performance. This phenomenon
was proposed to occur using zinc borate in metal hydroxide
based systems. Zinc borates are multifunctional fire retardants
containing different proportions of zinc and boric oxides.136
They are recognized for their ability to suppress smoke and
after-glow that may occur during the burning of polymers.137
It was reported that the addition of Firebrake1 415
(4ZnO?B2O3?H2O) and Firebrake1 ZB (2ZnO?3B2O3?
3.5H2O) in a magnesium hydroxide (MDH)/ethylene vinyl
acetate (EVA) copolymer blend leads to a sharp improvement
of the fire retardant performance of the material.138 LOI
Oligomerically modified Reduction in
clay (wt%) PHHR/kW m22 PHRR (%)
1967 50
817 40 59
467 5 76
3 677 38 66
10 592 18 70
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Fig. 11 EVA/MDH (a) and EVA/MD/ZB (b) residues after heat
treatment at 700 uC in a furnace.
increases from 38 vol% for EVA/MDH 40/60 to 43 vol% when
Firebrake1 415 substitutes 3% of the metal hydroxide while
maintaining a UL94-V0 rating. The mechanism of action was
attributed to the formation, in the presence of ZB, of a vitreous
protective residual layer, which reduces the combustion rate
and act as a physical barrier and as a glassy cage for polymer
fragments. It was also shown using rheological analysis139
that EVA/metal hydroxide/ZB systems show a significant
modification of the structure resulting from the presence of
zinc borate. This latter reinforces the metal oxide structure
changing it from a thin fragile structure to an expanded
foamed one with increased hardness (Fig. 11).
Similarly to what was proposed for ZB, a suitable amount of
fumed silica can increase the fire performance of EVA/MDH
decreasing the total amount of additive in the blends.140 The
synergistic flame retardant mechanism of SiO2 was attributed
to its physical effect in the condensed phase. The accumulation
of fumed silica near the ignited sample surface was observed.
This fumed silica incorporates MDH and it leads to the
formation of a charred layer inhibiting heat and mass transfer
between surface and melting polymer.
In intumescent systems, synergistic agents are often used to
pass specific test required by the legislation. For instance for
electrical applications, V0 rating is required at the UL94 test.
The requirement for V0 rating is now needed for 0.8 mm thick
samples whereas 1.6 mm or even 3.2 mm were acceptable few
years ago. As a consequence the development of even more
effective flame retardant systems is required. Synergistic agents
in intumescent systems affect the materials in various ways
(chemical and/or physical effects). The mechanical properties
of the intumescent shields developed in the case of fire are
particularly important since internal pressure (due to degrada-
tion products) or external environment can easily destroy it
leading to a loss of insulating properties of the protective layer.
Synergistic agents can act in increasing the mechanical
properties of the intumescent shield either by a physical effect
(reinforcement) or by a chemical effect.
A physical reinforcement of the intumescent shield can be
achieved using particles presenting high aspect ratio. As an
example, the addition of a layered inorganic filler (MMT or
LDH) in an EVA/APP/PA6 intumescent system leads to
classification in the UL94 test (respectively V0 and V2)
whereas the formulation without layered filler is unclassified
regarding this test.141 The mode of action of the layered
inorganic fillers was attributed to the high aspect ratio of the
fillers which is responsible for the increase in the rigidity of the
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Fig. 12 Mechanical resistance at 400 uC of intumescent EVA/APP/
PA6 based formulation and its blends with MMT and LDH (this
measurement was carried out in a planplan rheometer. A sample
(diameter = 25 mm, thickness = 1 mm) was located in the oven of the
rheometer and heated at 400 uC for 4 min before measurement in order
to enable the development of the intumescence without any perturba-
tion. Then the upper plate was placed in contact with the material and
linearly (0.02 mm s21) lowered. The compression force was followed
versus the distance between the two plates (the gap)).
intumescent shield. Higher mechanical stability of the
intumescent shield avoids the formation of cracks and so the
heat and mass transfer are limited, leading to interruption of
the combustion triangle. This is shown using a novel approach
measuring the destruction force of the intumescent shield at
high temperature by rheometry (Fig. 12).
The chemical effect can be related to the formation of a
chemical structure exhibiting higher mechanical properties
when the intumescent system degrades. The formation of rigid
crystalline domains in the presence of synergists, for instance,
modifies the mechanical properties of the intumescent shield.
In that case, two phenomena are concomitant. The rigid
crystalline domains are initiators for the formation of cracks in
the protective coating which has a negative effect but rigid
domains can also increase the mechanical properties of the
protective shield. As a consequence, the amount of synergist in
a formulation has to be adapted in order to increase the
mechanical properties of the intumescent but in such a way
that the formation of cracks is avoided. This aspect was parti-
cularly investigated in the first studies dealing with the develop-
ment of synergistic effects in intumescent systems142145 which
demonstrated that the incorporation of a small amount of
zeolite in the intumescent ammonium polyphosphate (APP)
pentaerythritol (PER) system leads to a synergistic effect. The
presence of the zeolite leads to an increase in the stability of the
material at high temperature (T . 550 uC). The increase in
thermal stability in the presence of zeolite was attributed to the
formation of localized turbostatic carbon in the structure.
The zeolite permits retention of the comparatively unorganized
carbon species in the high-temperature range while rigid
domains are proposed as initiators for the formation of cracks
in the coating. The relationship between the formation of a
coherent macromolecular network and the improved fire-
retardant performance of the APP-PER/zeolite system was
proposed. The synergistic agent may also have a chemical
effect promoting the charring properties and the thermal
J. Mater. Chem., 2007, 17, 22832300 | 2295

stability of an intumescent system leading to an increase of its
efficiency. Divalent and multivalent metallic compounds were
reported as catalysts for the flame retardancy performance
of intumescent systems working on this mechanism.146 The
catalytic effect of the divalent ions on the APP-PER system in
PP146 was correlated with their ability to favor crosslinking
and dehydration reactions, whereas multiple valency metal
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ions favor oxidation reaction.
Synergistic agents exhibit not one mode of action but rather
a number of concomitant mechanisms of action in intumescent
systems. This is particularly the case for nanoparticles.147150
In intumescent EVA, the synergistic effect of montmorillonite
(MMT) was partially explained by the increase in the mechani-
cal properties of the intumescent shield due to chemical
interactions between the particles and the intumescent system
leading to the presumed formation of aluminosilicophosphate
complexes and/or to the reinforcement due to the presence of a
lamellar structure.147 Moreover, it was also observed that
the viscosity of the burning polymer is sharply modified in
presence of nanoparticles. This phenomenon leads to an
increase in the fire performance of the intumescent system.148
Indeed, the viscosity of the material in the high temperature
range (that is to say in the range of temperature corresponding
to the development of the intumescence) is an important
parameter in particular regarding dripping. Moreover, since
the intumescent process is a dynamic process due to low
diffusion of gaseous products in a viscous carbonaceous
matrix, this parameter is even more important compared with
other fire retardant additive classes. Additionally, concomitant
schematic mechanisms of action of MMT in intumescent
PP were also proposed.150 The silicate layers can limit the
oxygen diffusion to the substrate or give a less disturbing low
volatilization rate, which produces a positive effect on the fire
properties. At the same time, an ablative reassembling of the
silicate layers can hinder NH3 and other degradation products
from swelling, and this leads to a negative effect on the fire
properties.
6. Surface treatment: a novel route for preparing
fire retardant polymers and multifunctionality
opportunities
The use of surface treatment is one of the easiest and one of the
most efficient ways to protect materials against fire.8,151
Indeed, it presents several advantages: it does not modify the
intrinsic properties of the materials such as for example the
mechanical properties, it is easily processed and it can be used
on several materials such as metallic materials,152 polymers,153
textiles154 and wood.155 Moreover, while inflammation occurs
usually on the surface of a material it is important to con-
centrate the protective action at this location. Intumescent
coatings designed for the fire protection of metallic structures
have been reported in section 3 of this paper. This part of the
paper will present novel approaches to develop fire retardant
polymers using low pressure or cold plasma technologies.
Cold plasma technologies are surface modification pro-
cesses. Hence the inherent advantages of the substrates can
be kept and materials exhibiting various properties can be
made.156 The plasma contains several reactive species such as
2296 | J. Mater. Chem., 2007, 17, 22832300
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electrons, atomic or molecular ions, energetically excited
atoms or molecules. Cold plasma reactive species can then
promote surface functionalization reactions or generate
organic or inorganic thin layers as a result of recombination
of radicals or molecular fragments species on the surfaces. This
is this second approach that has been used to develop fire
retardant protective coatings for polymeric materials. In this
field, one may distinguish the plasma enhanced chemical vapor
deposition (PECVD) and plasma induced graft-polymerization
(PIGP) techniques. Within the first technologies, a monomer is
injected in the plasma. The monomers, non-functionalized
monomers which are not utilized in conventional polymer
synthesis, become excited and partially decomposed in the
plasma157 with the subsequent formation of a highly cross-
linked polymer thin film at the surface of the substrate. The
properties of the plasma polymers formed are naturally
affected by the molecular structure of the starting monomer
as well as by the operating parameters such as power input,
monomer flow rate and pressure in the reaction chamber.
Silicon-containing organic compounds (organosilicones) are
widely used as monomers in low-pressure plasma deposition
due to their availability, liquid state, volatility at room
temperature, safe handling and low cost.158 The structure of
the formed deposits is very dependent on the more or less
energetic character of the plasma and can be, in fact, turned
from SiO2-like inorganic coatings to silicon-like polymers,
depending on whether the plasma conditions are hard or soft.
As an example, thin films obtained from tetramethyldisiloxane
(TDMS) monomer pre-mixed with oxygen are presented in
Fig. 13. The deposits are dense and the films are composed of
cauliflower shaped [articles, the sizes of which increase as the
oxygen flow rate increases. Oxygen addition could inhibit the
TMDS fragmentation leading to the formation of a film
exhibiting larger grain size.159 Flame retardant properties of
polyamides and polyamide nanocomposites can be improved
using this deposit.160164 LOI of the coated PA-6 nanocompo-
sites is strongly improved as soon as a film thickness equal to
0.6 mm is deposited. It grows from 22 vol% for uncoated PA6
nanocomposite to 45 vol% for coated materials. The mode of
action of this barrier was attributed to the fact that when
burning, the nanocomposite structure of the polymer leads to
the formation of a surface protective layer the action of which
is reinforced by the coating. The carbonaceous and silica-like
layer acts as a barrier limiting mass and heat transfers between
the flame and the polymer and slows the toxic gas emission
produced by polymer combustion.
Fig. 13 Scan electron micrographs of deposits at 3 sccm (a) and
195 sccm (b) oxygen flow rate (from ref. 161).
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Fig. 14 Experimental procedure for the plasma-induced graft-poly-
merization of monomers (from ref. 167).
The plasma induced graft-polymerization technique consists
of the simultaneous grafting and polymerization of function-
alized monomers, such as acrylate monomers, on the surface of
a material. This technology requires the experimental proce-
dure reported in Fig. 14. The monomer (mixed with or without
photoinitiators and solvent) is placed on the substrate by
dipping, padding, back-coating or other techniques. The
coated substrates are then introduced in the plasma reactor.
The reactor is then evacuated, the gas flow rate is adjusted and
the discharge is initiated. The coated materials are then washed
to remove non-grafted monomers or polymers and dried.
This approach has been used advantageously to flame retard
polyamide using fluorinated acrylate165,166 and textiles using
phosphorus-based acrylates.167169 Grafting and polymerizing
of 1,1,2,2-tetrahydroperfluorodecyl acrylate onto the PA6
surface leads to efficient fire retardant properties. A decrease
in the peak heat release rate (cone calorimeter 35 kW m22) of
50% was observed in comparison with uncoated PA6. This
effect was attributed to a reaction of radicals in the gas phase
with different fragments of polymer evolved during the
thermal degradation leading to a dilution of the combustible
gases.165 The flame retardancy of the fabrics (cotton, cotton/
polyester and polyacrylonitrile) treated with acrylate phos-
phate, phosphonate and phosphoramidate monomer is also
improved. The flame retardant effect is closely linked with the
chemical structure of the monomer. As an example, it was
shown that phosphoramidate monomers lead to higher
performance167 probably because of the presence of nitrogen
which causes a synergistic enhancement in the efficiency of
phosphorus-based flame retardants.130
Considering this approach, two or more properties can be
provided simultaneously to materials with a minimum number
of treatment steps. Indeed, the need to produce materials
combining various properties such as flame retardancy, water
repellency, antibacterial, etc., has increased. The plasma
induced graft-polymerization procedure could be efficiently
used for these purposes. This approach has been successfully
applied to provide a water-repellent and a flame retardant
character to textiles.168
7. Conclusion and outlook
In this paper, we have discussed recent developments of flame
retardant polymers. Three approaches have been considered,
i.e. inherently flame retardant polymers, chemically modified
polymers and flame retardants as additives for polymers. We
have mainly focused our comments on the flame retardants
and nanofillers. The quick overview of the mechanisms of
action reveals that the formation of a charred insulating layer
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is almost always involved. The development rate and the
quality of this layer are therefore of the primary importance
and research work should focus on this. A typical example is
the intumescence exhibiting the formation of an expanded char
acting as a thermal shield.
Research work in intumescence is very active. New
molecules and new concepts have appeared recently including
microencapsulation and new solutions of mineral intumes-
cence. In this case, the basic mechanism is always the same
but those approaches permit the development of new applica-
tions (e.g. higher efficiency in the protection of steel).
Nanocomposites represent a relatively new technology in the
field of flame retardancy. Polymer nanocomposites are FR
polymers in specific scenarios (high heat flux) but fail
flammability tests (LOI, UL-94). The mechanism of protection
is the formation of a mineral layer associated with char
promotion but the protective layer is not efficient enough to
provide the highest standard of protection. This technology
gives the best results combined with conventional flame
retardants and leads to synergistic effects. As an example,
intumescent nanocomposites exhibit superior flammability
properties as well as other enhanced properties such as
mechanical properties. Very promising developments in the
synergy aspects are then expected and efforts should be
made in this direction. The last approach suggested in this
paper is to use plasma treatment to deposit thin protective
films on polymers. FR performance is significantly enhanced
and synergistic effects are observed on polymer nanocompo-
sites. It is very promising because only one treatment of a
coating of about 10 mm thick on a polymer results in low
flammability and the development of multifunctional materials
might be expected.
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