Materials 2010, 3, 4476-4499; doi:10.

3390/ma3084476

OPEN ACCESS

materials
ISSN 1996-1944
www.mdpi.com/journal/materials

Review

New Trends in Reaction and Resistance to Fire of Fire-retardant

Epoxies
Caroline Gérard 1,2,3,4, Gaëlle Fontaine 1,2,3,4 and Serge Bourbigot 1,2,3,4,*
1
Univ Lille Nord de France, F-5900 Lille, France; E-Mails: cgerard@enscl.fr (C.G.);
Gaelle.Fontaine@ensc-lille.fr (G.F.)
2
ENSCL, ISP-UMET, F-59652 Villeneuve d’Ascq, France
3
USTL, ISP-UMET, F-59655 Villeneuve d’Ascq, France
4
CNRS, UMR 8207, F-59652 Villeneuve d’Ascq, France

* Author to whom correspondence should be addressed; E-Mail: Serge.Bourbigot@ensc-lille.fr;

Tel.: +33-320434888; Fax: +33-320436584.

Received: 1 July 2010/ Accepted: 4 August 2010 / Published: 25 August 2010

Abstract: This paper focuses on current trends in the flame retardancy of epoxy-based
thermosets. This review examines the incorporation of additives in these polymers,
including synergism effects. Reactive flame-retardants—which are incorporated in the
polymer backbone—are reported and the use of fire-retardant epoxy coatings for materials
protection is also considered.

Keywords: epoxy; fire-retardant; reaction to fire; resistance to fire; coatings

1. Introduction

Polymeric materials have substituted many materials in our everyday life. Their numerous
advantages are also associated to a serious drawback: their poor resistance to fire. Fires cause every
year 10 to 20 deaths per million inhabitants in industrialized countries. The number of injured people is
ten times higher [1]. Over time, different strategies have been developed in order to enhance the
reaction to fire of these materials: use of inherently flame retardant polymers [2], modification of the
polymer backbone [3,4] or incorporation of flame retardants into polymers. Because inherently flame
retardant polymers can lead to high production costs, the modification of already existing systems is
Materials 2010, 3 4477

still valued by industries. The modification of the polymer backbone by inclusion of P, Si, B or N often
provides good fire properties to the newly synthesized polymer [5]. Even if the range of achievable
materials seems unlimited, the obtained copolymer has mechanical properties that are often modified
compared to the reference material. Finally, the incorporation of flame retardant particles in polymers
is still widely used. It is a simple and cost-effective way for flame-retarding polymers. However, the
high levels required for ‘traditional’ flame retardants often induce detrimental modifications of the
mechanical properties of the final materials and the use of nanoparticles as flame retardants has been
developed. Very different mechanisms are involved in the reaction to fire of polymers containing
flame-retardant particles, and these effects are often mixed. Physical actions are encountered when an
insulating protective layer is formed on top of the polymer during combustion (intumescent systems) [6],
when the degradation of the additive is an endothermic reaction (‘cooling’ effect, e.g., with metallic
hydroxides) [7] or when inert gases are released by the additive upon degradation (e.g., calcium
carbonate). All these protective ways are associated with a barrier effect. Chemical effects are also
involved, for example when the flame retardant or its degradation products disturbs the radical mechanism
occurring in the flame and leads to its extinction (halogen-, phosphorus-based flame retardants).
Among the many polymeric materials used, epoxy resins are one of the most problematic: they are
used in sectors such as electronics or public transportation, where standards are particularly restrictive.
Unfortunately, they tend to burn easily while releasing high quantities of smoke and gases [8]. Because
of their use as printed-wire boards, epoxy resins have to be highly flame- and one of the traditional
solutions is the incorporation of halogen-containing flame-retardants, especially bromine-based. Part
of the standard resin has to be replaced by the bromine-containing monomer, leading to Br contents
between 20 to 55 wt %. Furthermore, a higher coefficient of thermal expansion, a higher viscosity and
a lower thermal stability are induced by the use of such modified monomers. Another solution is the
incorporation of aluminium trihydroxide, but contents up to 65 wt % are necessary in order to get
suitable fire properties, resulting in degraded mechanical properties.
Therefore, the effort for enhancing the reaction to fire of epoxy resins has been further developed
and innovative solutions have been looked for. This review focuses on the most recent developments
in this field and the reported literature has been selected in order to cover the major trends in the flame
retardancy of epoxy materials. The first part of this paper is dedicated to the growing use of
nanoparticles for enhancing the reaction of epoxies to fire. The current status as well as the difficulties
encountered will be reviewed. Then, the evaluation of phosphorus- and silicon-modified resins will be
conducted, as well as their possible interactions with nanoparticles. Finally, because of the importance
of this application field for epoxies, the developments in flame retardant coatings will be assessed.
Considering the modifications induced by the use of carbon or glass fibers (modified heat distribution),
reinforced composites will not be considered in this article.

2. Incorporation of Additives

The additive route has always been widely used to fire-retard polymers, in particular epoxies. It is
generally a cheap and easy way of achieving sufficient levels of flame retardancy. However, the
traditional additive flame-retarding solutions tend to show their limits. The use of halogen-containing
flame-retardants is being questioned: if some of them are suitable for the European market, possible
Materials 2010, 3 4478

bioaccumulation and effects on workers handling pure substances have been mentioned and
environmental issues are still considered. Furthermore, alternatives solutions are required by possible
restrictions due to REACH enforcement [9]. REACH stands for Registration, Evaluation and
Authorization of Chemicals and this directive from the European Commission will influence the
choice of the components used in many areas, in particular in plastics. Metallic hydroxides, such as
aluminium or magnesium hydroxide, are efficient at very high loadings (50 wt % or more), but this
results in degraded mechanical properties and difficult processing. Therefore, the incorporation of
nanoparticles has attracted much interest in the last ten years. Indeed, apart from providing fire
properties to the materials, low loadings achieved do not modify the other properties or even enhance
some of them, such as mechanical properties [10]. Survey of the literature with SciFinder for different
keyword combinations helps to identify the tendencies in the use of nanoparticles. The incorporation of
nanoparticles in epoxies for enhancing mechanical properties is widely described (Figure 1, ‘epoxy’
and ‘nanoparticle’). An overview of the literature shows that the occurrences are more limited when
coming to the incorporation of nanoparticles in epoxy for flame retardancy (“epoxy” and
‘nanoparticle’ and ‘flame retardant’). However, the use of nanoparticles as flame retardants in other
polymers is well-known (‘nanoparticle’ and ‘flame retardant’). The following section is therefore
devoted to a screening of the different nanoparticles commonly used as flame retardants, then the
results obtained for nanoparticles incorporated in epoxies and the expected developments in this field.

Figure 1. Number of publications per year for different keyword combinations (Scifinder,
April 2010).

A wide range of nanoparticles has been incorporated in epoxies. The effect of the incorporation of
layered silicates, then the potential fire retardant properties of layered double hydroxides, polyhedral
oligomeric silsesquioxanes and carbon nanotubes will be discussed.
Materials 2010, 3 4479

2.1. Organoclays

Among the different nanoparticles used in flame retardancy, layered silicates have attracted much
attention in the litterature. As for other nanoparticles, their effect as flame-retardant has been linked to
their dispersion state in the matrix [11]. Capability of layered silicates for being exchanged with
organic cations at commercial level led to an easier dispersion in various polymers, especially in
epoxies. Hartwig et al. [12] reported the combustion behaviour of clay-filled epoxies. Two different
bentonites based on a phosphonium or an ammonium cation as surfactant were incorporated in an
epoxy matrix at 5 wt %. Dispersion studies were conducted by Transmission Electron Microscopy
(TEM) and showed a non-uniform distribution of the bentonites in the matrix. For both cations, the
morphology is a mixture of intercalated and exfoliated areas, and a slightly better dispersion is
obtained with the phosphonium bentonite. The flame-retardant properties of these clays were evaluated
by various tests. Limiting Oxygen Index (LOI—ASTM D2863—ISO 4589) gave information about
the flammability of the samples: LOI values remain low for nanocomposites and the differences
between the virgin polymer and the nanocomposites are not relevant (Table 1).

Table 1. Flammability characteristics of clay-filled epoxies. Data from [12].

Horizontal burner test
Samples LOI (%)
Time for burning 150 mm in horizontal position (s)
Virgin epoxy 18.3 260
Epoxy + ammonium clay (4.7 wt %) 19.7 434
Epoxy + phosphonium clay (4.7 wt %) 19.6 464

The flame spread was evaluated by the horizontal burner test (Aerospace standard AITM
2.0003—FAR 25.853), in which the time required for burning 150 mm of the sample is recorded (Table
1). Therefore, the longer the time, the better the behaviour. The time required for burning the sample is
drastically increased by the incorporation of bentonites in the matrix. Furthermore, contrary to non-filled
epoxy, the nanocomposites do not drip. Finally, the fire behaviour was studied by cone-calorimetry.
After a similar beginning, the curves for the virgin resin and the nanocomposites are different: the
first increase is followed by a further increase for the non-filled epoxy, whereas a plateau is reached
for the nanocomposites, before a second peak occurs. Different external heat fluxes were used and the
influence of the incorporation of nanocomposites depends on the used heat flux. The biggest
reductions of the peak of heat release rate (pHRR) are observed for the nanocomposites and are
reduced by 1/3 for an external heat flux of 70 kW/m², and no significant difference between the two
nanocomposites was observed. The enhancement brought by nanoparticles depends strongly on the
heat flux: the reduction of 1/3 at 70 kW/m² is only 1/5 at 30kW/m². Extrapolating this curve leads to an
absence of effect for non-radiant tests such as UL-94 or LOI. Therefore, from this point of view, the
results obtained before for the LOI test are consistent with the results for the cone-calorimeter. As a
first conclusion, the authors pointed out the barrier effect of nanoclays in epoxy. However, in this case,
the barrier effect is limited.
Schartel et al. [13] also worked on an epoxy system: a bisphenol A diglycidylether-based resin was
cured with 4-methylhexahydrophtalic anhydride, and the reaction was accelerated by
Materials 2010, 3 4480

1-methyl-imidazole. Different phosphonium-based clays were incorporated at 5 wt % in order to study

the influence of the morphology and the distribution of clay in this system: clays with different
morphologies were obtained by changing the drying conditions of the exchanged clay obtained by
synthesis. The BET surface of modified bentonite was determined by nitrogen adsorption and used to
evaluate the powder morphology. It varied from 6.7 m²/g for a commercial ammonium bentonite used
for comparison up to 175 m²/g for the freeze-dried phosphonium bentonite. Scanning Electron
Microscopy (SEM) and Transmission Electron Microscopy (TEM) showed that the distribution of clay
in the matrix is strongly influenced by the characteristics of the clay. It seems that the higher the BET
surface of the powder, the better the distribution. Taking into account the results from Hartwig [12],
the authors supposed that the incorporation of modified clays alone would not bring sufficient fire
properties to the materials. Therefore, they developed mixed systems containing clays and aluminium
trihydroxide (ATH). They also used a mixture of unreactive and reactive phosphorus containing flame
retardants: triphenylphosphate (unreactive) and Struktol VP3735 (reactive). Struktol VP3735 is the
product of the reaction between 9,10-dihydroxy-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO) and
an epoxy novolac (no further details available). LOI investigations showed that a small increase is
achieved by incorporating clays in the epoxy matrix and the higher LOI is reached with
phosphorus-based flame retardants: 23–23.4% depending on the phosphonium clay used, instead of
20.9% for the neat resin and 32.9% for the phosphorus-based flame retardant. It should be noted that
combinations between clays and Struktol or ATH led to a small antagonistic effect in terms of LOI.
The fire behaviour was further studied by cone-calorimetry: the pHRR was decreased by incorporating
layered silicate, ATH or organo-phosphorus flame retardant. The highest decrease is achieved by the
organo-phosphorus flame retardant whereas the smallest is reached with clay. The drying conditions of
clay, and therefore the morphology, have an influence on the pHRR. As seen before, the dispersion
was strongly linked to the drying conditions of the MMT powder and a better nanodispersion leads to
reduced pHRR, up to 51% at an external heat flux of 70 kW/m². Another study by Schartel et al. [14]
on similar systems showed a strong relationship between the clay morphology before mixing and the
nanocomposite formation, and thus on the reduction in pHRR. The authors concluded that even if the
nanocomposite formation in thermosets in less easy to achieve than in thermoplastics, a homogeneous,
nano-scaled dispersion of clay is critical for producing a homogeneous residue surface layer during
combustion that is able to provide the desired fire retardancy. Therefore, the need for an even
dispersion has been confirmed. However, achieving a perfectly exfoliated nanocomposite is not
necessary, and an intercalated structure might provide good fire properties, as long as no big
inhomogeneities are present in the material.
More effective systems have been reported by Camino et al. [15] with different organo-modified
montmorillonite (OMMT) in epoxy at 10 wt %. Such a high loading does not allow the formation of a
‘real’ nanocomposite, i.e., a microcomposite is probably synthesized. However, differences in the
dispersion state, depending on the exchanged cation, can be observed. The authors showed that the
composite containing Nanofil 848 (octadecyl ammonium montmorillonite), which has the best
dispersion, observed by TEM and Wide Angle X-Ray Diffraction (WXRD), gives good results but not
as good as Cloisite 30B (bis(2-hydroxyethyl) ammonium montmorillonite) (Table 2). On the contrary,
Cloisite 25A (dimethyl hydrogenated-tallow(2-ethylhexyl) ammonium montmorillonite) leads to a
smaller decrease of pHRR. Such enhancements remain isolated and Zammarano [16] suggested that
Materials 2010, 3 4481

the particularly high decreases observed for the nanocomposites in this case may be related to different
curing conditions between neat resin and the nanocomposites. In fact, 1 wt % imidazole catalyzed the
curing for neat resin whereas it was not considered as necessary for the nanocomposites since clays
have been reported to catalyze the epoxy ring opening reaction [17]. But it seems that the use of such
catalyst decrease the onset of decomposition temperature. If this phenomenon effectively occurs in this
case, the materials containing clays cannot be properly compared with the virgin resin. The virgin resin
would artificially be easily degraded and the effect of the incorporation of clay overestimated. This
could explain why no similar high decreases of pHRR by clays have been reported in epoxy since then.

Table 2. Cone-calorimeter data of epoxy-nanocomposites at 50 kW/m²[15].

Sample Time to ignition (s) pHRR (kW/m²) pHRR decrease (%)

Pure epoxy 34.5 2,030 -

Epoxy/Nanofil 848 (10 wt %) 34.5 1,250 48
Epoxy/ Cloisite 30B (10 wt %) 34.5 650 68
Epoxy/ Cloisite 25A (10 wt %) 44.0 1,570 23

Even if such high effects are isolated for clays in epoxy, it is worth considering that the higher
decrease was not brought by the filler with the best exfoliation. Therefore, the authors mentioned a
possible additional effect of the chemical nature of the surfactant in addition to the physical barrier
effect of clay. This effect has not been identified up to now. As a general conclusion, it seems that
organoclays do not always show their full potential as flame retardants in epoxies, probably because of
the difficulties for controlling their morphology in this matrix. However, their barrier effect could be
useful in combination with other flame retardants.

2.2. Layered Double Hydroxides

Layered double hydroxides (LDHs) are another type of layered crystals and are called anionic clays,
by analogy with some lamellar cationic clays. Their incorporation into polymers also provides
interesting fire retardant properties: they absorb heat during their decomposition and release water and
carbon dioxide, which dilutes flammable gases, enhances the heat absorption and reduces the heat
release during combustion. Furthermore, a protective ceramic layer is formed on top of the sample,
providing a barrier effect [16]. They could be used as a replacement for magnesium hydroxide and
aluminium trihydroxide, which are effective, but need to be incorporated at high loadings.
Zammarano et al. [18] have noticed the self-extinguishing behaviour of epoxy/LDH nanocomposites at
the horizontal UL-94 HB test. High reductions of the peak of heat release rate during cone-calorimeter
experiments have also been observed. They depend strongly on the LDH anion: 40% and 51% pHRR
decrease are reached with 4-toluenesulfonate and 3-aminobenzosulfonate, respectively. Samples
containing montmorillonite were also tested for comparison: a 27% pHRR decrease was observed.
Finally, samples based on ‘traditional flame retardants’ such as ammonium polyphosphate (APP) and
aluminium trihydroxide were also tested. Even if LDH provided reduced fire behaviour compared to
that obtained with APP (80% decrease of the pHRR), the ignition time was close to that of virgin resin
for the LDH-containing samples, whereas it was reduced by the incorporation of APP. Furthermore,
Materials 2010, 3 4482

LDHs are also likely to enhance mechanical properties and APP degrades them. In fact, in this case, it
seems that LDHs act as a nano-intumescent system (intumescent systems produce a cohesive and
insulating layer on the surface of the polymer, which is blown by the gases produced during the
decomposition of the underlying polymer) where the epoxy resin itself is the source of the char, the
sulfonate from the LDH is the charring agent, while water and CO2 are the blowing agents in addition
to those of the degrading epoxy. Therefore, the incorporation of modified-LDH in epoxy seems an
effective way for providing good fire properties to this polymer.

2.3. Polyhedral Oligomeric Silsesquioxanes

Among the many particles incorporated in epoxy, Polyhedral Oligomeric Silsesquioxanes (POSS)
are one of the most studied in recent years. Their effect on the mechanical and the thermal properties
of epoxies as well as their influence on the kinetics of curing has often been reported but the fire
properties of the obtained materials have rarely been discussed [19-21]. On the other hand, the interest
of POSS as fire-retardant in other polymers has been reported [22-24]. POSS are structurally
well-defined compounds composed of a silicone-oxygen framework having the general formula
(RSiO3/2)n (n = 6, 8, 10…).The most typical species is the octahedron (n = 8) (Figure 2).

Figure 2. Structure of cage hexahedral silsesquioxane (RSiO3/2)8.

R can either be hydrogen or any alkyl, alkylene, aryl, arylene or organo-functional derivatives of
alkyl, alkylene, aryl or arylene group. These molecules are well-defined and their sizes range from 1 to
3 nm, which makes them the smallest version of colloidal silica. Depending on the reactivity of the
organic group, R, POSS can be classified as non-functional or functional.
Functional POSS are widely studied in epoxies, probably because of the possible reactions
occurring between their reactive moieties and the epoxy rings of the resin. An enhancement of LOI has
been reported by different authors: 5 wt % of cyclohexyltrisilanol POSS leads to a LOI of 32.8%
instead of 22.6% for the virgin resin used by Lu et al. [25]. Similar trends were observed by
Lu et al. [26] for cyclohexyldisilanol POSS: the LOI increased from 26% for the virgin resin up to
32% for a POSS content of 25 wt %. Another reactive POSS obtained by the reaction between
trisilanolisobutyl POSS and triglycidylisocyanurate was incorporated at higher contents (10 wt %) by
Wu et al. [27]. Due to the unreacted epoxy ring of the modified POSS, the authors suggested a possible
reaction between the hardener and the POSS, leading to a hybrid network. They investigated the
reaction to fire using micro-scale calorimetry. The curve corresponding to the hybrid network shows
two overlapping peaks instead of one sharp peak and a lower peak of heat release rate compared to the
Materials 2010, 3 4483

one for virgin resin. Therefore, the peak of heat release rate is decreased by 30%, showing the interest
of the incorporation of reactive POSS in epoxies. Even if such loadings appear high for nanoparticles,
the incorporation of POSS in the matrix seems beneficial for the flammability. One question still
remains: do these results stem from the presence of the reactive moiety of this POSS, the high loading
resulting in significant inorganic content or a combination of these parameters?
Wu et al. [28] studied a DGEBA/phenyltrisilanol POSS mixture. An aluminium complex was used
in order to catalyze the reaction between these two reagents. The morphology of the obtained
composites was characterized by SEM (Figure 3).

Figure 3. SEM micrographs of POSS composites cured with and without Al.
(a) Epoxy/POSS, (b) Epoxy/POSS [Al], (c) higher magnification of (b) [28].

The size of POSS particles is decreased when the reaction is catalyzed. In fact, the authors report
that the uncured mixture without Al was clear and became cloudy during curing, whereas it remained
clear for the samples containing Al. They investigated the effect on the reaction to fire of the resin by
cone-calorimetry. All curves are made of two peaks, the first being the highest. The incorporation of
POSS in the formulation did not give any significant decrease of the peaks. The effect was higher for
the formulation containing both aluminium and POSS: the pHRR was decreased by 33% and the curve
is flattened. The morphology of the residues obtained after burning was characterized by SEM: the
combination between POSS and Al produces a compact, uniform char, whereas holes were observed
when POSS are incorporated without Al (Figure 4).

Figure 4. SEM micrographs of residues for Epoxy/POSS[Al] (left) and Epoxy/POSS (right).
Materials 2010, 3 4484

This difference is probably due to the more even dispersion of POSS when combined with Al. This
is important to point out that in this case, the dispersion is not at the nanoscale. However, the addition
of aluminium in the formulation led to far more homogeneous dispersion. This is certainly the main
reason for the enhanced fire behaviour: increasing the interfacial area between the polymer and the
nanofiller helps the formation of a protective layer during combustion. This conclusion is similar to
that done by Schartel et al. for organoclays [14]. In this case, the authors suggested that the aluminium
complex, by favouring the compatibilization reaction between the resin and the reactive moiety of the
POSS, leads to the better fire behaviour of the system. However, as a general conclusion on reactive
POSS, one does not know if the better reaction to fire observed with reactive POSS is due to the
presence of the reactive part or simply to the presence of POSS itself. This last study with the
aluminium catalyst showed the potential interest in controlling the reaction between the resin and the
POSS in order to take full advantage of the POSS properties.
In order to get higher enhancements of the fire properties, combinations between octavinylPOSS
and a phosphorus-containing resin have recently been reported by Wang et al. [29]. The phosphorus
content in the uncured mixture was kept constant (2 wt %) and the silicon content varied from 0 to 3 wt %.
(i.e., 0 to 10 wt % POSS). TEM pictures of the sample containing 3 wt % POSS showed a
homogeneous material and no aggregate could be identified. The reaction to fire was evaluated by
means of a micro-scale calorimeter. The curves are made of a single peak, which is sharp for the resin
without POSS. Incorporation of POSS in the matrix leads to a decreased pHRR (−44% for the sample
containing 3 wt % silicon) and the shape of the curve is modified, the peak broader. Based on the
literature, the authors attributed the positive effect of the incorporation of POSS on the pHRR to the
POSS capability for promoting char formation instead of making evolving fuels.
A comparison between reactive and non-reactive POSS was conducted by Franchini et al. [30].
Three different POSS were incorporated in an epoxy matrix: octaphenyl-, glycidoxypropyl-
heptaphenyl- and glycidoxypropyl-heptaisobutyl POSS (Figure 5).
This selection lets investigate the effect of the non-reactive ligand type and the presence of reactive
moieties on the reaction to fire of the samples. Cone-calorimeter at 35 kW/m² was used in this purpose.
For each type of POSS, a decrease of the pHRR was observed at 3.7 wt % inorganic part. The
phenyl-based POSS led to higher decreases: the reduction of the pHRR was −25%, −34% and −40%
for glycidoxypropyl-heptaisobutyl POSS, octaphenyl POSS and glycidoxypropyl-heptaphenyl POSS
respectively. Therefore, the phenyl-based POSS led to the highest decreases. The cross-section of the
residues was observed and revealed that the sample leading to 40% reduction has a sponge-like
structure. This characteristic was not found in the other samples. Such an observation suggests a better
thermal insulation and it would be worth observing the residues into details. UL-94 tests were also
conducted and the samples were not classified. However, visual observations show differences
between the samples: those containing glycidoxypropyl-heptaphenyl POSS did not release drops
during burning, 96 wt % of the sample remained after burning and it was self-extinguishing. The other
samples burnt completely and released incandescent drops. The effect of POSS content was finally
investigated: two different POSS content were used i.e., 1.50 or 3.70 wt % of inorganic part. Small
differences were observed and the main conclusion is that the performances obtained with 3.7 wt %
loading can be reached with 1.5 wt % loading. An influence on the UL-94 test was observed since the
Materials 2010, 3 4485

final residue was 70 wt % for 1.5 wt % POSS instead of 96 wt % for 3.7 wt %. These results highlight
once more the potential of POSS as efficient flame-retardants in epoxy.

Figure 5. Chemical structures of octaphenyl POSS (left), glycidoxypropyl heptaphenyl

POSS (middle) and glycidoxypropylheptaisobutyl POSS (right) [31].

2.4. Carbon Nanotubes

Carbon nanotubes (CNT) have been incorporated in various polymers, showing strong fire-retardant
effects [24,32,33]. Numerous papers deal with the use of raw or functionalized CNT in epoxy resins
and the improvements induced, in particular concerning the mechanical properties and the thermal
stability of the prepared materials. However, up to very recently, the effects on the reaction to fire of
the resin had never been reported. Kuan et al. [34] functionalized CNT with vinyltriethoxysilane and
incorporated them in an epoxy matrix via a sol-gel method. Materials containing up to 9 wt % CNT
were obtained and tested for their reaction to fire by LOI and vertical UL-94. The LOI gradually
increases along with the CNT content and reaches 29% for the samples containing 9 wt % CNT,
instead of 22% for the virgin polymer. The UL-94 classification is also increased from V-1 for the
virgin resin to V-0 for 3 wt % CNT in the matrix. The authors linked these results to the strongly
modified mechanical properties of the materials. The glass transition (Tg) of the polymer is affected by
the incorporation of CNT: it increases for CNT contents higher than 3 wt %, but no Tg could be
recorded for the sample containing 9 wt %. This result gives a first idea of the potential effect of
modified CNT in epoxies. It would however be useful to incorporate unmodified CNT in the sol-gel
system in order to observe their effect on the Tg, since it seems closely related to the enhanced
behaviour at the UL-94 test. Rahatekar et al. [35] studied the effect of highly-aligned CNT in epoxy
matrix on the peak mass loss rate (PMLR) during gasification. The system used is similar to a
cone-calorimeter, with a nitrogen atmosphere instead of air. Therefore, as pointed out by the authors,
the condensed phase is studied in the absence of oxidation and there is no feedback from combustion
in the gas phase. The results show the mass loss rate as a function of time. A very small amount i.e.,
0.0025 wt % of highly-aligned CNT resulted in a 45% reduction of the PMLR and the total time
needed for complete mass loss is delayed (Figure 6).
Materials 2010, 3 4486

Figure 6. Mass loss rate versus time for different CNT-containing epoxies (heat flux:
50 kW/m², N2 atmosphere) [35].

The reduction in PMLR is slightly lower for the 0.005 wt % CNT sample. Based on these results
and their modelling, the authors suggest that two mechanisms compete. Re-radiation is identified as
the main protection mechanism. The nanoadditives form a protective layer on the surface of the
sample. As the temperature rises, the thermal energy reaching the underlying polymer is decreased. At
higher loading, this effect is disturbed by the high thermal conductivity brought by CNT: the heat
transfer to the degrading polymer below the charring layer increases. Therefore, the fire-retardant
effect is less impressive at higher contents. This study provides helpful data for the comprehension of
the reaction to fire of epoxies containing nanoparticles. The exceptional results for CNT/epoxy
composites might also come from the use of highly-aligned carbon nanotubes, which debundle more
easily. This is a major advantage compared to ‘traditional’ carbon nanotubes.
As a conclusion, different nanoparticles have been evaluated in epoxy resins and provide protection
against fire. Nanoparticles have already been identified as valuable for the flame retardancy of
thermoplastics. One of the involved mechanisms is an increase of the viscosity of the polymer. This effect
may be also useful in epoxies since a viscosity drop around 350 °C in epoxy has been identified [36] and
could be limited by the incorporation of nanoparticles. However, up to now, the barrier effect is
considered as the major effect for protecting this matrix with nanoparticles: an even dispersion of the
particles seems essential in order to form a protective barrier on top of the sample. Another conclusion
is that for some clays, conclusions are different between the authors. This can be attributed to a wider
range of morphology achieved with montmorillonite. For example, working with montmorillonite
leads to very different fire-retardant effects depending on the used MMT and the composite synthesis
method. Carbon nanotubes have not proven a strong fire-retardant effect in epoxy regarding standard
methods yet. LDH seem promising, but the current limited range of industrially available ion-exchange
limits their potential use at larger scale. Therefore, until the morphology of MMT/epoxy is controlled,
one of the best nanoparticles for enhancing the fire properties of epoxy seems to be POSS, even if they
are not nanodispersed at the chosen loadings.
Materials 2010, 3 4487

3. Reactive Flame Retardants

3.1. Phosphorus-Containing Networks

The use of phosphorus-containing flame-retardant has been significantly developed in various

polymers as an alternative to halogen-containing flame-retardants [37-39]. This is also the case for
epoxies. Moreover, due to the multiple possibilities for creating phosphorus-based monomers or
hardeners, incorporation of phosphorus directly in the backbone of the resin has been intensively
studied, as pointed out by Levchik et al. [8,40,41] and Jain et al. [42]. The incorporation of the flame
retardant directly in the polymer backbone has different advantages, among them avoiding migration
of the flame retardant in the polymer before burning. One of the most studied phosphorus reactant is
9,10-dihydro-9-oxa-10-phosphaphenanthrene (DOPO) [40,43-45]. It is a commercially available
compound and is recommended as part of the curing system of epoxies. However, its main drawback is
its monofunctionnality, and therefore it cannot be used as curing agent on its own. Numerous
references deal with the chemical modification of DOPO, leading to phosphorus containing epoxies
and curing agents [40,46,47]. Only recent works will be commented on in the following section.
Hergenrother et al. [48] synthesized different P-containing hardeners and epoxies. The obtained
components were used in different formulations. The flammability properties were evaluated by
microscale calorimetry, cone calorimetry, Ohio State University (OSU) test and flame resistance (non
standard test). In the flame resistance test, the time required for self-extinguishing after removal of the
flame is recorded. The reference formulation exhibited self-sustained burning in air but formulations
containing the P-containing hardener extinguished immediately. P-content above 0.9 wt % provided a
self-extinguishing behaviour. In the case of P-containing epoxies, all the samples containing more than
1 wt % phosphorus extinguished immediately whereas the other burnt between 1 and 2s. Therefore, a
minimum P-content in the epoxy or the hardener is required in order to get interesting
self-extinguishing behaviour. The reaction to fire was further studied by means of microscale
calorimetry. The curves exhibit two peaks, which are shifted to lower temperature when 3 wt % P is
incorporated in the systems compared to reference formulations. Furthermore, the height and area of
these peaks are also divided by≈ 2. The authors suggest that similarly to a catalytic mechanism, P
reduces both the temperature and activation energy for pyrolysis. The efficiency of P in reducing heat
release capacity and enhancing char formation seems to be linked to the oxidation state of phosphorus:
PO4 >:PO3 ≈ RPO3 > R3PO. Similar conclusions have been drawn by Braun et al. [49] on carbon-fiber
reinforced composites. Taking advantage of the presence of PO4 acting through a condensed phase
mechanism also limits the amount of phosphorus acting in the gas phase. Therefore, the effects in the
gas phase, such as a delayed ignition, are less present. This has to be taken into account depending on
the final applicability and therefore the standard to pass. Finally, cone-calorimetry confirmed the
presence of intumescence for P-containing samples. For some samples, there was even a complete
suppression of heat release rate for 1–2 min after ignition. Therefore, this study showed the interest for
phosphorus-based epoxies as low-flammable materials.
Combinations between phosphorus-modified resins and nanoparticles have been studied by
different authors. Hussain et al. [43] synthesized organo-phosphorus epoxy resins by reaction between
DOPO and bi- or tetrafunctional resins (bisphenol A diglycidylether –DGEBA- or
Materials 2010, 3 4488

N,N,N’,N’-tetraglycidyl-4,4’-methylenedianiline -TGDDM-), and clay (octadecylammonium-modified

montmorillonite, Nanocor I.30) was also incorporated in the systems. DSC measurements showed a
catalytic effect of clay on the curing of both DGEBA and TGDDM. Phosphorus-modified resins
showed different behaviours depending on the resin type: a decrease in curing temperature, indicating
an increased reactivity of the DGEBA system was observed, whereas the contrary was recorded for the
TGDDM systems. The authors attributed the difference to the modification of TGDDM with DOPO,
which led to a big and stable molecule. The morphology of the composites with clay was also
characterized by XRD and TEM. The clay-DGEBA system, either P-modified or not, showed
intercalated morphology according to the authors. Clay-TGDDM systems behaved differently: clay in
the unmodified resin is exfoliated, and thus better dispersed than in the P-containing resin where an
intercalated structure was observed. Therefore, the modification of the resin with phosphorus does not
seem to have an influence on the dispersion for the DGEBA systems, but the TGDDM system is
affected. The evaluation of the reaction to fire of the systems was evaluated by means of cone-
calorimetry at an external heat flux of 50 kW/m² and LOI. Incorporation of 7.5 wt % organoclay or 3 wt %
phosphorus in the DGEBA enhances the reaction to fire: the pHRR is respectively decreased by 40%
and 50%. However, combination of phosphorus-modified DGEBA and organoclay led to an
antagonistic effect since only a 38% decrease was observed. Similar results were found with the
TGDDM system: clay alone provides a 17% pHRR decrease, while it is reduced by 52% for 3 wt %
phosphorus in the matrix. No synergistic effect was observed for the combination of the two flame-
retardants (48% pHRR decrease). LOI experiments led to similar conclusion: the LOI is increased by
incorporation of phosphorus or clay in DGEBA, but the combination between the two fire-retardant
systems is less efficient. Similar results are obtained for TGDDM. Kiliaris et al. [50] recently reviewed
these results. They suggested that the lack of synergism between clay and the phosphorus-based resin
may be due to the phosphorus moiety hindering the dispersion of clay and leading to a less uniform
dispersion. This hypothesis is in accordance with the TEM results and is acceptable.
Liu et al. [51] studied further these systems by reacting DGEBA and TGDDM with a
phosphorus-containing hardener [bis(4-aminophenoxy)phenyl phosphonate, BAPP] and incorporating
the same organoclay at 5 wt % in the resin. Diethyltoluenediamine (DEDTA) hardener was used as
reference. An exfoliated or highly intercalated structure for the DGEBA and a more ordered structure,
probably intercalated for TGDDM, is claimed by the authors by XRD analysis. However, even if XRD
helps to investigate the morphology of nanocomposites, TEM images are required for a definitive
conclusion. The reaction to fire was evaluated by cone-calorimetry. Impressive reduction of pHRR is
obtained by using BAPP as hardener for both DGEBA and TGDDM systems without clay. In
accordance with the conclusions by Hussain et al. [43] little evidence of a synergistic effect brought by
clay was found. Incorporation of clay in the resins cured with DEDTA showed either as small decrease
or an important increase of the pHRR for DGEBA and TGDDM respectively. When the organoclay
was combined with the phosphorus-based hardener (BAPP), there was no modification for the
TGDDM system whereas a strong antagonistic effect was observed in DGEBA. The incorporation of
phosphorus in the epoxy backbone was successfully exploited and the incorporation of nanoclay in
epoxy was found to be tricky.
Toldy et al. [52] also studied combinations between phosphorus reactants and clays in epoxy. Two types
of molecules, phloroglucinol and calixresorcinarene, were partially or fully phosphorylated (Figure 7).
Materials 2010, 3 4489

Figure 7. Monophosphorylated phloroglucinol (left), partially (K4P4OH, middle) and fully

(K8P, right) phosphorylated C-methylcalix [4] resorcinarene [52].

The best results are obtained with the modified calixresorcinarene. They were identified from the
beginning as unable to cure the system and were therefore used as simple additives. Cone-calorimetry
revealed that the pHRR is decreased by increasing the quantity of additive. One of the sample
corresponding to 2.5% P (named K8P, Figure 7) in the system showed a 61% pHRR decrease. Another
additive (named K4P4OH, Figure 7) also provided a delayed pHRR. DSC measurements showed that
the reactivity of the system was decreased when K8P or K4P4OH was part of the system. Therefore,
the enhancement of LOI is limited (4–5% for K4P4OH and 3–7% for K8P, depending on the filler
content). Two types of montmorillonite were then incorporated in the resin at 1–2 wt %: a
well-dispersed montmorillonite or the same MMT with K8P intercalated between the clay platelets.
However, the enhancements expected from the incorporation of montmorillonite were not reached: the
LOI of MMT-K8P is similar that achieved with K8P alone, whatever the clay dispersion. Furthermore
the UL-94 classification was degraded from V-0 for K8P alone to HB for the formulations with clay.
The authors suggested that this lack of enhancement, compared to thermoplastic matrices, could be due
to the crosslinked structure of thermosetting matrices, which hinders the migration of the platelets to
the surface and the rapid formation of the protective layer.
Combinations between clays and phosphorus-containing species were further reported by the same
group [53]. A phosphorus-containing reactive amine (called TEDAP, without further explanation) was
synthesized and combined with montmorillonite and sepiolite for the production of epoxy samples
containing 1 wt % clay. The effect of the incorporation of TEDAP in the system was investigated by
DSC. The results showed that TEDAP can fully replace the traditional curing agent in this system.
Therefore, formulations where TEDAP partially substituted the traditional curing agent were
developed and tested for fire resistance. LOI, UL-94, cone calorimeter and glow-wire flammability
index showed the superiority of this new curing agent: substituting the original curing agent by 60 wt %
TEDAP permits to reach the UL-94 V-0 classification. Total replacement of the original curing agent
also led to a LOI value of 33% instead of 21% for the reference resin and the UL-94 classification
Materials 2010, 3 4490

remains V-0. Furthermore, this formulation showed a 80% decrease of the pHRR and a significant
shift in the time to ignition and time to pHRR. It also passed the GWFI test at 960 °C, indicating that
this epoxy cured with TEDAP is suitable for electrical equipment. Montmorillonite and sepiolite were
then incorporated in the original and the TEDAP-based systems. Slight decreases of the enthalpy of
crosslinking were observed by DSC and attributed to the adsorption of the crosslinking agents on the
surface of the clay. In the absence of TEDAP, montmorillonite had no effect on the fire properties of
the system, whereas sepiolite leads to a small increase of the LOI (from 21% for virgin epoxy to 25%).
The combinations between clays and TEDAP seemed moderately interesting since the LOI is increased
from 33% for TEDAP alone to 34% for the sepiolite and 36% for the montmorillonite.
Phosphorus-containing epoxies have therefore widely proven their benefit for flame retarding
epoxies. The versatility achieved with such molecules opens a wide range of achievable formulations,
depending on the final properties needed. Furthermore, sufficient fire properties are achieved with very
low P content. Synergies between organoclays and phosphorus-based epoxies have been examined by
different authors. However, in accordance to what has been observed in the first part of this paper, the
incorporation of clays sometimes helps to enhance fire properties but can also degrade them.

3.2. Silicon-Containing Networks

Silicon-based products have proved to be flame-retardant, especially in epoxies. Considering how

well phosphorus incorporated in the epoxy networks works, synthesis of hybrids based on epoxy and
silicon has been developed. Recent work in this field will be reviewed in the next part:
organic-inorganic networks obtained by mixing an epoxy prepolymer with a silicon-containing
monomer are often encountered. In order to enhance the reaction to fire, simultaneous incorporation of
phosphorus and silicon in the material has also been evaluated.
Mercado et al. [54] reacted DGEBA with diglycidyloxymethylphenylsilane (DGMPS) and cured
the obtained resin with diaminodiphenylmethane. Several DGMPS/DGEBA molar ratios were used in
order to obtain silicon contents varying from 0 to 8 wt %. It is important to note that the 8 wt % silicon
content corresponds to a material based only on DGMPS (without DGEBA). The curing cycle was
modulated taking into account the modified reactivity of the system when DGEBA is substituted by
DGMPS. Mixed epoxy systems exhibit a single Tg, suggesting a homogeneous material. The
flammability was evaluated by means of LOI. It is increased when silicon is incorporated in the epoxy
network: 24.1% for the virgin epoxy, 26.1% for the composite made from the 50 wt % DGEBA/50 wt %
DGMPS mixture and 36.0% for the sample made from DGMPS only. Even if outstanding values are
claimed, the best results are obtained for the sample containing no DGEBA but only the
silicon-bearing part of the formulation. The increase for the sample DGEBA50%/DGMPS50% is far
less impressive: 2%. The silicon-based resin therefore appears as an alternative to more common
epoxy resins. Canadell et al. [55,56] synthesized a silicon-containing spiroorthoester and mixed it with
DGEBA (Figure 8). DSC showed that the curing exotherm for both homopolymerization occurs at
lower temperature than for the mixed system. The curing cycles for the different materials were chosen
by taking this into account. Similarly to what was obtained by Mercado et al. [54] the Tg of the mixed
material is between those of pure materials. LOI helped to evaluate the flammability. The authors
reported that measuring the LOI of the material made only from the spiroorthoester was impossible,
Materials 2010, 3 4491

due to its relatively low Tg (73 °C). LOI of virgin DGEBA was 20%, and that for
DGEBA/spiroorthoester was 20.9%.

Figure 8. Spiroorthoester containing silicon[56].

Harada et al. [57,58] studied silsesquioxane derivatives bearing epoxy rings. First,
polyglycidyloxypropyl silsesquioxane (PGSQ) was mixed with titanate and cured with DDM. Two
different shapes of titanate were used: an organo-layered and a spherical titanate. DGEBA was
prepared in the same way for comparison. Horizontal UL-94 tests were conducted in order to evaluate
the flammability of the materials. DGEBA/organo-layered titanate and PGSQ/spherical titanate (5 wt %)
burnt completely without self-extinguishing, but the PGSQ/organo-layered titanate system
extinguished after 8 s and was classified V-0. SEM showed aggregates in the composite containing
layered titanate. On the contrary, the spherical titanate showed a uniform dispersion. These results
highlight the importance of the shape of the used particles for flame-retardant purpose: different shapes
for similar materials can lead to completely different dispersions. In a further study, Harada et al. [58]
chose poly(glycidyloxypropyl)phenylsilsesquioxane (PGPSQ), mainly because of the reported
capability for enhancing flammability properties of phenyl groups. PGPSQ was then mixed with the
same organo-titanate as before and cured with DDM. Similarly to what was observed for the PGSQ
system, TEM micrographs indicated that a microscopic phase separation occurred. UL-94 horizontal
burning test showed that the self-extinguishing behaviour was achieved with only 1 wt % titanate in
the PGPSQ system. In order to obtain a hybrid material, DGEBA was mixed with PGPSQ and the
titanate. Up to 10–20 wt % DGEBA in the system increases the extinguishing time but the samples are
still classified as V-0. For the composite containing 30 wt % DGEBA, no self-extinguishing behaviour
could be observed, whatever the titanate content. These studies show the potential of silicon in
epoxies. However, the enhancement of the fire performance is often very limited and the best materials
are often that containing very small amounts of epoxy resin.
Mixing P- and Si- containing compounds in epoxy matrices have also been considered, but the
contribution of Si to the flame retardancy of the systems is not often well identified. Hsiue et al. [59]
Materials 2010, 3 4492

synthesized materials containing P and Si via sol-gel method. A phosphorus-based compound bearing
epoxide rings (BGPPO) was mixed with DGEBA and TEOS (tetraethylorthosilicate, often used in
sol-gel systems) and cured with DDM. The amounts of BGPPO and TEOS varied. The flammability
was evaluated by LOI. First, resins without phosphorus were prepared. The Si content varied in order to
identify the effect of Si in the system. The reference resin without Si had a LOI of 26.0%. It increased
gradually along with the Si content, up to 31.0% for 8.73 wt % and 10.20 wt % Si. BGPPO alone has a LOI
of 36.1% and it is increased for the hybrid material: the LOI reaches 44.5% for the sample containing
4.35% P and 15.63% Si. Therefore, the use of phosphorus-modified epoxy resins is advantageous, and their
flame retardancy may be enhanced by the incorporation of small amounts of silicon.
In summary, similarly to what has been done with the incorporation of phosphorus into epoxy
backbone, silicon-containing epoxies led to hybrid materials. Limited enhancements of the reaction to
fie are obtained by the incorporation of Si. On the other hand, materials mainly based on silion appear
as an alternative to epoxy in terms of fire retardancy. Finally, combinations between phosphorus and
silicon are promising, with phosphorus being the main flame-retardant and silicon acting as synergist.

4. Coatings

Fire-protective coatings are widely used for building, steel or polymer protection. They are often
based on intumescent systems. This concept is based on the formation of a protective layer which
insulates the underlying material from heat and fire. Such intumescent systems require three major
components: an acid source (generally ammonium polyphosphate), a carbon source (such as char
forming polymers or polyols) and a blowing agent (e.g., melamine). Chemical reactions between these
ingredients lead to the formation of the protective intumescent char. A general mechanism has been
widely accepted: the acid source decomposes and yields a mineral acid, then it takes part in the
dehydration of the carbon source and finally the blowing agent produces gaseous products. These
gases are trapped in the char resulting from the carbon source dehydration and make it swell. In the
next section, intumescent epoxy systems, as well as novel approaches like phosphorus-containing
UV-curable coatings will be reviewed. Finally, the effect of the incorporation of nanoparticles in
intumescent epoxy coatings has never been examined. However, the concept has been tested in
acrylate systems and the main tendencies will be presented.
Jimenez et al. [36,60,61] widely reported the use of an intumescent protective coating for steel, the
formulation optimization and the characterization of its performance. The system is an
epoxy-amine system in which two fire retarding agents have been incorporated, separately or
combined: a mineral acid (boric acid) and a commercial ammonium polyphosphate. The tests are
aimed at linking industrial tests (OTI 95 634) with small-scale lab tests (“Bunsen burner test”). During
the industrial test, the sample is heated vertically at high heating rate by a propane burner and the
temperature at the backside is recorded. The burning conditions fit as close as possible the ramp of
temperature of a hydrocarbon fire heating curve (about 200 °C/min-UL1709). It was observed that the
use of the formulation without fire retardants provides properties close to those of the steel plate only.
When APP is added to the formulation, an improvement is observed (time of failure 11.3 min
compared to 5 min for uncoated steel). However, the char does not adhere correctly to the steel plate
and falls off, causing the failure. Similarly, boric acid yields enhanced fire properties (time of failure
Materials 2010, 3 4493

18.2 min), but once more, the char falls off the plate. Finally, a combination between these two
fire-retardant additives was incorporated into the system and provides the best properties (time of
failure 29.5 min) and the char adheres to the plate. The enhanced behaviour was attributed in particular
to the combination of phosphates promoting adhesion to steel and of borates which produce a very
hard char, resulting in the formation of borophosphates. Experiments using a rheometer were
developed and showed that the degradation of the resin at 350 °C leads to a decreased viscosity. The
incorporation of boric acid in the formulation limits this decrease by creation of a hard glass (boron
oxide), which traps gases and allows a char with good mechanical resistance.
Wang et al. [62] reported another trend in epoxy coatings: the use of UV curable epoxy resins
modified with phosphorus. They synthesized such a system, tri(3,4-epoxycyclohexylmethyl)phosphate
(TECP) and evaluated its fire behaviour by LOI. Various epoxy/TECP ratios were studied. Epoxy
alone has a LOI of 21% and TECP alone reaches 35%. As TECP is mixed with epoxy, the LOI
increases and reaches 27% for the sample containing 50 wt % epoxy/50 wt % TECP. It reaches 35%
for the material based on TECP alone. Mechanical characterizations showed that homogeneous
materials are obtained when epoxy and TECP are mixed. Furthermore, the tensile strength of epoxy
was improved when TECP was incorporated in it. Therefore, this study suggests that accessing
enhanced fire behaviour of UV-curable coatings is possible and can also enhance other properties, such
as mechanical ones. Taking into account ecological issues, the use of solvent-free or waterborne
coatings will probably lift off, and the production of intrinsically fire-retardant coatings is therefore
very promising.
Few publications have recently reported coatings based on epoxy resins alone, but combinations
between polyester or acrylates and epoxy resins are found. The influence of the binder in waterborne
coatings was studied by Wang et al. [63]. An epoxy emulsion was combined with a self-crosslinked
silicone acrylate (SSA) emulsion to get a waterborne intumescent coating. In this system, the
well-known APP/pentaerythritol/melamine intumescent system is combined with titanium dioxide,
kaolin and expandable graphite. Steel plates were coated by five formulations with epoxy/SSA ratios
varying from 39/0 to 27.8/11.2 The samples were tested by recording the temperature on the backside
of a heated plate. The shape of temperature profiles is similar for all the coatings. At the beginning of
the test, there is almost no difference between them, then, after 20 min, a steady state is reached and its
temperature depends on the coating formulation: for epoxy/SSA ratios ranging from 39/0 to 33.4/5.6,
the temperature is gradually decreased from 270 °C to 243 °C. When the SSA content increases further,
the tendency reverses and the temperature reaches 290 °C. Because the efficiency of an intumescent
coating is also linked to the morphology of the char, SEM showed that reasonable amount of SSA in
the system led to the formation of dense foam. Too big amount of SSA gives rise to large cells,
therefore decreasing the insulation, as was observed during the fire test.
Polyester or acrylate intumescent coatings enhanced by nanoparticles have been reported. Their
study gives clues about the interest for the incorporation of such particles in epoxies. Wang et al. [64-66]
reported in a series of three papers the effects of nano-LDH and nano-TiO2 on intumescent coatings
based on mixed acrylate/silicone resins. The aim of the incorporation of these additives was the
enhancement of the physical and chemical properties of the char layer, especially adhesion with the
substrate. First, a LDH masterbatch was prepared in order to fight the tendency to aggregation of
nanoparticles with the aid of dispersant. The dispersion of nanoparticles in the coating was
Materials 2010, 3 4494

characterized by TEM and compared with the result obtained by the standard procedure. The
masterbatch method using dispersant leads to highly enhanced dispersion and was used in the rest of
the study. Four coatings containing levels of nano-LDH from 0 up to 3 wt % were tested for their
fire-resistant properties on steel. The temperature on the back-side of the sample was recorded by
means of a thermocouple. The sample was heated following ISO-834 curve and the fire-resistant time
was defined as the time before reaching 300 °C on the backside of the plate. It can be seen that the
incorporation of LDH in the coating up to 1.5 wt % gradually increased the protection. However, when
the LDH content reached 3 wt %, the tendency reversed. The fire-resistant time of the reference
coating is 62 min. Incorporation of 0.5 wt % LDH leads to a similar result but the time reaches 100
min for the coating containing 1.5 wt % LDH. When the LDH content is 3 wt %, the time falls to 48
min. The observation of the residues showed that the intumescence was well-developed for the sample
containing 0, 0.5 or 1.5 wt % LDH (char thickness about 18 mm), but it was nearly absent for the
higher LDH content (4.3 mm). Various experiments were conducted in order to elucidate this
behaviour. The thermal stability of the coatings was then studied by TGA-DTA. The main conclusion
is that the incorporation of LDH in this system may enhance the fire protection. Thermal analyses
show that the thermal decomposition of LDHs can catalyze the esterification between ammonium
polyphosphate and pentaerythritol due to the enhancement of acid activity. XRD showed the presence
of aluminium and magnesium oxides. The char containing these oxides seems more resistant and
effective than a simple char. LDHs have to be incorporated at a specific content (1.5%): an increase of
the LDH content leads to an increased reticulation density, and thus, to a decreased mass loss, but a too
high LDH content hinders intumescence. Indeed, incorporation of too much LDH probably increases
the viscosity of the system and the formation of the protective layer is more problematic. Furthermore,
Castrovinci et al. [67] identified an antagonistic effect between ammonium polyphosphate (APP) and
aluminium trihydroxide (ATH). APP and ATH reacted together, decreasing the APP amount available
for the formation of the intumescent layer. A similar phenomenon could occur for the acrylate
intumescent coating since LDH is an organo-modified magnesium-aluminum mixed hydroxide. A
further study was conducted on a similar intumescent system containing LDHs (0.9 wt %) and
nano-TiO2 particles (0.9 wt %). They found that the incorporation of TiO2 mechanically reinforced the
char by reacting with ammonium polyphosphate or phosphoric acid and forming TiP2O7. Finally,
coatings containing TiO2 and no LDH were reported and showed that 1.6 wt % nano- TiO2 in an
intumescent system already containing micrometric TiO2 improves slightly the fire-resistant time from
81 min to 96 min. In this case, nanoparticles are not used as the main ingredients bringing fire
properties, since it is incorporated in an intumescent coating. However, they prove their efficiency for
enhancing the existing acrylate system when used at an appropriate content. Therefore, it would be
interesting to see if such particles bring also interesting properties to epoxy coatings.
As a conclusion, even if fire-resistant coatings are mainly based on ‘classical’ intumescent systems,
research in this field is very active and many parameters in the formulation can increase the fire
retardancy. Mixing resins, acrylate, silicon or epoxy, opens a new range of available properties. The
incorporation of nanoparticles in acrylate systems have shown their potential interest and their
transposition to epoxy may be useful. Therefore, depending on the substrate and the use, tailored
epoxy coatings can be developed for fire retardancy.
Materials 2010, 3 4495

5. Conclusions

Current trends in the flame retardancy of epoxy resins have been evaluated. The use of additives
still remains a simple way of improving the reaction to fire of epoxy resins. In particular, incorporation
of nanoparticles gives the possibility for enhancing the fire properties while maintaining or even
improving the mechanical properties of materials. Different particles are used: while carbon nanotubes
have not proven yet a strong effect as flame retardants in epoxies, modified layered double hydroxides
or polyhedral oligomeric silsesquioxanes turned out to be efficient at low loadings, if not always
nanodispersed. The particular case of organoclays is trickier since many factors seem to influence the
morphology of the composite and therefore the potential fire-retardant effect.
The incorporation of flame-retarding species such as phosphorus or silicon into the backbone of
epoxy resins is also an attractive approach: it provides good fire properties to the matrix while at the
same time simplifying the final formulation. Phosphorus is very effective in this type of system at low
contents and incorporating it in the epoxy avoids phenomena such as migration during storage.
However, it seems that silicon is less effective at bringing suitable fire properties on its own: a
synergism between phosphorus and silicon in these systems has been identified.
Finally, the particular case of epoxy coatings was studied. Current systems are mainly based on
‘classical’ intumescent systems. Considering the various available substrates, the different standards to
be reached and the presence of new additives, their versatility is still a strong advantage for the
development of tailored protective systems.
These three approaches are still promising for flame-retarding epoxy resins. The solution depends
on the final properties needed: for bulk materials, nanoparticles show many advantages, among them
the low loadings achieved and the often enhanced mechanical properties. However, they have not
proven yet on their own their benefit for fire retardancy. Therefore, if chemical modification of the
resins is possible for the chosen application, flame retardancy by incorporation of phosphorus into the
epoxy backbone appears as the solution providing the highest fire performance. Another wide
application of field of epoxies is flame-retardant coatings. Taking into account the different
possibilities offered by intumescent systems, sometimes enhanced by nanoparticles, this field still
focuses huge interest.

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