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Macromolecular

Chemistry and Physics

Talents & Trends


Trends in Polymer Science

Combinations of Elements: a New Paradigm


for Fire Retardancy
Thirumal Mariappan, Charles A. Wilkie*

This trend article describes some recent work related to the development of ame retardancy
of six common plastic materials, polypropylene, polystyrene, poly(methyl methacrylate),
unsaturated polyester, polyurethane, and epoxy resin. Conventionally, a single re retardant element is used to achieve
re retardancy but in this paper, there is a description of combinations of re retardant elements, including a nano-sized
material.

Introduction
In modern society, there is an
increasing use of plastic materials
to replace metals due to the lighter
weight and high specic strength of
plastic materials. However, the utilization of plastics carries a re risk that is
not seen with metals and this brings
about the need for re retardancy.
Plastic materials, when exposed to
high temperatures, decompose with
the release of heat, smoke, soot, and
toxic volatiles with smoke considered as the primary cause of death in
most res rather than heat.[1] There
are two ways to render a plastic ame
retardant (FR): 1) the plastic can be
blended with FRs (additive approach)
and 2) an FR element can be introduced into the plastic via a chemical
reaction (reactive approach). Both
T. Mariappan, C. A. Wilkie
Department of Chemistry and Fire
Retardant Research Facility, Marquette
University, PO Box 1881, Milwaukee,
WI 53201, USA
E-mail: Charles.wilkie@marquette.edu

classes of FRs have advantages in different applications.[2,3] The additive


approach has been most often followed. High loadings are sometimes
necessary, which can have a negative
impact on the mechanical properties
and impair the processing ability of
plastic materials. With the reactive
approach, only a little amount of the
FR may be necessary but it may be
very expensive.[4,5]
There are a variety of elements
that are considered the backbones
of the FRs, these include halogens,
phosphorus, nitrogen, silicon, minerals [typically aluminum trihdroxide (ATH) and magnesium
hydroxide (MDH), boron, iron, tin,
and antimony]. The last three are
typically not used alone but rather
are synergists that can make other
elements, usually halogens, more
effective. It should be noted that the
well-used monomeric halogen-based
re retardants have been at least
partially banned world-wide; it may
be expected that only polymeric halogen-based FRs will be used in the
future.[1]

Macromol. Chem. Phys. 2012, 213, 19871995


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Fire retardancy may occur in


the vapor phase, by trapping the
hydrogen and hydroxyl radicals that
make up the ame, or in the condensed phase, changing the course of
the thermal degradation of the polymer from one that produces volatile
to one that produces char. The minerals ATH and MDH decompose endothermically with the elimination of
water so the heat goes to decompose
the mineral and not to decompose
the polymer.
There are several laboratory tests
that are used to evaluate re retardancy; those must often used are the
limiting oxygen index (LOI), the UL-94
protocol and the cone calorimeter.
LOI measures the minimum concentration of oxygen required for a material to burn; the higher one can drive
up this minimum concentration,
the more re safe a material may
become. The UL-94 protocol evaluates
the ease of extinction of a polymer,
the shorter the time for which a
material burns the safer it may be.
The cone calorimeter measures the
heat release rate (HRR), that is, how

DOI: 10.1002/macp.201200363

1987

Macromolecular
Chemistry and Physics

T. Mariappan and C. A. Wilkie

www.mcp-journal.de

big is the re. It is unfortunate that


each of these evaluations measures
a different property of a re and one
cannot correlate the results from one
evaluation with those of a different
technique.
The situation in the past has been
that most often a single FR element,
perhaps with a synergist, has been
used. This is not to suggest that the
typical FR package does not contain several different materials but
usually only one of these is the re
retardant. The premise of this work
is that, in the future, we will see
combinations of re retardant elements used together. One obvious
example that has not been often
exploited is the combination of an
FR that functions in the vapor phase
with one that is condensed phase
active. In this case, one might expect
that the amount of volatiles will
be reduced and that the halogen or
phosphorus can then trap what is
produced.
For more than 10 years, many
groups have been studying nanodimensional materials, typically
montmorillonite (MMT) and related
clays, and it has been found that this
reduces the peak HRR as evaluated
by the cone calorimeter.[69] Polymers
containing MMT, or other nanodimensional materials, typically show
no improvement when evaluated
by other re retardancy evaluative
protocols. The utilization of a nanodimensional material also offers
enhanced mechanical performance
so that if it is combined with another
re retardant, the loss of properties
due to this material may be at least
partially offset by the presence of the
nanodimensional material.[6]
This trend article addresses the
combination of conventional re
retardants together with nanodimensional materials for six different
common plastic materials, polypropylene, polystyrene (PS), poly(methyl
methacrylate), unsaturated polyester/vinyl ester resin, polyurethane,
and epoxy resin.

1988

Charles A. Wilkie retired from Marquette University in 2009 and is


now professor emeritus. His research group has been studying re
retardancy for more than 30 years and polymer nanocomposites for
more than 10 years. The group currently is focused on the utilization of
nanocomposites to enhance the re retardancy of polymers.
Thirumal Mariappan obtained his M.Tech. degree (after bachelor and
master in Chemistry) in Polymer Technology from Cochin University of
Science and Technology. Before his Ph.D. work, he worked for 6 years
in some of the research projects from various Indian Government
R&D Institute like CSIR, DRDO, and an Engineering College. In 2010, he
received his Ph.D. in re retardancy of polyurethane foam from Indian
Institute of Technology, Kharagpur. He is currently a postdoctoral fellow
at Marquette University.

Flame Retardancy of
Polypropylene
Polypropylene (PP) burns readily in air
(LOI = 17%) with melting and dripping
and produces virtually no soot nor
leaves any residual char. PP starts to
degrade thermally above 290 C, via
a random scission mechanism with a
complex mixture of gaseous pyrolysis
products of C4, C5, and C6 hydrocarbon
fragments with only small amounts of
propylene monomer present. The FR
requirements for PP are generally similar to those for other polyolens.[10]
The re retardancy of PP usually relies
on the use of endothermic additives,
which requires about 60% additive
and thus the mechanical properties
are severely impacted, vapor-phase
additives, or intumescent compositions.[11] Many commercially available
FRs are not completely compatible and
tend to bleed out; FRs for PP have to
be thermally stable at the processing
temperature of about 250 C.
Intumescent compositions swell
when heat is applied and thus form
a thick layer of insulating material,
which can limit the ow of heat to
the polymer. The classical intumescent (IFR) composition contains three
basic components, acid [ammonium
polyphosphate (APP), char-former
(pentaerythritol), and blowing agent
(melamine)]. A minimum of 30 wt%
of IFR loading is necessary for
Macromol. Chem. Phys. 2012, 213, 19871995
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

effective ame retardancy (UL-94 V-0


rating) in PP.[12] A potential problem
for IFR compositions is the water
solubility of both APP and pentaerythritol. Microencapsulated APP has
a lower water solubility and thus may
show some improvement.
Various nanodimensional materials have been incorporated into IFR
PP formulations. He et al.[13] showed
a V-0 rating with 25% of IFR loading
with addition of organoclays. The
addition of organobentonite can
improve the FR properties of IFRPP
due to an increase of the char residue,
which acts as an effective barrier for
heat and oxygen, thus improving
the ame retardancy of intumescent
ame-retarded PP samples, as well as
an increasing the LOI value.[14] A synergistic effect was observed from the
combination of clay and decabromondiphenyl ether (Deca) plus Sb2O3 in PPg-MA system.[15] Hu et al.[16] studied
the ammability of PP/clay and PP/
clay/nano-CaCO3 nanocomposites and
showed a synergistic FR effect of nanocomposites with IFR additives. Zhang
and Wilkie[17] have studied the re
retardancy of PP using metal hydroxides (ATH and MDH) and clay combinations. The addition of clay imparts
good re retardant properties with
lower amounts of metal hydroxide.
Addition of clay could improve both
thermal stability and re retardant
properties of PP lled with FRs.[18]

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Macromolecular
Chemistry and Physics

Combinations of Elements: a New Paradigm for Fire Retardancy

www.mcp-journal.de

Table 1. LOI and UL94 data of FR lled PP with different loading of sepiolite. (Reproduced
from ref. [19] with permission).

Sample
[wt%]

IFR
[%]

Sepiolite
[wt%]

LOI
[%]

UL 94 test

Dripping

PP - 100

17.6

No rating

Yes

PP - 75

25

34.4

V-1

No

PP - 75

24

36.0

V-0

No

PP - 75

23

35.8

V-0

No

PP - 75

22

35.8

V-1

No

PP - 75

21

32.3

V-2

No

Sepiolite is part of a family of


brous hydrated magnesium silicate with the theoretical formula
Si12O30Mg8(OH)48H2O characterized
by a needle-like morphology. Sepiolite showed synergistic FR effect
with IFR lled PP and a V-0 rating
was observed with 24% of IFR and
1% sepiolite clay (Table 1); higher
loadings of sepiolite decrease the FR
properties.[19,20]
A synergistic FR effect was observed
for the combination of fumed silica
and IFR in PP. The amount of fumed
silica is critical; less than 1% fumed
silica loading increases both thermal
stability and re retardant properties
of IFR lled PP, because the fumed
silica promotes the formation of a
compact intumescent char layer and
prevents the cracking of the char
layer, which effectively protects the
underlying polymer from burning.
However, a high loading of fumed
silica restricts the formation of
charred layers with P-O-P and P-O-C
complexes formed from burning of
polymeric materials and destroys
the swelling behavior of intumescent
charred layers, which deteriorates the
FR and thermal properties of the PP/
IFR blends.[21]
The
layered
phosphate,
-zirconium phosphate [-Zr(HPO4)2.
H2O] is used in intumescent re
retardant PP systems as a synergistic
agent. PP with low loading (2.5 wt%)
of organically modied -ZrP with
22.5 wt% IFR (APP + PER) provides a
UL-94 V-0 rating with an LOI of 37%.

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In this case, -ZrP acts as a solid


acid that can catalyze dehydrogenation of the polymer, acting as
an effective crosslinking agent.[22]
Another study showed that nanoZrO2 is also synergistic in IFR lled
PP.[23] Yi et al.[24] also found a synergistic effect of llers, such as ZnO,
nano ZnO, zeolite 4A, and aluminum
hypophosphite, with IFR lled PP.
Wang et al.[25] studied the effect of
different metallic oxides (titanium
dioxide, lanthanum trioxide, zirconium dioxide, molybdenum trioxide,
and manganese dioxide) on the re
retardancy of PP lled with IFR. The
results showed that ZrO2 and Cr2O3
exhibit better ame resistance (V-0
rating in UL-94) than do the other
oxides. Du and Fang[26] investigated
the effects of carbon nanotubes
(CNTs) on the ammability of PPIFR
system; the introduction of CNTs
enhances the thermal stability of PP,
but showed a severe deterioration of
ame retardancy.[26]
Deodhar et al.[27] studied the ame
retardancy of calcium carbonate
nanoparticles combined with APP in
PP and showed that better burning
rates are caused by the formation
of calcium metaphosphate with
the evolution of ammonia, water,
and carbon dioxide. A low loading
(2 phr) of expandable graphite (EG)
gives higher LOI values for PP lled
with IFR and increasing the loading
of EG, deteriorates the FR activity
of IFR lled PP. Moreover, EG shows
better ame resistance than natural
Macromol. Chem. Phys. 2012, 213, 19871995
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

graphite at the same loading in PP


lled with IFR.[28]

Flame Retardancy
of Polystyrene
Polystyrene (PS) is intrinsically highly
ammable (LOI = 18%) and has a tendency to depolymerize when exposed
to high temperatures, and the volatile
products, styrene monomer, dimer,
and benzene and lower alkyl benzenes, have high fuel value. Since the
fuel is aromatic, it is able to condense
to large polycyclic structures, resulting
in a very smoky or sooty ame. Yang
et al.[29] showed that nanosilica
could effectively improve the ame
retardancy of brominated PS. Beach
et al.[30] found that a low loading of
sulfur could improve the LOI values
of PS lled with triphenylphosphate.
Synergy was observed between
phosphate and bromine re retardants and clay[31,32]; signicant deterioration of mechanical properties is
observed upon the addition of conventional FR but, the addition of clay can
ameliorate this. Improvements in re
performance of PS/IFR composites by
the partial substitution of nanollers,
including clay, OZrP, CNT, Fe2O3, and
nickel catalyst have been reported. The
presence of these additives changes
the structure, yield, and thermal
stability of the char, which leads
to composites with different ammability performance. The claycontaining sample showed the lowest
ammability. OZrP modied with
different salts had various effects,
depending on the cations, on the FR
efciency of IFR system.[33] A synergistic effect of CNT with Deca/Sb2O3
was observed in PS system.[34]
Nyambo et al.[35] showed synergistic effects in both TGA and cone
calorimetry for PS formulations containing both MgAl-LDH and APP.
Physical and chemical interactions
between MgAlLDH and APP are
responsible for the observed synergy in thermal stability and re

1989

Macromolecular
Chemistry and Physics

T. Mariappan and C. A. Wilkie

www.mcp-journal.de

performance. Tutunea and Wilkie[36]


studied the effect of nanosized llers
such as layered silicate and MWCNT
on the re properties of PS lled with
different FR additives (Deca/Sb2O3,
ATH, and RDP). The combination of
MWCNT with either ATH or RDP did
not improve FR properties of PS compared with the sample containing FR
alone. In contrast, there is a synergistic interaction between MWCNT
and Deca and a greater reduction of
peak HRR was observed.
The effect of nanosilica and attapulgite clay as nanollers on the
ame retardancy of PS has been
investigated. Both attapulgite and
silica nanocomposites improve the
vertical burning ame retardancy
of FR lled PS by reducing dripping;
char formation is promoted and the
total heat released during burning is
reduced.[37]
Flame Retardancy of Poly(methyl
methacrylate)
Poly(methyl methacrylate) (PMMA)
ignites readily (LOI = 17%) and softens
as it burns; the pyrolysate contains
much monomer and little, if any,
high-molecular-weight
products.
Depolymerization, rather than chain
scission, causes PMMA to drip less
during burning than most other polymers. Depolymerization together with
the presence of oxygen in the ester
group, probably accounts for the lower
smoke formation per unit weight in
comparison with that of hydrocarbon
polymers under most burning conditions.[38] Halogenated compounds
have been used to reduce burning
rates and ease of ignition of PMMA,
but less effort has been devoted to the
re retardation of PMMA than to that
of other polymers. This lack of effort
is due partly to the realization that
it is difcult to inhibit the unzipping
depolymerization mechanism characteristic of this polymer. In addition,
excellent transparency and aging
characteristics are critical properties
in most applications for PMMA; re

1990

retarding additives usually detract


from one or both of these properties.
Pack et al.[39] showed that a mixture
of MWCNT and clay nanosized materials can enhance ame retardancy of
PMMA to a greater degree than the
addition of either of the nanoparticles alone. Addition of nanoparticles,
including the standard FR formulations, decrease the time to ignition.
The combination of MWCNT and clay
signicantly reduced the HRR and
mass loss rate relative to compounds
with only one type of nanoparticles.
Moreover, they showed a V-0 rating
with the addition of a small amount
of MWCNT to the Deca/Sb2O3 lled
PMMA sample. A synergistic effect
of nano-ZrO2 with TPP in PMMA was
observed by cone calorimetry.[40]
Isitman and Kaynak[41] investigated the effect of organophosphinate
FR with nanollers (nanoclay and
MWCNT) in PMMA; nanoclays were
better than CNT in improving the re
properties of FR lled PMMA samples
assessed by cone calorimetry. The
observed behavior was explained as
due to the restriction of intumescence
by strong CNT networks formed on
the aming surfaces during combustion but enhanced intumescent chars
by nanoclays.
The FR properties of PMMA
modied with a zinc aluminum undecenoate LDH and/or melamine were
studied. Higher loadings of melamine are required to obtain enhancement in re properties, whereas LDH
seems to give similar reductions in
PHRR at lower loading (10%). The
effect of the two additives on the re
behavior of the PMMA samples was
dictated by the additive, with melamine increasing the time to PHRR
and lowering the amount of smoke
produced relative to the LDH-rich
PMMA composites. Both melamine
(10%) and LDH (5%) showed better
performance when considering the
reduction in PHRR, FIGRA, and FPI.[42]
A synergistic effect was observed
between EG and silica in PMMA in
terms of LOI.[43]
Macromol. Chem. Phys. 2012, 213, 19871995
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Cinausero et al.[44] found synergistic re properties in PMMA and PS


between nano-sized oxides (alumina
and silica) and APP. It is noteworthy
that the decrease of peak HRR and
smoke as well as an increase of LOI
were noticed with hydrophobic silica
combined with APP both in PMMA
and PS. This behavior was ascribed
mainly to the formation of a specic
silicon metaphosphate (SiP2O7) crystalline phase, which promotes charring and an efcient insulating layer.
Laachachi et al.[45,46] studied the
effect of oxide nanoparticles (TiO2,
Al2O3) on the ammability of PMMA
lled
with
organophosphinates
and APP. The combination of either
phosphinate or APP with metal
oxide nanoparticles can enhance
the thermal stability as well as re
retardancy of PMMA. The nanoparticles aid the catalytic effect and the
reinforcement for the carbonaceous
layer promoted by the FR additives.
However, TiO2 does not improve the
re behavior of the composites significantly as compared with Al2O3.

Flame Retardancy of
Unsaturated Polyester
Unsaturated polyester resins are lowmolecular-weight prepolymers or
precursors, which are prepared by the
condensation of a glycol, an unsaturated acid, and a saturated aromatic
acid. Styrene or methyl methacrylate is most commonly employed
as the cross linking agents for the
polyester resin. Cast and glass ber
reinforced resin constitute a large
proportion of the high volume composite materials currently in use.
They are employed in a wide range
of applications such as ooring, surface coatings, boats, transportation,
and buildings; res may arise in these
uses at any time, giving great importance to re hazards.[47] Because of the
aromatic content (styrene) in polyester resins, large amounts of smoke
can be released. When low smoke

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Combinations of Elements: a New Paradigm for Fire Retardancy

Macromolecular
Chemistry and Physics
www.mcp-journal.de

properties are required in a product,


the use of methyl methacrylate or
dicyclopentadiene in place of styrene
is advantageous.
The combination of expandable
graphite (EG) and APP mixtures
showed synergistic FR behavior
with polyester resin.[48] Nazare
et al.[49] studied the ame and smoke
retardant properties of polyester
resin lled with the combination of
APP, Cloisite 25A, and smoke suppressants [zinc borate (ZB), zinc stannate
(ZS), and zinc hydrostannate (ZHS)].
Flame retardancy was observed for
the resin lled with APP and ZB due
to the cross-linking of APP in the
presence of zinc borate, but zinc stannates do not promote cross-linking
of APP and hence show no improvement in ame retardancy. APP alone
is a good smoke suppressant and in
the presence of ZB and ZS there is
further smoke suppression. Addition of Cloisite 25A to the APP lled
sample shows reductions in smoke
formation in both well-ventilated
and under-ventilated re conditions.[49,50] Another study showed
that the improvement of ame resistance depends on the nature of the
surfactant in the clay. For example,
polyester resin lled with APP and
Cloisite 10A show good ame resistance compared with Cloisite 15A and
25A. Furthermore, they also showed
that clay could improve the ame
retardancy of polyester resin lled
with APP rather than melamine phosphate, IFR mixture, and ATH.[51,52]
Atkinson et al.[53] studied the inuence of inorganic tin oxide and stannate additives such as ZS and ZHS
on the ammability of halogen-containing polyester resin; stannates are
more effective than tin oxide. Tibiletti
et al.[54] studied the effect of different
metallic oxides such as alumina,
ATH, and fumed silica on the FR properties of polyester resin. This study
shows that one particle alone has
little inuence on the re behavior of
polyester resin; however, a mixture
of particles led to a strong decrease of

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ammability, particularly the combination of fumed silica and ATH


showed greater reduction of peak
HRR as compared with the mixture
of alumina with ATH and dehydrated ATH at the same loading. Horrocks et al.[55,56] reviewed the inuence of stannate additives on the
ammability of different polymers
such as PVC, PP, PA, ABS, polyester,
and epoxy resin. The effect of ZHS,
Sb2O3, and ATH on the ammability
of polyester resin containing decabromodiphenyl ether and dibromoneopentyl glycol (DBNPG) was also
studied; the addition of Sb2O3 to
both brominated resins provides a
V-0 rating with higher LOI values
compared with either ZHS or ATH
added alone or in combination
with ZHS and Sb2O3. Both halogenated samples containing Sb2O3 and
ZHS give lower smoke compared with
the lled sample alone (Figure 1).
Kandare et al.[57] studied the ammability of poly vinyl ester resin using
RDP, copper hydroxy dodecyl sulfate
modied LHS and Cloisite 15A. They
found that the combination of RDP
with nanollers showed antagonistic
FR effect. On the other hand, POSS
and organoclay with conventional FRs
showed a synergistic effect.[58]
Flame Retardancy of Polyurethane
Polyurethanes or/polyureas (PU) represent a broad group of polymeric

materials made by reacting diisocyanates with diols or/diamines.


Depending on the ratio of reactants
and their types, catalyst, reaction conditions, etc., various kinds of PU materials useful for the manufacture of
foams (exible or rigid), elastomers,
coatings, and adhesives can be produced. Polyurethanes are readily ammable (LOI = 16%22%) with release
of toxic smoke. The ammability of
PU strongly depends on the structure
of the polyol, degree of cross-linking,
density, and isocyanate index, especially foams. Jayakody et al.[59] showed
the synergistic effect of conventional
FR with polydimethylsiloxane in polyurethane elastomer. Bashirzadeh and
Gharenhbaghi[60] studied the ammability of exible PUF using melamine
and EG. Cone calorimetry showed that
the melamine lled sample had higher
ignition time, while greater reduction of both peak HRR and smoke was
observed from the EG lled sample and
synergistic behavior with the combination of melamine and EG was observed.
Triethylphosphate (TEP) and red
phosphorus (RP) are useful coadditives in combination with EG; the
presence of TEP helps to decrease the
heat conductivity of the foam and
overcome the poorer physical properties because of plasticization. TEP
acts predominantly in the gas phase
and the improved results obtained
for TEP/EG lled foams are due to
the simultaneous FR action both

Figure 1. PHRR, TSR, and smoke values of polyester resin containing DBNPG under
35 kW m2. (Reproduced from ref. [56] with permission).

Macromol. Chem. Phys. 2012, 213, 19871995


2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

1991

Macromolecular
Chemistry and Physics

T. Mariappan and C. A. Wilkie

www.mcp-journal.de

in the solid and in the gas phases,


while for RP/EG lled foams the FR
action is effectively only in the solid
phase.[61] Both APP and EG improve
the ame retardancy of PU materials
but EG was better than APP in terms
of both re and smoke retardancy.[62]
For example, 15 wt% of both EG and
APP used alone in rigid PUF gave
LOI values of 32% and 24.5%, respectively. The optimal ratio of APP to EG
in rigid PUF is 1:1 by weight (total
loading is 15 wt%) and the LOI value
was 30.5%.[63]
Fly ash, a by-product of coal-red
power stations, containing SiO2,
Al2O3, Fe2O3, CaO, SO3, MgO, Na2O,
K2O, MnO, TiO2, and P2O5, could
improve the ame retardancy of IFR
lled rigid PUF.[64] Zatorski et al.[65]
investigated the ammability of
polyurethane-polyisocyanurate foam
(PIR) containing different FRs such as
brominated triol, phosphorus polyol,
zinc stannate, expandable graphite,
and layered silicates. The addition of
clay improves the ame retardancy
of foam containing EG and ZS.
Modesti et al.[66] showed that phosphonium-modied clay improves
the ame retardation of aluminum
phosphinate lled rigid PUF, while
unmodied and ammonium modied clays do not. The inuence of
hollow microspheres and whisker
silicon oxide on the properties of EG
lled PUF was investigated by Bian
et al.[67,68] There is no change in ame
resistance of PUF lled with hollow
microsphere and whisker silicon
oxide separately, whereas a high
loading of EG with hollow microspheres improves the ame retardancy of PUF and moreover, whisker
silicon oxide performs better than
the hollow microsphere in combination with EG.
Bourbigot et al.[69] studied the
ame retardancy of TPU using APP
and MWCNT. The substitution of APP
by MWCNT is not benecial in terms
of PHRR (Figure 2), even though a
higher quality char is formed. The LOI
of TPU/APP (30 vol%) is not improved

1992

Figure 2. HRR as a function of time of TPU and TPU/APP-MWCNT (heat ux 35 kW m2).


(Reproduced from ref. [69] with permission).

by the substitution of APP by MWNT


but a V-0 rating at 3.2 mm (TPU/
APP exhibits a V-2 rating without
MWCNT). Hence, they believed that
the nanocomposite approach gives
the best results combined with conventional FRs and leads to synergistic
effects.
The addition of organoclay and
phosphate ester FRs in TPU gave a
better re performance index (FPI)
than organoclay and phosphate ester
lled TPU (Table 2). The FPI (ratio of
the time to ignition and the peak
HRR) is used to characterize the ame
retardancy of materials. It is important because it correlates to the time
to ashover and indicates the time
available to escape in a full-scale re
situation. Therefore, it may be considered as a good individual indicator
of the overall re hazard. The higher
the FPI value, the better is the ame
retardancy of a material.[70]
The addition of nanoclay with
3-chloro-1, 2-propane diol as chain
Table 2. Effect of organoclay on the re
performance index of TPU. (Reproduced
from ref. [70] with permission).

Materials

Fire
performance
index (FPI)

TPU

0.073

TPU + 5% organoclay

0.130

TPU + phosphate ester

0.071

TPU + phosphate ester


+ 5% organoclay

0.199

Macromol. Chem. Phys. 2012, 213, 19871995


2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

extender improves the thermal stability, ame retardancy, and also


mechanical properties of segmented
PU elastomer compared with commercial PU containing 1,4-butane
diol as a chain extender.[71] Kozlowski
et al.[72] studied the effect of butyl
acrylate-modied clay on the ammability of polyurethane lled with
melamine polyphosphate, starch, and
dextrin. Butyl acrylate-modied clay
improves the ame retardancy of the
IFR lled PU sample.
Awad et al.[73] studied the ammability of polyurea nanocomposites
containing APP and EG; the addition of nanoller such as clay, POSS,
MWCNT, gives a slight improvement
of ame retardancy of FR lled PU.
Flame Retardancy of Epoxy Resin
Epoxy resin is a specialty thermosetting plastic that has developed a
signicant market as adhesives and
coatings in reinforced laminates, and
in molding and casting applications
because of a unique combination of
properties. Epoxy resins are relatively
low-molecular-weight prepolymers
capable of being processed under a
variety of conditions. The diglycidyl
ether of bisphenol A (DGEBA) is the
most commonly used liquid diepoxide.
Although epoxy resins normally are
ammable (LOI = 22%), their ammability can be reduced considerably
by the use of a variety of phosphorus
and halogen additives or monomers.

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Macromolecular
Chemistry and Physics

Combinations of Elements: a New Paradigm for Fire Retardancy

www.mcp-journal.de

Table 3 Fire retardancy of epoxy lled with clay and conventional FRs. (Reproduced from
ref. [76] with permission).

Sample

LOI (%) UL 94
1

tig
(S) 3

THE/ML Residue
THE
[MJ m2] [MJ g m2] [%] 2
10
0.2

EP

20.5

HB

102

140

2.4

5.0

EP + Clay

21.2

HB

90

130

2.3

9.2

EP + 5 MB

23.3

HB

60

142

2.4

9.8

EP + Clay + 5 MB

23.5

HB

60

135

2.4

12.5

EP + 10 MB

24.1

HB

53

129

2.3

12.0

EP + 10 APP

23.8

HB

62

105

1.9

15.6

EP + Clay + 10 APP

21.9

HB

63

116

2.2

21.1

EP + 15 APP

28.9

V0

66

84

2.0

35.3

Many applications of epoxy resins


require the system to be re resistant,
for example, electrical laminates for
PCB and certain structural composites.
A common method of imparting this
re resistance is the incorporation
of tetrabromobisphenol-A (TBBA) or
the diglycidyl ether of TBBA into the
resin formulation. However, mainly
because of environmental concerns
and recycling issues, there has been a
growing interest in halogen-free FRs.
The use of ATH and TPP in epoxy resin
displays notable ame-retardant synergism[74]; the combination of APP and
boric acid leads to the best IFR protective coating in epoxy resin compared
with their use separately.[75]
Schartel et al.[76] studied the FR
properties of epoxy lled with phosphonium-modied clay with conventional FR additives (melamine
borate and APP) and showed that the
ame retardancy efciency does not
increase linearly with the MB and
APP concentrations (Table 3). The
combination of clay with MB or APP
shows antagonism as result of inhibition of the intumescent behavior.
However, the combination of phosphonium-modied clay with ATH
is a promising approach for ame
retardancy.[77]
Another study also showed that
the incorporation of clays did not
give the desired FR effect to epoxy
resin probably due to the increased

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heat conductivity and lower mobility


of clays due to the cross-linked structure.[78] Katsoulis et al.[79] showed
better ame retardation of epoxy
lled with APP and clay than clay
with RDP and TBP. Clay alone gives
better ame resistance in epoxy
than CNT, whereas the combination
of APP and CNT shows greater ame
retardation than that of the APP
clay mixture. Furthermore, there
is no improvement when both clay
and CNT are used with APP. Camino
et al.[80] studied the combined re
retardant action of phosphonates
2,2-bis(3-diethyloxyphosphonyl-4hydroxyphenyl)propane (BisP) and
5,5-bis(diethyloxyphosphonyl)-6,6dihydroxy-3,3,3,3-tetramethyl-1,1spirobiindane (SpiroP) and clay and
found synergistic and additive effects
from SpiroP and BisP with clay when
evaluated in terms of peak HRR reduction. Wu et al.[81] found synergistic
FR behavior epoxy resin lled with
phosphonium-modied clay and lowmelting phenylsiloxane glass.
Harada et al.[82] showed that the
ame retardancy of epoxy lled
with poly(glycidyloxypropyl) phenyl
s i l s e s q u iox a n e / o r ga n o - l aye r e d
titanate system was superior to
the poly(glycidyloxypropyl) silsesquioxane/organo-layered
titanate
system probably because the presence of phenyl promotes charring.
No synergistic effect was observed
Macromol. Chem. Phys. 2012, 213, 19871995
2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

in epoxy resin lled with POSS and


triglycidyl isocyanurate.[83] Wang
et al.[84] studied the effects of metal
compounds on the ame retardancy
of epoxy resin lled with APP; the
addition of APP and metal compounds improves the re safety of
epoxy resin signicantly presumably because the metal compound
show a catalytic effect. Song et al.[[85]
studied the effect of metallic oxides
(TiO2, La2O3) on the FR properties of
APP lled epoxy resin; APP alone in
EP obtains a V-0 rating at a loading of
20%. Addition of La2O3 causes the formation of a more compact char with
smaller carbonaceous microstructure.
Liu and Chou[86] studied the effect
of silicon additives such as nanosilica, tetraethoxysilane, and diglycidylether-terminated polydimethylsiloxane on the ammability of
epoxy resin lled with phosphorus;
the addition of silicon compounds
enhances the thermal stability and
char yields of epoxy resins. Nanosilica
did not migrate to the surface of the
epoxy during thermal degradation
and showed antagonism with phosphorus. In the case of tetraethoxysilane, the diglycidylether-terminated
polydimethylsiloxane lled sample
showed signicant silicon migration
and could form a protective layer to
prevent further degradation of the
char. However, another study showed
that synergistic efciency of phosphorus and silicon was not observed
in terms of LOI.[87] In general, thermal
stability and ame retardancy of
epoxy resin are improved by the combination of silicon- and phosphoruscontaining compounds[88,89] because
phosphorus provides the char formation and silicon provides the enhancement on thermal stability of the char
during combustion.[90,91]

Summary
Nanodimensional materials have
three major areas of application,
enhancing ame retardancy, barrier

1993

Macromolecular
Chemistry and Physics

T. Mariappan and C. A. Wilkie

www.mcp-journal.de

properties, and mechanical properties.


Based upon the very large number of
investigations into the properties of
these materials, since their discovery
in the mid-1990s, it is surprising to
many that there are only a small
number of products that have reached
the market place. This is particularly
true in the eld of ame retardancy
where many feel that this too shall
pass. Some companies that were initially involved with polymerclay
nanocomposites have left this business and are focusing on other uses of
clays.
In this trend article, it is shown
that there have been a great number
of examples where nanodimensional
materials have been combined with
conventional ame retardants and
improved performance has been
obtained. This is true considering
only the re performance but the
addition of a nanodimensional material has the opportunity to enhance
all of the properties noted above, so
there use can be a signicant advantage. The authors feel that the future
of nanocomposites in re retardancy
is their usage as adjuncts with conventional re retardants.
Of the six polymeric materials that
are covered in the trend article, the
reader will observe that there are
far fewer cases for polystyrene and
poly(methyl methacrylate). For PS,
the typical ame retardant is a halogenated material and, since these
are in disfavor, there is not a strong
reason to attempt to discover combinations with nanomaterials. In the
case of PMMA, there is currently no
ame retardant for this material and
it is most commonly used with one.
Thus efforts on these two polymers
are more directed toward identifying
suitable ame retardants.
There are a large number of nanodimensional materials. In many
ways, it is quite fortunate that the
MMT-type clays were the rst investigated because they have shown the
best properties up to this time. This
does not mean that there may be

1994

another nanomaterial that has not


yet been evaluated and will excel in
some areas but it does mean that one
should be a little suspect when trying
a new nanomaterial.
It is hoped that through this trend
article, scientists and engineers will
consider combinations of ame
retardant elements as they continue
to develop new ame retardant
additives.
Received: June 28, 2012; Revised: July 13,
2012; Published online: August 23, 2012;
DOI: 10.1002/macp.201200363
Keywords: epoxy resin; ame retardancy;
poly(methyl methacrylate); polypropylene;
polystyrene; polyurethane; unsaturated
polyester
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Combinations of Elements: a New Paradigm for Fire Retardancy

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