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Flame retardant polymer/layered double hydroxide

nanocomposites
Cite this: DOI: 10.1039/c4ta01030b
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Yanshan Gao,a Jingwen Wu,a Qiang Wang,*a Charles A. Wilkieb and Dermot O'Hare*c

Received 28th February 2014
Accepted 27th March 2014
DOI: 10.1039/c4ta01030b
www.rsc.org/MaterialsA
Recently, there has been rapid growth in research related to the synthesis and application of flame retardant
polymer–layered double hydroxide (LDH) nanocomposites. In order to outline the potential and to promote
further developments in the field we have prepared a critical review of the most recent progress in the area.
We discuss the techniques and indices (e.g. micro calorimetery, limiting oxygen index, cone calorimetry and
UL-94) for evaluating the flame retardant properties. The flame retardant mechanism of LDHs, the types of
polymers studied, the effect of LDH chemical composition and the synergistic effect with other fire
retardants are reviewed. It is hoped that this review will not only introduce the synthesis, characterisation
and application of polymer–LDH nanocomposites for flame retardancy, but also prompt new discussion
on the use of LDH dispersions in polymer-based materials.

1. Introduction
Due to the rapid development in polymer chemistry, polymer-
based materials are now recognised as key components in many
important industries such as construction, automotive, elec-
tronic and aerospace due to their outstanding physical and
electronic properties, cost-effectiveness, high versatility, and
portability. However, one severe problem with many polymers is
a
College of Environmental Science and Engineering, Beijing Forestry University, 35
Qinghua East Road, Haidian District, Beijing 100083, P. R. China. E-mail: qiang.
wang.ox@gmail.com; qiangwang@bjfu.edu.cn; Tel: +86 13699130626
b
Department of Chemistry and Fire Retardant Research Facility, Marquette University,
P.O. Box 1881, Milwaukee, Wisconsin 53201, USA
c
Chemistry Research Laboratory, Department of Chemistry, University of Oxford,
Manseld Road, Oxford, OX1 3TA, UK. E-mail: dermot.ohare@chem.ox.ac.uk; Tel:
+44 1865 272686
that they are highly ammable and can produce large amounts
of toxic smoke during combustion, which poses a great threat to
human safety and signicantly restricts their applications in
many areas.1,2 In order to tackle this problem, effective methods
are needed to add compatible nano-sized ame retardant llers
into polymer matrices.
Halogen-based ame retardants have been the most widely
used because they have high re retardant efficiency and low
cost, and require only a low loading.3,4 However, these ame
retardants have some critical disadvantages. For example, the
burning of these compounds will produce smoke and bromi-
nated dioxins, which may threaten human health.5 Thus the use
of halogen-containing ame retardants has been gradually
reduced or even banned in some jurisdictions.6–8 Organic
phosphorus compounds are particularly effective additives in
oxygen or nitrogen containing polymers. But the main

Yanshan Gao is currently a PhD Jingwen Wu, is now a fourth-

candidate in the College of year undergraduate student in
Environmental Science and the College of Environmental
Engineering, Beijing Forestry Science and Engineering, Beijing
University in China. She Forestry University in China.
received her Bachelor degree in She is currently focusing on the
Beijing Forestry University as phosphate-intercalated layered
well. She is currently focusing on double hydroxides (LDHs) for
the application of layered ame retardant polymer–LDH
double hydroxides (LDHs) in nanocomposites.
environmental areas, such as
ame retardant polymer–LDH
nanocomposites, and NOx
storage and reduction (NSR)
catalysts, etc.

This journal is © The Royal Society of Chemistry 2014 J. Mater. Chem. A


Journal of Materials Chemistry A
disadvantage of phosphorus ame retardants is that the pres-
ence of phosphates in polymers causes plasticisation, which
leads to a decrease of mechanical properties of the polymers.
Melamine (1,3,5-triazine-2,4,6-triamine) and related
compounds have also been used as re retardants because they
have fairly high thermal stability and can promote non-aming
dripping during combustion, but the formation of non-aming
drips is not a common mechanism for re retardancy and this
may have limited applicability.9–11 Metal hydroxides are the
largest commercially manufactured ame retardants and have
been widely used in wire and cable insulation products,
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synthetic marble and onyx, latex for carpet back-coatings,
phenolic and epoxy (EP) resins, and unsaturated polyesters
(UP).12 The endothermic decomposition process of magnesium
hydroxide (MH) and aluminum hydroxide (ATH) can decrease
the temperature of the burning material and release water into
the gas phase to dilute the ame.8,13–15 In addition, the presence
of anhydrous alumina can help acid-catalysed dehydration of
Professor Qiang Wang received
BSc (2003) and MSc (2005) from
Harbin Institute of Technology in
China, and PhD (2009) from
POSTECH in South Korea. In
2009–2011, he worked as
Research Fellow in the Institute
of Chemical and Engineering
Sciences under A*STAR, Singa-
pore. In 2011–2012, he worked as
postdoctoral associate in the
Department of Chemistry,
University of Oxford. From 2012,
he holds a full professor position in the College of Environmental
Science and Engineering, Beijing Forestry University. His research
interests are heterogeneous catalysis and materials chemistry. He
was awarded China 1000 talents plan for young scholars in 2013.
Charles A. Wilkie is currently
Professor Emeritus at Marquette
University. He received the B.S.
degree from the University of
Detroit and the PhD in inorganic
chemistry from Wayne State
University, then joined Mar-
quette University. He has been
assistant professor, associate
professor, professor and retired
as the Habberman-Pett-
schinger Professor in 2009. He
has worked in re retardancy for
more than 35 years.
J. Mater. Chem. A
View Article Online
Application
some polymers and consequently enhance char formation.
Since both anhydrous alumina (Al2O3) and magnesia (MgO) are
white and highly refractory powders, they provide heat insu-
lation by reecting heat when they accumulate on a surface.16
The main disadvantage of MH and ATH is their low ame
retardant efficiency which requires high loadings combined
with their inherent poor compatibility with hydrocarbon-based
polymers. As a result addition of large amounts of either MH or
ATH leads to severe deterioration of the mechanical properties
of polymers.17
Layered double hydroxides (LDHs) are a class of anion-
exchangeable lamellar compounds made up of positively
charged brucite-like layers with an interlayer region containing
charge compensating anions and solvation molecules. Owing to
their exible, tunable chemical composition and high anion-
exchange capacity, LDHs have found many potential applica-
tions, including in pharmaceuticals, adsorbents, catalysis, and
inorganic llers.18,19 In addition, LDHs are emerging as a new
generation of ame retardant materials, which can offer good
ame retardancy and smoke suppression properties due to their
unique chemical composition and layered structure. These are
potentially eco-friendly ame retardants for polymer applica-
tions. Besides, by properly intercalating certain anions, such as
borate into LDHs, LDHs might combine the advantages of both
MH, ATH and zinc borate (xZnO$yB2O3$zH2O; known in the
trade as Firebrake™).
In the past few years, there has been a rapid growth in
publications related to the synthesis and application of new
ame retardant polymer–LDH nanocomposites. In order to
promote continued developments in this eld we have
composed a critical review of the most recent progress. Matu-
sinovic et al.20 wrote an excellent review on re retardancy and
morphology of layered double hydroxide nanocomposites.
However, this review was focused mainly on the dispersion of
the LDHs within the polymer matrix and how the dispersion
affects the re retardant properties of the polymer–LDH nano-
composites. Feng et al.13 have briey reviewed the work on LDHs
Professor Dermot O'Hare
received both his M.Chem and
D.Phil from Oxford University.
He was elected to a Tutorial
Fellowship at Balliol College
and a University Lectureship in
Chemistry at Oxford in 1988. He
was the RSC Sir Edward Frank-
land Fellow in 1996/97. In 1996
the Institüt de France named
him as one of the top 50 leading
scientists in Europe. He was
been awarded the Exxon Euro-
pean Chemical and Engineering Prize and 1998 he was awarded
the RSC Corday Morgan Medal and Prize. In 2009 the University of
Oxford Teaching Excellence award and in 2010 the RSC Ludwig
Mond prize.
This journal is © The Royal Society of Chemistry 2014

Application
as ame retardant and thermal stabilisers for polymers. Given
the rapid progress in this eld, their discussions on ame
retardancy now needs updating. Here we summarise the tech-
niques and indices for evaluating ame retardant properties,
the ame retardant mechanism of LDHs, the types of polymers
that have been studied, and the effects of varying the LDH
chemical composition on performance. We also comment on
the effects of adding additional compatibilisers, and the
synergistic effect of LDHs with other re retardants.
2. Techniques and indices for
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determining flame retardancy
performance
In order to measure the ame retardancy of a polymer,
different standards and indices need to be considered. To
date, four approaches are commonly used to evaluate the re
properties of a polymer–LDH nanocomposites; microcalo-
rimetry (MCC), limiting oxygen index (LOI), cone calorimeter
(CONE) and UL-94.
2.1 MCC
MCC also known as pyrolysis combustion ow calorimetry
(PCFC), is a convenient and fast method for laboratory evalua-
tion of the ame properties; it is based on a TGA-like degrada-
tion of the polymer in nitrogen, followed by combustion of the
gases produced in air. Test standard committees of ISO and
ASTM have also been formed to establish a standard test
method for MCC.21,22 The parameters include the heat release
rate (HRR), heat release capacity (HRC) and temperature of
degradation. Moreover, this measurement only requires small
amounts of material so it can be used on developmental
materials. The disadvantage is that there is not a large database
of materials that have been evaluated by this and any effects due
to physical changes or ame quenching are not observed.
2.2 LOI
LOI is widely used to evaluate the ame retardant properties of
materials.23 The fraction of oxygen in a nitrogen–oxygen mixture
required to support combustion is measured. The higher the
number, the more difficult it is for combustion to occur. It has
been formalized in the USA as ASTM D2863, the latest version
being D2863-87.24 However, the LOI value is merely expressed as
a number indicating the percentage of oxygen required for self-
sustained combustion of any materials, but does not give any
useful information about the burning behaviour.25 Small
changes in the LOI are not meaningful; if the LOI increases
from 20 to 24, this likely has no effect on the actual burning
characteristics of the polymer.
2.3 CONE
CONE is able to provide useful information about the
combustion of the polymers and is the most effective method
for the laboratory evaluation of the ame retardant properties of
polymers.26 The technique measures the HRR and peak heat
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Journal of Materials Chemistry A
release rate (PHRR); these are considered the most signicant
parameters. A highly ame-retardant system normally shows a
low PHRR value. Total heat released (THR) is another important
parameter, which represent the sum of heat released until the
ame is extinguished. Besides, average specic extinction area
(ASEA), a measure of smoke, average mass loss rate (AMLR) and
the time to ignition (tig, also known as TTI) are also essential
parameters.27
2.4 UL-94
UL-94 (Underwriters Laboratories) as a plastics ammability
standard it is one most widely used performance standards
for a plastic material. It is used to evaluate the extinguishing
ability of a material aer it is ignited. UL-94 testing is carried
out following two standards: one is the vertical burn test
(UL-94 V) and the other is the horizontal burn test (UL-94 HB).
UL-94 V gives useful information regarding the dripping
behavior of the nanocomposites. The dripping of the burning
melt directly inuences the spread of ame through
secondary aming during real life burning situations.28 This
standard is divided into ve parts: HB, V-2, V-1, V-0 and 5 V
with the increasing ame retardancy of plastic materials. A
good re retardant material should reach the UL-94 V-0 rating
and have no dripping during the test. This is primarily an
evaluation that is used to qualify a product. But the UL-94 test
is very dependent on operators and which version of the
standard is used, so different labs maybe obtain different
results.
While there are several evaluative measures that are used,
all of them measure something different and thus none of
them capture all of the elements of a re. Results from one
procedure cannot be used to predict performance in another
evaluation.
3. The mechanism of flame
retardancy using LDH
LDHs, commonly also called anionic clays, are a class of anionic
lamellar compounds made up of positively charged brucite-like
layers with an interlayer region containing charge compen-
sating anions and molecules of solvation.18 Most LDHs have a
general molecular formula of [M1
x2+Mx3+(OH)2]x+An
x/n$zH2O,
where M2+ and M3+ are divalent and trivalent metal cations,
such as Mg2+, Al3+, respectively, and An
is an intercalated
inorganic or organic anion, such as CO32
, NO3
, and SO42
,
RCO2
, and x is normally between 0.2–0.4.29–35 Occasionally a
monovalent or tetravalent cation may be substituted for the
divalent or trivalent ions respectively, such as Li+ or Ti4+.36 Fig. 1
shows a schematic representation of the hydrotalcite structure.
Due to the layered structure and high anion exchange capacity,
LDHs have a wide range of applications in many elds, for
example, as catalysts or catalyst precursors,37,38 absorbents,
anion exchangers,39 thermal stabilisers, drug delivery hosts,40
cement additives,41 hosts for nanoscale reactions and media for
gas absorption.42,43
J. Mater. Chem. A
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Fig. 1 Schematic structure of an LDH.

The origin of the excellent ame retardancy and smoke

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suppression properties of LDHs is derived from their unique

chemical composition and layered structure. Just like cationic
clays, LDHs can be modied by intercalating organic anions
into the interlamella galleries. These organic-modied LDHs
can be used as nanollers for the synthesis of polymer–LDH
nanocomposites.3,44 Radical trapping and a barrier mecha-
nism are the most widely accepted mechanisms for ame Fig. 2 Schematic of a possible mechanism for char formation using an
retardancy for silicate clay containing nanocomposites. LDH.53 Reproduced with permission from ref. 53. Copyright © 2008,
Elsevier.
Although no mechanism has been proposed for the ame
retardant mechanism of LDH nanocomposites,45–47 it is
generally believed that the ame retardant mechanism of
producing bridges between APP chains. The formation of a
LDHs is different from that of silicate clay-based nano-
small number of such bridges will induce a stabilization of
composites.48 During thermal decomposition, LDHs will lose
APP and a decrease in the volatility of phosphorus, and thus
the interlayer H2O, decomposition of the intercalated anions
more APP will be available for phosphorylation and char
(e.g. CO32
) and the metal hydroxide network will produce H2O
formation. The crosslinks will, in effect, increase the degree of
and other gases e.g. CO2. The effects for these processes will
polymerization of poly(phosphoric acid), which will then
reduce fuel available for combustion, which will lower heat
increase the viscosity of the melt during pyrolysis and
release and eventually stop the combustion when there is not
combustion, and therefore enhance the formation of compact
enough fuel to propagate the reaction, and promote the
and dense charred layer. Another scheme is that during the
formation of an expanded carbonaceous coating or char. Char
combustion process PVA chains will dehydrogenate,
formation protects the bulk polymer from exposure to air thus
producing double bonds on the backbone, and LDHs could
reducing the heat release during the combustion and sup-
function as a catalyst for the cyclization reaction to produce a
pressing smoke production.49,50 In summary, the ame retar-
precursor of char.
dant mechanism of LDHs can be attributed to the
As nanollers, LDH can not only improve ame retardant
combination of the following three functions: (1) heat
and smoke suppression, but also increase the mechanical and
absorption, (2) gas dilution, and (3) char formation. Conse-
rheological properties, gas permeation properties, photo-
quently, the mass loss rate will be signicantly reduced due to
stability and IR absorption properties of polymer–LDH nano-
the combination of the above mentioned three functions. For
composites.54–58 In addition, the chemical composition of LDHs
instance, Camino et al.51 used a MgAl LDH as a ame retardant
can be precisely controlled which enables purity levels to be
for ethylene vinyl acetate (EVA) and observed good ame-
determined and biocompatibility established by eliminating
resistant performance. During the thermal decomposition of
any toxic elements. As a result, LDHs are increasingly regarded
the LDH, three clear endothermic events at 207  C, 291  C, and
as a promising new type of green ame retardant for polymer
416  C are observed, which can be attributed to the loss of
applications.
interlayer water, the decomposition of interlayer CO32
, and
the decomposition of hydroxyl groups of the pristine LDH
layers, respectively. Furthermore, MgO and MgAl2O4 were 4. Polymers used in fire-retardant
formed at 500  C and 850  C respectively, which are benecial polymer–LDH nanocomposites
to the formation of char. This residue would slow subsequent
burning by reducing the oxygen supply to the bulk phase Polymers such as polypropylene (PP), polystyrene (PS), poly-
under the burning surface.52 Zhao et al.53 studied the oxidized ethylene (PE), EVA, poly(methyl methacrylate) (PMMA),
residue of poly(vinyl alcohol)/ammonium polyphosphate poly(vinyl chloride) (PVC), acrylonitrile–butadiene–styrene
{NH4PO3}n/LDH {PVA/APP/LDH} nanocomposites and (ABS), UP, EP, poly(lactic acid) (PLA), ethylene–propylene–
concluded that LDH can promote char formation. The mech- diene terpolymer (EPDM) and polyamide 6 (PA 6) have been
anism for the promotion of char formation of LDH is proposed extensively studied across a broad range of applications.
in Fig. 2. One scheme is that the LDH layers may react with However, most of these are quite ammable materials and
poly(phosphoric acid), releasing water molecules and can emit a large amount of smoke on burning. LDHs have

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Table 1 Summary of the polymers that have used as components in Table 1 (Contd. )
flame retardant polymer–LDH nanocomposites
Polymer LDHs PHRR reductiona Ref.
Polymer LDHs PHRR reductiona Ref.
MgAl–oleate 48% (10 wt%)
PP MgAl MgAl–LDH: 4% (10 wt%) 59 CuAl– 0% (6 wt%) 73 and
OMgAl–LDH: 21% (10 wt undecenoate 109
%) CoAl– 7% (6 wt%)
CoAl–DBS 29.6% (6 wt% with 6% PP- 62 undecenoate
g-MA) ZnAl– 16% (6 wt%)
ZnAl–borate 63.7% (15 wt%) 90 undecenoate
PS MgAl–Cn MgAl–C10: 56% (10 wt%) 48 MgAl– 24% (6 wt%)
MgAl–C11: 36% (10 wt%) undecenoate
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MgAl–C12: 52% (10 wt%) CaAl– 36% (6 wt%)

MgAl–C14: 47% (10 wt%) undecenoate
MgAl–C16: 34% (10 wt%) NiAl– 36% (6 wt%)
MgAl–C18: 19% (10 wt%) undecenoate
MgAl–C22: 21% (10 wt%) ZnAl– 46% (10 wt%)
ZnAl– 35% (5 wt%) 67 undecenoate
undecenoate NiAl2– 16% (10 wt%) 33
CaAl–B 42% (10 wt%, bulk 20 undecenoate
polymerization); 24% (10 ZnAl2– 26% (10 wt%)
wt%, melt blending) undecenoate
MgAl–CO3 LOI: from 18 to 28 (80 wt%) 74 CoAl2– 41% (10 wt%)
PE ZnAl–SA 55% (5 wt%) 67 undecenoate
ZnAl–oleate 58% (10 wt%); 72% (20 wt 63 and Ca3Fe– 34% (10 wt%) 3
%) 94 undecenoate
MgAl–oleate 29% (10 wt%) 63 Ca3Al– 54% (10 wt%)
MgAl–DS 14.5% (5 wt% with 5 wt% 66 undecenoate
LDPE-g-MA) PVC MgAl LOI: from 28 to 28.7 74 and
MgAl–NO3 5% (5 wt% with 5 wt% (30 wt%) 111
LDPE-g-MA) ABS MgAl LOI: from 19 to 27; from 74 and
MgAl–SA 27% (5 wt% with 5 wt% 17.8 to 27.5 (60 wt%) 75
LDPE-g-MA) ZnMgAl LOI: fron 17.8 to 28.3 75
MgAl–DBS LOI: from 18 to 22 (20 wt%) 28 (60 wt%)
EVA MgAl–CO3 66.4% (60 wt%) 68, 70, UP MgAl MgAl–A: 46.9% (1 wt%) 77
LOI: from 18 to 40 (60 wt%) 92, MgAl–S: 32.5% (5 wt%)
LOI: from 21.4 to 34.1 105 EP MgAl NA 49, 52
LOI: from 21.3 to 30 (60 wt and NiFe 46.5% (2 wt%) and 79
%) 110 PLA NiFe–DS LOI: from 20 to 29 80
66.4% (50 wt%) NiAl–DS (2 wt% with 8 wt% HPCP)
91.8% (60 wt%) NiCr–DS
MgAl–borate LOI: From 21.3 to 29.2 (60 70 EPDM MgAl–DBS 25.2% (40 wt%) 81
wt%) 55.2% (2 wt% with
MgAl–PO4 76% (60 wt%) 68 38 wt% FR)
MgAl–PAHPA 42.7% (5 wt%) 72 Nylon6 MgAl–(H-DS) 37.6% (5 wt%) 92
MgAl–ASA 39% (3 wt%) 67 54.4% (10 wt%)
ZnAl–oleate 33% (10 wt%) 71 68.3% (20 wt%)
MgAl–oleate 36% (10 wt%) a
ZnMgAl–CO3 LOI: from 21.4 to 40.2 70 The weight percent values in the bracket represent the LDH loadings.
MgAlFe–CO3 28.4% compared to MgAl– 88 PP: polypropylene, PS: polystyrene, PE: polyethylene, EVA: ethylene vinyl
acetate, PMMA: polymethyl methacrylate, PVC: polyvinyl chloride, ABS:
CO3 (50 wt%)
acrylonitrile–butadiene–styrene, UP: unsaturated polyesters, EP: epoxy,
MgAl–borate 74% (40 wt%) 69 PLA: poly(lactic acid), EPDM: ethylene–propylene–diene terpolymer.
ZnAl–borate 77% (40 wt%)
PMMA MgAl–Cn MgAl–C10: 56% (10 wt%) 48
MgAl–C11: 36% (10 wt%)
MgAl–C12: 52% (10 wt%)
MgAl–C14: 47% (10 wt%) been investigated as ame retardants to reduce the amma-
MgAl–C16: 34% (10 wt%) bility of these polymers; a summary of all the ame retardant
MgAl–C18: 19% (10 wt%)
polymer–LDHs nanocomposites reported in the literature is
MgAl–C22: 21% (10 wt%)
MgAl–DPHPA 35.1% (5 wt%) 100 presented in Table 1.
MgAl–DBS 46% (10 wt%) 11
MgAl–NO3 20% (10 wt%) 47 4.1 PP
MgAl–CO3 30% (10 wt%)
MgAl–C16 51% (10 wt%) PP is a widely used polymer in the preparation of nano-
ZnAl–oleate 28% (10 wt%) 63 composites. It is preferred to other polymers due to its wide
availability, high stability, and relatively low cost.59–61 In order to

This journal is © The Royal Society of Chemistry 2014 J. Mater. Chem. A


Journal of Materials Chemistry A
improve its ame retardancy, various LDHs including MgAl–
potassium lauryl alcohol phosphoric acid monoester (MAPK),
CoAl–dodecyl benzene sulfonate (DBS), Zn2
yMgyAl–oleate,
ZnAl–dodecyl sulfate (DS), MgAl–DS, CaAl–DS, CuAl–DS, NiAl–
DS have been added to PP matrix. For example, Wang et al.59
synthesised MgAl–MAPK LDH as ame retardant for PP and
found that the PHRR could be reduced by around 21% with 10
wt% LDH loading. In addition, the PHRR can be signicantly
decreased by 63% by adding 10 wt% of MgAl–MAPK LDH and 10
wt% of zinc borate as a synergist. A similar result was observed
with CoAl LDH intercalated with DBS. The PHRR of PP was
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reduced by around 30% at 6 wt% LDH loading.62 Manzi-Nshuti
et al.63 added oleate intercalated Zn2
yMgyAl LDHs with varying
Zn–Mg ratios into PP, and found that the optimal LDH is
Zn0.5Mg1.5Al, with which the PHRR can be reduced by 38% at 4
wt% LDH loading. With the addition of a polypropylene-gra-
maleic anhydride (PP-g-MA) compatibiliser to improve the ller
dispersion, the PP/PP-g-MA (1 : 1) 4 wt% LDH resulted in a
signicantly larger reduction in the PHRR (up to 68%). Zhang
et al.64 systematically investigated the inuence of DS interca-
lated ZnAl, MgAl, CaAl, and CuAl LDHs on intumescent ame
retardant (IFR) PP/LDH nanocomposites. They found that the
PP/IFR/ZnAl–LDH nanocomposite showed a signicant PHRR
reduction – around 75%. The LOI value reached 33 and
obtained the UL-94 V-0 rating. To date, all the LDHs studied in
the PP system are organically-modied LDHs. The major reason
for this is that PP is a nonpolar macromolecule and so has
intrinsically poor compatibility with the hydrophobic interca-
lated LDHs. The data also suggest that LDHs alone are not
sufficient and generally require another material to deliver the
required ame retardant performance.
4.2 PE
PE is another important nonpolar polymer and is used in
many applications such as packaging materials, thin lms
and bottles. For PE, most of the LDHs studied in literature are
MgAl and ZnAl based. For instance, MgAl LDHs intercalated
with various anions such as NO3
, DS, stearate anion (SA),
and DBS have been investigated.28,65,66 With 5 wt% MgAl–NO3
LDH loading, the PHRR reduction was only 5%. However,
aer modifying with the DS or SA anions, the PHRR reduction
was increased to 15% and 27%, respectively.66 Furthermore,
intercalating the same oleate anion, the ame retardant
performance of ZnAl and MgAl LDHs were comparatively
studied. The result indicated that ZnAl LDH had a better
ame retardant effect than MgAl LDH in PE system. With 10
wt% LDH loading, the PHRR reduction with ZnAl LDH was
58%, much higher than that of MgAl LDH (29%).63 On the
other hand, MgAl LDH was more effective in PMMA than ZnAl
LDH. The char with ZnAl LDH is denser than that with MgAl
LDH. In addition, ZnAl LDH with SA showed better dispersion
at the nanometer level and the PHRR reduction reached
55%.67 Therefore, it may be concluded that ZnAl LDHs are
preferred for the PE system and the organic modication of
LDHs can generally lead to a better ame retardant
performance.
J. Mater. Chem. A
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4.3 EVA
EVA over 20 papers have been published describing the ame
retardant properties of EVA/LDH nanocomposites. A range of
various LDHs including MgAl–CO3, ZnMgAl–CO3, MgAlFe–CO3,
MgAl–borate, ZnAl–borate, MgAl–PO4, MgAl–oleate, ZnAl–
oleate, MgAl–N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-yla-
mino)-hexyl)acetamide-2-propyl acid (MgAl-PAHPA), MgAl–2-
aminotoluene-5-sulfonic acid (ASA) have been studied. More
inorganic LDHs have been used in the EVA system than with PP
or PE. Since EVA contains polar groups the overall effect will be
to exhibit better compatibility with LDHs. Ye et al.68 prepared
MgAl–CO3 and MgAl–PO4 LDHs and compared their ame
retardant properties in EVA. With 60 wt% LDH loading, the
PHRR reduction for MgAl–CO3 and MgAl–PO4 LDHs was 66%
and 76%, respectively, suggesting that MgAl–PO4 possesses
better ame retardant performance than MgAl–CO3. The inu-
ence of divalent cations of Mg and Zn has also been investigated
in the EVA system. Nyambo et al.69 introduced MgAl–borate and
ZnAl–borate LDHs into EVA and observed signicant PHRR
reductions for both LDHs. When the LDH loading was 3 wt%,
the PHRR reduction for MgAl–borate and ZnAl–borate LDHs
was 42% and 36%, respectively. The PHRR reduction increased
with an increase in the LDH loadings. When the LDH loading
was 40 wt%, the PHRR reductions for MgAl–borate and ZnAl–
borate LDHs reached 74% and 77%, respectively. ZnMgAl–CO3
LDH was also investigated,70 the results showed that ZnMgAl–
CO3 LDH had a better ame retarding effect than MgAl–CO3.
The LOI value of ZnMgAl–CO3 and MgAl–CO3 LDHs was 34 and
40, respectively. Organic modied MgAl LDHs, such as those
containing PAHPA, oleate, or ASAall reveal good ame retardant
properties, where the PHRR reduction was 43% (5 wt% loading),
36% (10 wt% loading), and 39% (3 wt% loading), respec-
tively.67,71,72 So we can infer that ZnAl, MgAl and ZnMgAl LDHs
are all promising ame retardant additives for EVA.
4.4 PMMA
PMMA has been a widely used polymer mainly due to its
excellent optical, mechanical, thermal, and electric properties.
However, it is also highly combustible so ame retardation is
needed for many applications.11 For PMMA, various LDHs,
including MgAl–alkyl carboxylates, MgAl–DBS, MgAl–oleate,
ZnAl–oleate, MgAl–N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-yl-
amino)-N-hexyl)formamide-2-propenyl acid (MgAl-DPHPA),
MgAl–CH3(CH2)NCOO
, MgAl–undecenoate, ZnAl–undecenoate,
CuAl–undecenoate, CaAl–undecenoate, CoAl–undecenoate, NiAl–
undecenoate, and CaFe–undecenoate, MgAl–PO4, MgAl–NO3,
and MgAl–CO3, have been investigated. Among the LDHs
studied, most are intercalated with organic anions containing
long hydrocarbon chains. Nyambo et al.47 investigated the effect
of organic modication of LDHs on the combustion properties of
LDH–PMMA composites. The combustion was studied by cone
calorimetry and showed that the PHRR was signicantly reduced
(51%) in the composites consisting of an organically modied
MgAl LDH, while it was reduced by only about 30% in unmodi-
ed MgAl–CO3, MgAl–NO3, and calcined LDH composites.
Improved physical interaction and good nano-dispersion may be
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Fig. 3 (a) PHRR values for PMMA/MgAl–Cn LDHs nanocomposites,
and (b) HRR curves for PMMA/MgAl–C18 LDH nanocomposite at 50 kW
m
2.48 Adapted from ref. 48.
the reason for the observed enhanced thermal and combustion
properties. Nyambo et al.48 evaluated the long-chain linear alkyl
carboxylates (CH3(CH2)nCOO
, n ¼ 8, 10, 12, 14, 16 and 20)
intercalated MgAl LDHs as ame retardant llers for PMMA.
With 10 wt% LDH loading, the PHRR was reduced by 49–58% for
all the nanocomposites, as shown in Fig. 3. They found that the
PHRR reduction increased with the increase in the LDH loadings.
A similar result was observed for MgAl–DBS LDH, were the PHRR
was reduced by 46% at 10 wt% LDH loading.11 In order to
compare the role of the divalent metals on re properties of
PMMA, a qualitative difference in ame retardant properties of
undecenoate intercalated ZnAl, MgAl, CoAl, NiAl, CuAl, and CaAl
LDHs was observed.33,48,73 At 6 wt% LDH loading, the reduction in
PHRR follows the order: CaAl (36%) ¼ NiAl (36%) > MgAl (24%) >
ZnAl (16%) > CoAl (7%) > CuAl (0%). The role of trivalent cations
including Al and Fe was also studied by Manzi-Nshuti et al.3 Both
Ca3Fe and Ca3Al LDHs give promising ame retardant perfor-
mance, resulting in PHRR reductions of 54% and 34% for Ca3Al
and Ca3Fe LDH at 10 wt% loading respectively. Therefore, in
PMMA it can be concluded that both the divalent and trivalent
metals within the LDH inuence combustion, and organic
modication is important to achieve highly efficient ame
retardancy.
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4.5 PS
The effects of ZnAl, MgAl, and CaAl LDHs on PS have been
reported. Zhang et al.74 evaluated the ame retardant perfor-
mance of PS on addition of MgAl–CO3, the results showed that
the LOI value was increased from 19 to 27 at 50 wt% LDH
loading, with much less smoke produced compared to pure PS.
Costache et al.67 prepared PS/ZnAl–undecenoate LDH nano-
composites and observed a PHRR reduction of 35% at 5 wt%
LDH loading. PS/CaAl–benzoate LDH nanocomposites prepared
by in situ bulk polymerization and melt-blending also showed
good ame retardancy, with a PHRR reduction of 42% and 24%
respectively at 10 wt% LDH loading.27 Nyambo et al.48 interca-
lated alkyl carboxylate into MgAl LDH and synthesized PS/
MgAl–Cn (n ¼ 12, 14, 16, 18, 22) LDH nanocomposites. The best
PHRR reduction (56%) was observed with MgAl–C10 at 10 wt%
loading, followed by MgAl–C12 (52%).
4.6 ABS
ABS resin is a thermoplastic polymer that has a wide variety of
industrial applications; however it suffers from ammability
and can generate a large amount of smoke and toxic gases on
combustion. MgAl and ZnMgAl LDHs have been introduced
into ABS as ame retardants, resulting in a signicant reduction
in PHRR. In addition, ZnMgAl LDHs provided a higher LOI
value and a longer combustion time, indicating that ZnMgAl
LDHs have a better ame retardant efficiency in ABS.75 Apart
from the polymers discussed above, many other polymers such
as PVC,74,76 UP,77 EP,49,52,78,79 PLA,80 EPDM,81 and poly(butyl
acrylate-vinyl acetate) (P(BA-VAc))82 also have been studied with
different LDHs, and all showed enhanced ame retardant
properties.
5. The effect of the LDH on
nanocomposite performance
5.1 The effect of divalent cations in the metal hydroxide
layers
Fire retardant properties of polymer–LDH composites can be
mainly assigned to the thermal degradation of LDHs and the
formation of a ceramic-like material, both of which depend on
the characteristics and stoichiometry of the metal cations, the
interlayer anions, the LDH particle size, and the extend of the
dispersion of LDHs in the polymer matrix. So the proper
selection of metal cations in LDH is an important factor to
enhance the re retardancy of polymers. The metal cations in
LDHs can signicantly inuence the dispersion of LDHs in the
polymers, the morphology and the char information of the
polymer–LDH composites. The rst LDH to be used as a ame
retardant was a MgAl LDH; the LDH was a component in a ame
retardant composite (synthetic hydrotalcite 60 wt%, (dibutyl)
tin-maleate 4 wt% and butyl stearate 2 wt%) was added to a vinyl
chloride resin. The result was a signicantly increased oxygen
index from 48.4 to 63.13 To date, a wide range of aluminum-
containing LDHs with different divalent cations and organic
modiers have been synthesised in order to improve the re
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Fig. 4 HRR curves of PMMA–LDH nanocomposites with 5 wt% and 10
wt% of NiAl, ZnAl, and CoAl LDHs at 50 kW m
2.33 Reproduced from
ref. 33.
retardancy and thermal stability of polymers. Those various
divalent cations include Mg, Zn, Ni, Co, Cu, and Ca.
In order to clarify the effect of divalent cations on the ame
retardant performance of LDHs, several systematical studies
have been carried out by xing the trivalent cations and inter-
layer anions. For example, Manzi-Nshuti et al.33 synthesised
M1
x2+Alx–CH2]CH(CH2)8COO
LDH with M2+ ¼ Co, Ni, and
Zn, and compared their ame retardant properties in the PMMA
system. Fig. 4 compares NiAl, ZnAl, and CoAl LDHs at 5 wt%
and 10 wt% loadings in PMMA. At 5 wt% LDH loading, PMMA–
ZnAl2 and PMMA–CoAl2 shows small reductions in PHRR while
no reduction is noted for the PMMA–NiAl2 system. At 10 wt%
LDH loading though, a larger reduction is observed for the
PMMA–CoAl2, followed by the PMMA–ZnAl2 system. The best
reduction in PHRR (41%) is found with the CoAl2 LDH, while
addition of ZnAl2 and NiAl2 LDHs resulted in a PHRR reduction
of 26% and 16%, respectively. In a more comprehensive study,
Manzi-Nshuti et al.73 compared the ame retardant efficiency of
MgAl, CaAl, CoAl, NiAl, CuAl, and ZnAl LDHs with CO32
as the
interlayer anion in PMMA. At 6 wt% LDH loading, the CaAl and
NiAl LDHs gave the largest PHRR reduction (36%), followed by
MgAl (24%), ZnAl (16%), and CuAl (0%). The high efficiency of
NiAl and CaAl LDHs is attributed to a benecial polymer–LDH
agglomerate interaction. Zhang et al.64 performed a similar
study with ZnAl, MgAl, CaAl, and CuAl LDHs with DS as the
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interlayer anion in an intumescent ame retardant PP system.
In the cone calorimetric analysis, the PHRR reduction follows
the order of Zn > Mg > Ca > Cu. However, the LOI and UL-94
analyses gave a different order, which is Zn ¼ Cu > Mg > Ca.
Since each evaluation measures a different ame retardant
property, LOI is ease of ignition, UL 94 is ease of extinction,
cone is heat release, it is not surprising that the various evalu-
ations show different results.
Moreover, previous studies have demonstrated that Zn-con-
taining materials can promote material charring and smoke
suppression.83 Shi et al.70 introduced Zn2+ into the MgAl–CO3
LDHs in order to improve the ame retardancy and smoke
suppressing properties of EVA-28/LDH composites. Manzi-
Nshuti et al.84 introduced it to PP/MgAl–CO3 LDH and Xu et al.75
introduced it to ABS/MgAl–CO3. For the EVA-28 composites, the
LOI values are; EVA-28/ZnMgAl–CO3 (40.2) > EVA-28/MgAl–CO3
(34.1) > EVA-28 (21.4). Compared with pure EVA-28, the decrease
in the smoke density (Dm) of the composites was 59.1% and
34.9% for EVA-28/ZnMgAl–CO3 and EVA-28/MgAl–CO3 respec-
tively, indicating a very effective smoke suppression effects on
EVA-28. In PP composites, the 4 wt% loading of ZnMgAl–CO3
LDH additive performs better than the two-metal LDHs, but
reduction in the PHRR was lower than previously reported for
PP/MMT composites.85,86 The author suggested predispersing
these llers in similar polymers that are functionalised with
polar groups (such as PP-g-MA, polyethylene-gra-maleic anhy-
dride (PE-g-MA) and PE-random-vinyl acetate (PE-r-VA),
etc.).46,84,87 In terms of ABS composites, there was a signicant
increase in the LOI value of the composites from 17.8 (pure ABS)
to 27.5 and 28.3 for the ABS/MgAl–CO3 and ABS/ZnMgAl–CO3
LDH nanocomposites, respectively. In addition, a 38% and 27%
decrease in the smoke density was observed for the ABS/
ZnMgAl–CO3 LDH and ABS/MgAl–CO3 LDH nanocomposites
compared with pure ABS.
Currently, there is no clear mechanistic understanding of
how the divalent cations in LDHs affect their ame retardant
performance. The data available in the literature is not suffi-
ciently comprehensive to make any convincing conclusions
regarding which LDH is optimal for a specic polymer. It is
generally believed that the performance enhancement must be
a complex interplay of a number of factors that include the
thermal stability of the LDH, the LDH particle size, the extent of
the dispersion of the LDH throughout the polymer matrix, and
interaction of the LDH surface with the polymer chains.
Apparently, a zinc-containing LDH is more effective in non-
polar polymers while a magnesium-containing LDH is more
effective in more polar polymers. One may speculate that the
hard, acidic Mg2+ cations may interact more strongly with the
hard, basic oxide functional groups so that magnesium is
preferred in polar polymers. A useful area of future investiga-
tion is the role of the divalent cation.
In the above mentioned studies, LDHs containing different
intercalated anions such as CH2]CH(CH2)8COO
, CO32
, and
DS were evaluated in polymer such as PMMA, EVA, and PP. As
will be discussed in the following section, the nature of the
interlayer anions also has an inuence on the ame retardancy,
this is probably due to inuencing the interactions between
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LDHs and polymers. Thus, in order to have a clearer under-
standing of the effect of divalent cations in different polymer
system, we suggest xing the interlayer anions (either inorganic
or organic) while varying the divalent cations and polymers.
What's more, the size and shape of LDHs should also be
considered. In addition to selecting the optimal divalent cations
for certain polymers, it may be promising to explore the use of
two or more divalent metals an LDH in order to further improve
the ame retardant and smoke suppression efficiencies.
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5.2 The effect of trivalent cations in the metal hydroxide
layers
In order to study the effect of trivalent cations on the
morphology and the combustion properties of polymer–LDH
composites, Manzi-Nshuti et al.3 synthesised Ca3Al–undece-
noate LDH and Ca3Fe–undecenoate LDH containing PMMA–
LDH composites. Increasing the LDH loading from 1 to 10 wt%
resulted in an increase in the ame retardancy of the compos-
ites. At 5 wt% LDH loading, the TEM images of PMMA–Ca3Fe
LDH composites showed poor dispersion of this LDH within the
polymer matrix; while PMMA–Ca3Al LDH showed a better
dispersion with a mixed intercalated-exfoliated morphology
(Fig. 5). At 10 wt% LDH loading, the PMMA–Ca3Al LDH
composites exhibited the greatest reduction in the PHRR (54%),
the analogous gure for PMMA–Ca3Fe LDH composites was
only 34%. The authors suggest that when considering the role of
trivalent metals, the differences in the degree of dispersion also
needs to be taken into account. The nickel-containing LDHs
(NiFe, NiAl, and NiCr) with interlayer DS anions have also been
compared in the PLA/hexaphenoxycyclotriphosphazene (HPCP)
composites. The LOI values of pure PLA and the PLA/HPCP (10
wt%) composite are 20 and 30, respectively. By adding 2 wt% of
a Ni containing LDH into the PLA/HPCP (8 wt%) composites, no
difference was observed among the Fe, Al, and Cr trivalent
cations, and all resulted in a LOI value of ca. 29.80 Jiao et al.88
Fig. 5 (a and b) TEM images of PMMA–Ca3Fe LDH composites at
different magnifications, and (c and d) TEM images of PMMA–Ca3Al
LDH nanocomposites at different magnifications.3 Reproduced with
permission from ref. 3. Copyright © 2009, Elsevier.
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substituted Fe3+ for Al3+ in MgAl–CO3 LDHs in order to syn-
thesise the EVA/MgAlxFey–CO3 LDHs composite with different
Mg/Al/Fe molar ratios. The results showed that the LOI values of
the EVA/MgAlxFey–CO3 LDH composites were about 5% higher
compared to the EVA/MgAl–CO3 LDH composites at the same
LDH loading. Regarding the UL-94 evaluation, there was no
rating for the EVA/MgAl–CO3 LDH composite at 50 wt% additive
loading, and dripping was observed. However, the Fe3+ con-
taining EVA/MgAlxFey–CO3 LDH composites at the same LDH
loading reached the V-0 rating, and the dripping disappearing.
The greatest value of LOI is 41 for the EVA/MgAlxFey–CO3 LDHs
with Mg/Al/Fe molar ratio 6.0/1.5/0.5, which is 5% more than
that for EVA/MgAl–CO3 LDHs. In addition, the PHRR value of
that composite was 277 kW m
2, 28% lower than that of the
EVA/MgAl–CO3 LDH composite (387 kW m
2).
To conclude, similar to divalent cations, the effect of triva-
lent cations might also be related to thermal stability and the
dispersion within polymer. Among all the trivalent cations (Al,
Fe, and Cr) studied, no major differences were noted, in most
cases aluminum is always the rst choice. The introduction of a
given amount of Fe3+ cations into MgAl LDHs might be a
promising method to further increase the ame retardant and
smoke suppression performance.88
5.3 The effect of inorganic anions in the interlayer galleries
To date, only a few inorganic anions intercalated in LDHs have
been investigated as ame retardant additives for polymers, the
most likely reason is the poor compatibility between inorganic–
LDHs and the polymers. Currently, the only intercalated inor-
ganic anions in LDHs that exhibit ame retardancy are
carbonate, borate, and phosphate. Carbonate is the rst and the
one most extensively investigated, carbonate intercalated LDHs
have been shown to be highly efficient in improving the thermal
stability and re properties of polymers, with the important
parameters such as the PHRR, LOI and UL-94 improved
compared to pristine polymers. Zhang et al.74 studied the re-
retardancy of Mg3Al–CO3 LDH in various polymers. Filling PS,
ABS, HDPE, and PVC with Mg3Al–CO3 LDH at 60 wt% loading,
increased the LOI values to 28, 27, 26, and 33, respectively; none
of these values are indicative of outstanding performance but
they do indicate potential for the use of LDH carbonate in re
retardancy. Shi et al.70 observed that the LOI of EVA-28 can be
increased from 21 to 34 and 40 by adding Mg2Al–CO3 and
ZnMgAl–CO3 LDH, respectively.
Inspired by the fact that zinc borate is oen combined with
MH or ATH for improved smoke-suppressing properties, Shi
et al.89 were the rst to report the use of a Mg2Al–borate LDH as
a ame retardant ller for EVA. At 60 wt% LDH loading, Mg2Al–
borate showed a ame retardant performance similar to Mg2Al–
CO3, the LOI of EVA was increased from 21 to 29 (Mg2Al–borate)
and 30 (Mg2Al–CO3), respectively. However, Mg2Al–borate
showed a signicantly better smoke suppression. The smoke
density of EVA/Mg2Al–borate LDH nanocomposite was 45% less
than that of the pure EVA. Nyambo et al.69 studied the ame
retardant performance of ZnAl–borate and MgAl–borate LDHs
in EVA. Fig. 6 shows the HRR curves for the composites and the
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Fig. 6 HRR curves for (a) EVA/MgAl–borate LDH nanocomposites, (b)
EVA/ZnAl–borate LDH nanocomposite. The insets show the photo-
graphs of residual char from the samples with 40 wt% LDH loading.69
Adapted with permission from ref. 69. Copyright © 2009, Elsevier.
photographs of residual char from the samples with 40 wt%
LDH loading. At loadings of about 3 wt% of MgAl–borate and
ZnAl–borate LDHs, the PHRR is reduced by 42% and 36%,
respectively. As the loadings of LDH increased from 3 to 40 wt%,
the reduction in PHRR also increased. There is no signicant
difference in the PHRR reduction for the ZnAl–borate and
MgAl–borate LDHs. The char obtained from MgAl–borate was
so and powdery while the char from ZnAl–borate was hard (see
the insets in Fig. 6). Recently, Wang et al.90 synthesised PP/
Zn2Al–borate LDH and PP/Mg3Al–borate nanocomposites using
a modied solvent mixing method. Cone calorimetry analysis
indicates that PP/Zn2Al–borate LDH nanocomposites exhibited
superior performance to the equivalent PP/Mg3Al–borate LDH
nanocomposites. By considering both the thermal improve-
ment and the ame retardant performance, 15 wt% of the
highly dispersed Zn2Al–borate LDH in PP was found to be the
optimal loading. The 15% Zn2Al–borate LDH in pristine
(unmodied) PP resulted in a 64% reduction of the PHRR
(Fig. 7(b)). If the LDH loading is too high (e.g., 30 wt%), the
thermal stability of the nanocomposites is lowered and so it is
not appropriate for practical applications (Fig. 7(a)). It is
believed that borate promotes the formation of a ceramic-like
MgO or Al2O3-based coating that forms over the char which
forms on the surface of a polymer during combustion and
subsequently forms a vitreous phase which acts as a binder to
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Fig. 7 (a) TGA analysis of PP/Zn2Al–borate nanocomposites with
various LDH loadings (0, 3, 6, 9, 15, and 30 wt%). (b) HRR of PP/Zn2Al–
borate nanocomposites with various LDH loadings (0, 6, 15, and 30 wt
%).90 Adapted with permission from ref. 90. Copyright © 2013,
American Chemical Society.
reinforce this ceramic coating, preventing further
combustion.70
The phosphorus-containing ame retardants are oen used
alone or combined with MH or ATH,68 these compounds are
able to increase the conversion of organic matter to char during
burning. These kinds of charred layers can decrease the amount
of ammable volatile gases reaching the ame zone and reduce
the heat transfer from the ame to the polymer. Therefore, the
performance of LDHs with phosphate-intercalated anions in
the halogen-free ame retardant polymeric materials is of great
interest.68 Ye et al.68 studied the ame retardant properties of
MgAl–PO4 LDH in EVA. The result suggests the ame retardant
efficiency of MgAl–PO4 is higher than that of MgAl–CO3 in the
EVA blends; the LOI increases by about 2%, which is not
signicant, and the UL94 rating of V-0 can be reached at a
loading of 60%.
In conclusion, LDHs intercalated with inorganic anions,
including carbonate, borate and phosphate, are potentially
promising ame retardant llers for EVA. Borate and phosphate
seem slightly more efficient than carbonate, particularly in
regard to smoke suppression. A problem is that in order to be
classied as V-0 in the UL-94, a very high LDH loading of ca. 60
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wt% is required. The current published work has only focused
on one polymer, EVA. We believe the performance of LDHs in
other systems, such as PP, PE and PMMA, should also be eval-
uated. In addition, we suggest that other inorganic anions,
including Cl
, NO3
, SO42
and HCO3
, may also be worth
exploring.
5.4 The effect of organic anions with the interlayer galleries
Since the gallery distance between each pair of pristine LDH
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the hydrophilic surface of the LDH is incompatible with
hydrophobic polymers, which severely inhibits a homogeneous
dispersion of LDH layers within polymer matrix.63,76 Further-
more, the high charge density in the metal hydroxide layer leads
to a strong electrostatic interaction between the hydroxide
sheets making separation of these sheets (exfoliation) very
difficult. Therefore, it is important to modify LDHs with suit-
able organic anions to both increase the gallery distance and
reduce hydrophilic character of the surface. Table 2 gives the
organic anions that have been already used as ame retardants.
Du et al.91 were the rst to obtain LDH exfoliation in linear

layers is generally under 1 nm, it is difficult for macromolecules

to easily intercalate since this distance is too small. In addition, low-density polyethylene to give (LLDPE)/MgAl composites.

Table 2 Summary of organic anion modified LDHs added to polymers and their flame redardancy performancea

LDHs Organic anions Polymer Reduction in PHRR Ref.

MgAl Oleate PP 5% (2 wt%) 63 and 71

EVA 36% (10 wt%)
ZnMgAl Oleate PP 38% (4 wt%) 63
ZnAl Oleate PP 25% (4 wt%) 63, 71 and 94
PMMA 28% (10 wt%)
PE 58%(10 wt%), 72% (20 wt%)
EVA 33% (10 wt%)
PEBuA 13% (10 wt%)
MgAl Cn PMMA 49–58% (10 wt%) 48
PS 21–56% (10 wt%)
MgAl C16 PMMA 51% (10 wt%) 47
ZnAl Undecenoate PMMA 46% (10 wt%) 109
NiAl2 Undecenoate PMMA 16.2% (10 wt%) 33
CoAl2 41.0% (10 wt%)
ZnAl2 25.7% (10 wt%)
ZnAl3 34.6% (10 wt%)
CaAl Undecenoate PMMA 36% (6 wt%) 73
MgAl 24% (6 wt%)
ZnAl 16% (6 wt%)
NiAl 36% (6 wt%)
CuAl 0% (6 wt%)
CoAl 7% (6 wt%)
MgAl MAPK PP 21% (10 wt%) 59
MgAl BA PMMA 46.1% (10 wt%) 112
ABA 35.3% (10 wt%)
BS 28.4% (10 wt%)
BP 30.4% (10 wt%)
MgAl DPHPA PMMA 35.1% (5 wt%) 100
PAHPA EVA 42.7% (5 wt%) 72
MgAl DS LDPE 14.5% (5 wt%) 66
MgAl SA LDPE 27% (5 wt%) 66
MgAl ASA EVA 39% (3 wt%) 67
CoAl DBS PP 29.6% (6 wt% with 6 wt% PP-g-MA) 62
MgAl DBS EPDM 25.2% (40 wt%) 81
MgAl DBS PMMA 45% (10 wt%) 113
MgAl DBS PS 49%(10 wt%) 113
MgAl Adipate UP 46% (1 wt%) 77
MgAl MPS UP 32% (5 wt%) 77
MgAl SEHS PMMA 27% (10 wt%) 113
MgAl SEHS PS 32% (10 wt%) 113
MgAl HDEHP PMMA 37% (10 wt%) 113
MgAl HDEHP PS 33% (10 wt%) 113
a
The weight percentage in the bracket represents the LDH loading. MAPK: lauryl alcohol phosphoric acid ester potassium, BA: benzoic acid, BS:
benzene sulfonic, ABA: 4-amino benzoic, BP: benzene phosphonic, PAHPA: N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-ylamino)-hexyl)acetamide-2-
propyl acid, DPHPA: N-(2-(5,5-dimethyl-1,3,2-dioxaphosphinyl-2-ylamino)-N-hexyl)formamide-2-propenyl acid, DS: dodecyl sulfate, SA: stearate
anion, ASA: 2-aminotoluene-5-sulfonic acid, DBS: dodecyl benzene sulfonate, MPS: 2-methyl-2-propene-1-sulfonate, SEHS: 2-ethylhexyl sulfate,
HDEHP: bis(2-ethylhexyl) phosphate.

This journal is © The Royal Society of Chemistry 2014 J. Mater. Chem. A


Journal of Materials Chemistry A
They directly intercalated LLDPE into an MgAl–NO3 LDH in
which half of the interlayer nitrate anions were ion-exchanged
by DS anions, they called this MgAl–(H-DS) and compared the
properties of LLDPE/MgAl–(H-DS) with the fully DS exchanged
LLDPE/MgAl–DS LDH composites. According to the literature,
LLDPE can not be intercalated in MgAl–DS even if the content of
LDHs was merely 2 wt% while MgAl–(H-DS) had been exfoliated
in the LLDPE matrix even at 10 wt% loading. Other physical
properties, such as crystallinity, the endothermic peak
temperature, and thermal stability of the LLDPE/MgAl LDH
nanocomposites, were enhanced compared to pure LLDPE.
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Unfortunately, ame retardancy, such as LOI and the reduction
in PHRR, were not investigated in that work. In a subsequent
publication, Du et al.92 synthesised PA 6/MgAl–(H-DS) LDH
nanocomposites. The reduction in PHRR of the composites was
38% at only 5 wt% of MgAl–(H-DS) LDH. Ye et al.66 also syn-
thesised LDPE/DS-modied LDH composites and the PHRR
reduction was 15% compared with pure LDPE.
Several other experiments were conducted using DS modi-
ed LDHs together with other effective ame retardants to
improve the re properties of polymers. For example, Zhang
et al.93 synthesised EVA/hyperne magnesium hydroxide
(HFMH)/LDH nanocomposites using DS as the organic modi-
er. As the LDH loading increases, the LOI of composites
increases from 18 for pure EVA to 34 for EVA/HFMH/LDH
composite with 15 parts LDH per hundred resin (phr), and the
author suggested that the LDHs can act as a ame retardant
synergist and compatibiliser, signicantly improve the LOI
values and enhance the elongation at break of EVA/HFMH/LDH
nanocomposites. In a following experiment, Ye et al.65 studied
the LDPE/HFMH system and compared the re properties of
those compounds with different halogen-free ame retardant
synergistic agents, i.e. DS-organically modied LDH, micro-
encapsulated red phosphorus, and expandable graphite. Their
results also show that the exfoliated LDH layers can act as
synergistic disperser and compatibiliser of EVA to disperse the
HFMH particles in the LDPE matrix.
DS modied LDH has also been used as effective ame
retardants additives in IFR, APP and HPCP. Zhang et al.64
reported that the reduction in the PHRR of PP/IFR/ZnAl–DS
LDH was 37% compared with PP/IFR. The LOI of the composite
could reach 33 and obtained the UL-94 V-0 rating, which gives
further support that the ame retardant synergistic effects of
Fig. 8 Cone char of ZnAl–DS LDH based composites with different polymers: (a) PE/LDH, (b) PEBuA/LDH, (c) PMMA–LDH.63 Reproduced with
permission from ref. 63. Copyright © 2009, Elsevier.
J. Mater. Chem. A
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Application
LDHs with IFR can enhance the re properties of polymers. It
should be noted that the LOI of P(BA-VAc)/APP/LDH–DS con-
taining only 0.5 wt% LDH–DS increased to 30 compared with
pure P(BA-VAc) whose LOI value was 20 and its UL-94 increased
from no rating to V-0.82 Overall, the DS–LDHs are usually used
as ame retardants together with HFMH, IFR or APP, etc. Those
composites have been shown to have signicantly reduced
ammability and enhanced thermal stability.
Oleate anions are one of the common charge balancing
anions used in the ame retardant LDH-based additives, the
long chain organic anion acts to compatibilise the LDH with
many polymers, including PE, PMMA and poly(ethylene-co-butyl
acrylate) (PEBuA).63 Furthermore, the unusual packing of these
organic anions in the LDH gallery can facilitate dispersion in
the polymer, which will lead to more effective nanocomposite
formation. Oleate exhibits an excellent combination of high
thermal stability, good water solubility and relatively low cost,
and, as a result, is usually preferred to other possible surfac-
tants.94 Manzi-Nshuti et al.63 compared an essentially non-polar
polymer (PE) against a polar polymer (PMMA) with oleate-
modied LDHs, and a polymer with intermediate polar char-
acter PEBuA was also studied. With 10 wt% loading of ZnAl–
oleate LDH, it is noted that the largest reduction in PHRR was
for PE/LDH–oleate (58%), owed by PMMA/LDH–oleate (28%)
and PEBuA/LDH–oleate (2%). With 20 wt% loading of LDH,
investigated in another study, the reduction in PHRR can reach
72%.94 Fig. 8 shows the char remaining aer cone calorimetry
for each of the polymer–LDH nanocomposites at 10% additive
loading. It can be seen that PE/LDH–oleate has a more dense
char than PMMA/LDH–oleate and there is no compact inor-
ganic residue le aer cone calorimetry in the PEBuA systems.
The author concluded that ZnAl LDH intercalated with long
organophilic carboxylate anions may perform well with non-
polar polymeric systems.
In a further report, Manzi-Nshuti et al.84 synthesised PP
nanocomposites with a series of oleate-containing LDH with
varying Zn–Mg ratios. It found that Zn0.5Mg1.5Al–C18H33O2
nanocomposite showed the largest reduction in PHRR, 38%
with 4 wt% LDH loading. For Zn2Al–C18H33O2, with 2 and 4 wt%
LDH loading, the PHRR reductions are 25% and 5%, respec-
tively. However, the reductions in PHRR obtained are lower
than what has been reported for PP/MMT composites.95 Thus
the authors predispersed the LDHs in similar polymers that are
This journal is © The Royal Society of Chemistry 2014

Application
functionalised with polar groups (PP-g-MA) to increase the
compatibility between organically modied LDHs with non-
polar polymers, which will be discussed in detail in another part
of this review. Oleate-organically modied LDHs have also been
used in the EVA matrix. Wang et al.71 synthesised EVA/MgAl–
oleate LDH and EVA/ZnAl–oleate LDH composites. With 10 wt%
LDH loading, the PHRR reduction is 36% and 32% for MgAl–
oleate and ZnAl–oleate, respectively.
DBS is another important anion applied to modify LDHs for
ame retardant application. Costa et al.28 modied MgAl LDH
with DBS using the regeneration method and used this LDH to
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prepare LDPE/LDH nanocomposites with different LDH load-
ings. Fig. 9(a) indicates that the addition of a small amount of
LDH causes signicant reduction in PHRR. For unlled LDPE,
the PHRR is over 800 kW m
2.28,96 At higher LDH loadings (i.e.
8.95 wt%), the PHRR was lower, below about 300 kW m.
2
Fig. 9(b) shows that the ignition time (tig) can also be increased.
The unlled LDPE has a tig below 100 s and that increases to
above 120 s with the addition of 16.2 wt% LDH. In terms of LOI,
there is a slight improvement from 18 for pure LDPE to 22 at
16.2 wt% LDH loading. However, none of the LDPE/LDH
nanocomposites containing up to 16.2 wt% LDH could be
classied in the UL-94 V protocol. Wang et al.97 prepared LDH–
DBS composites with different polymers, i.e. PMMA and PS,
both by melt blending and bulk polymerization. Generally, it is
easier to disperse LDHs–DBS in PMMA than in PS (Fig. 10). The
best reduction in PHRR was 45% and 49% for PMMA and PS
Fig. 9 (a) HRR curves of LDPE/LDH with different LDH loadings. (b)
Variation of time of ignition (tig) and PHRR with LDH content.28
Reproduced with permission from ref. 28. Copyright © 2007, Elsevier.
This journal is © The Royal Society of Chemistry 2014
View Article Online
Journal of Materials Chemistry A
Fig. 10 TEM images of (a) and (b) PMMA and (c) and (d) PS with LDHs–
DBS.97 Reproduced with permission from ref. 97. Copyright © 2009,
Elsevier.
respectively. Wang et al.62 synthesised PP/CoAl LDH using DBS
as the organic modier through a novel method of producing
LDH–DBS in a single step with homogeneous composition and
structure. With 6.0 phr LDHs–DBS, the PP/LDH systems showed
reduced PHRRs, from 1071 W g
1 in PP to 754 W g
1 in PP/LDH
(tested by MCC-1, FTT), a more than 25% reduction. However,
the thermal stability of the compounds decrease slightly
compared to the base polymer.
Another two studies, conducted by Wang et al.,81,98 intro-
duced LDH–DBS to PLA/IFR and maleic anhydride graed
ethylene–propylene–diene terpolymer (mEPDM)/IFR systems.
For PLA, the reduction in PHRR of PLA/IFR/LDH was 62%
compared with pure PLA, but the reduction was less than that of
PLA/IFR (65%). However, the PLA/IFR/LDH composites had
more continuous, compact and unsmoothed char residues
(Fig. 11). For mEPDM system, the reductions in PHRR were 36%
and 32% for mEPDM/IFR/LDH and mEPDM/IFR, respectively.
Undecenoate anions are also chosen as the spacer in the
LDH since the volume of this anion is large and it contains a
polymerizable end group98 which can help to obtain exfoliated
nanocomposites according to previous work with montmoril-
lonite (MMT).99 Manzi-Nshuti et al.3,33 synthesised a series of
LDHs–undecenoate to prepare PMMA–LDH composites. The
cone calorimetric results showed that the PMMA/CaAl3–unde-
cenoate system gave the best reduction (54%) in PHRR at 10 wt
% loading of LDHs, followed by 41% reduction of PMMA/CoAl2–
undecenoate system.
Many other organically modied LDHs have also been
introduced to a range of polymers, this can result in impressive
re retardancy properties of the composites. For example,
Nyambo et al.48 prepared alkyl carboxylate {CH3(CH2)nCOO
, n
¼ 8, 10, 12, 14, 16, 20}-modied LDHs and used them as
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Journal of Materials Chemistry A Application

UL-94 results are required to evaluate their viability in real

applications.

5.5. The effect of dispersion

A paper by Matusinovic20 has been cited earlier in this manu-
script, which deals directly with the effect of dispersion. In that
work it was shown that a well-dispersed LDH is signicantly
more effective in the reduction of the PHRR than is a poorly
dispersed LDH. In the case of MMT-containing nano-
composites, a poorly dispersed system is ineffective in reducing
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the PHRR while a poorly dispersed LDH is effective. Thus for

Fig. 11 Images of samples studied after cone calorimeter test: (a) neat
PLA; (b) PLA-FR; (c) PLA-FR-LDH.114 Reproduced with permission from
ref. 98. Copyright © 2010, Elsevier.
MMT the extent of dispersion is the only thing that matters, this
is due to the mechanism by which MMT prevents combustion,
which is to reduce the mass loss rate by forming a barrier to
mass and thermal transfer. It was noted earlier that it was not
believed that the mechanism for an LDH is the same as that for
MMT. With an LDH, there are a plethora of processes that could
be involved, including endothermic decomposition of the metal
hydroxides, formation of a mixed metal oxide layer reecting
the heat and dispersion; of course, there may be other
unidentied processes involved for an LDH. The results of

nanollers for PS and PMMA. The most effective composite

formulation for PS are those with MgAl–C10 and MgAl–C12,
whose reductions in PHRR were 56% and 52%, respectively, at
10% loading. The lowest reduction was 21% for MgAl–C22.
There is a tradeoff between longer chains having more bulk,
and hence greater interlayer spacing, and longer chains having
more organic material which can burn. For PMMA, the largest
reduction in PHRR was 58% with 10% MgAl–C10 LDH loading
and the reductions for MgAl–C12, 14, 16, 22 were all around
50%. Pereira et al.77 prepared UP/LDH nanocomposites with
LDH-adipate and LDH-2-methyl-2-propene-1-sulfonate (LDH-
MPS). The reduction in PHRR was 46% and 32% by incorpo-
rating 1 wt% of LDH-adipate and 5 wt% LDH/MPS, respectively;
mass loss curves show enhanced char formation. Huang et al.72
modied MgAl–CO3 LDH with a phosphorus–nitrogen con-
taining compound, PAHPA. In comparison to pure EVA, the
PHRR of EVA/MgAl–PAHPA LDH nanocomposite was reduced
by 43%. Similar results were obtained with PMMA/MgAl–
DPHPA LDHs nanocomposite.100
Polymers combined with organic anion-containing LDHs
show signicantly enhanced ame retardancy compared with
the pure polymer matrix. Compared to inorganic anions inter-
calated LDHs, the organically-modied LDHs have much better
compatibility with polymers, and a much lower LDH loading is
required to deliver similar ame retardant performance.
However, it is important to note that the organic anions are
inherently combustible, thus the loading cannot be too high or
both the thermal stability and ame retardant properties will
decrease. For the polymer/organo-LDH nanocomposites, Fig. 12 (a) Comparison of the HRR of 6 wt% PP/LDH nanocomposites
currently most of the ame retardant evaluations were carried synthesized using solvent mixing and melt mixing methods. (b) SEM
image of 6 wt% PP/Zn2Al–borate nanocomposites synthesised using
out using either cone calorimetry or MCC; LOI and, especially
melt mixing method.90 Reproduced with permission from ref. 90.
Copyright © 2013, American Chemical Society.

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Matusinovic20 showed that a poorly dispersed system has a
PHRR reduction of 24% while a well-dispersed system gives a
42% reduction. This suggests that about one-half of the ame
retardant effect is due to dispersion and the other half is due to
other factors, some of which were noted above. It is important
that these other factors be fully identied so that they can be
used properly to achieve good ame retardancy.
Recently, Wang et al.90 also demonstrated that good disper-
sion is crucial for ame retardancy. They compared the HRR of
PP/Zn2Al–borate nanocomposite synthesized by solvent mixing
and melt mixing methods. It is clear that the solvent mixing is
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superior to melt mixing method. With 6 wt% of LDH, the
reduction in PHRR is 24% for melt mixing and 30% for solvent
mixing (Fig. 12(a)). Fig. 12(b) shows the SEM image of PP/Zn2Al–
borate LDH nanocomposite synthesized by the melt mixing
method. Big LDH particles with an average size of 60–100 mm
were clearly seen, which conrms that the melt mixing method
resulted in much poorer dispersion of the LDH.
6. The effects of polymeric
compatibiliser
Although LDHs are effective to improve the ame retardant
properties of polymers, due to the hydrophilic nature of LDHs,
they generally do not exhibit good compatibility with non-polar
polyolens. For example, it is difficult to obtain good dispersion
when PP is combined with cationic clays, like MMT and it is also
difficult to obtain a well-dispersed polymer–LDH nano-
composite. In order to meet the requirement for good disper-
sion in the polymer matrix and thus produce an effective
improvement in the re performance, polymeric compatibil-
isers are commonly used to predisperse the nanoller. The
principal is to gra a polar group such as maleic anhydride to
the polymer chains.
PE-g-MA, PP-g-MA, and low-density polyethylene-gra-maleic
anhydride (LDPE-g-MA) have been added to the polymer–LDHs
nanocomposites as compatibiliser. Chen et al.101 prepared PE-g-
MA/MgAl–DS LDH exfoliated nanocomposite for the rst time.
The polymer–LDH nanocomposite showed enhanced re-
retardant properties and thermal stability. With 5 wt% MgAl–DS
LDH loading, the PE-g-MA/MgAl LDH exfoliated nanocomposite
charred faster in the temperature range 210 to 390  C and was
more thermally stable above 390  C than was PE-g-MA. Manzi-
Nshuti et al.84 investigated the inuence of LDH composition
and of the presence of a polymeric compatibiliser, PP-g-MA, as
well as the dispersion and properties of PP/ZnAl–oleate, PP/
MgAl–oleate, PP/ZnMgAl–oleate LDHs system. Three ratios of
the non-polar matrix PP to PP-g-MA were evaluated; PP:PP-g-MA
ratios of 8 : 1, 4 : 1 and 1 : 1 were used. Fig. 13 provides a
comparison between the reductions in PHRR recorded at
different ratios of PP-g-MA. At the lower PP-g-MA contents of PP-
g-MA (8 : 1 and 4 : 1) the reductions in the PHRR are less than
when more PP-g-MA is present, 1 : 1. The compatibiliser is
important in enhancing the re retardancy properties. A similar
result was also obtained with PP/PP-g-MA/CoAl–DBS LDH
system.62 The PHRR decreased signicantly compared to pure
This journal is © The Royal Society of Chemistry 2014
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Fig. 13 The effect of PP/PP-g-MA ratio on the combustion properties
of modified LDHs; the reductions in PHRR of the composites relative
to the pristine polymers are plotted against the LDH loading. (AA:
Mg2Al, AC: ZnMgAl, AE: Zn2Al).84 Reproduced with permission from ref.
84. Copyright © 2009, Elsevier.
PP with addition of CoAl LDH and PP-g-MA, reaching 30% with
6 phr LDH and 6 phr PP-g-MA. Ye et al.66 prepared LDPE/MgAl–
NO3, LDPE/MgAl–DS, and LDPE/MgAl–SA LDHs nano-
composites. When the content of both LDH and LDPE-g-MA
were 5 phr, the PHRR was reduced by 5, 15, and 27%, respec-
tively. The compatibiliser is more important for the organically-
modied LDH than for the inorganic system.
The addition of polymeric compatibilisers can signicantly
improve the interaction between the polymers chains and the
LDH and enhance the ame retardant properties of these
composites. Probably the dominant effect is that these compa-
tibilising agents can improve the dispersion of the hydrophilic
LDHs within the non-polar (hydrophobic) polymer matrix.
7. Synergistic effects with other fire
retardants
First a small disclaimer, synergy means that there is a more
than an additive effect. This term is poorly used and quite
frequently synergy will be claimed simply because two or more
materials are used. Thus the reader must be careful to differ-
entiate mathematically proven synergy from simply claimed
synergy. In the eld of ame retardant technology, LDHs have
been found to have synergistic effects with many halogen free
ame retardant (HFFR) agents. The presence of an addition
additive can not only enhance the ame retardant properties of
polymer–LDH nanocomposites, but also reduce the required
loading of HFFR agents in polymer matrix so as to improve the
mechanical properties of polymer nanocomposites. These
agents include HFMH,93,102 APP,53,82,94 red phosphorus,65,103 zinc
borate,59 expandable graphite,65,104,105 and IFRs64,104 (Table 3).
Here the commonly used synergistic systems are summarized
and optimal synergistic effects between LDH and the other
HFFR materials are described.
MH is an example of a toxic-free, smoke-suppressing,
halogen-free ame retardant additive. However, its high loading
in the polymer matrix leads to signicant detrimental reduction
in the mechanical properties. The synergistic effects of MH and
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Table 3 A summary of the synergistic compounds using in combination with LDHs and their effects on the flame retardancy performance for
polymer nanocompositesa

Synergistic compounds LDHs Polymer Reduction in PHRR* Ref.

MH MgAl–DS EVA 87.7% (5 wt%, 45 wt%) 93 and 102

MgAl–DS LOI: 18 to 34(15 wt%, 85 wt%)
ZnAl–DS 78.3% (5 wt%, 45 wt%)
MgFe–DS 84.9% (5 wt%, 45 wt%)
APP ZnAl–oleate PE 43% (10 wt%, 10 wt%) 94
ZnAl–CO3 PVA LOI: 19.7 to 30.6 (0.3 wt%, 14.7 wt%) 53
NiAl–CO3 LOI: 19.7 to 33.9 (0.3 wt%, 14.7 wt%)
NiFe–CO3 LOI: 19.7 to 33.6 (0.3 wt%, 14.7 wt%)
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ZnFe–CO3 LOI: 19.7 to 32.8 (0.3 wt%, 14.7 wt%)

MgAl–DS P(BA-VAc) LOI: 20.0 to 30.7 (0.5 wt%, 14.5 wt%) 82
MgAl–undecenoate PS 42% (5 wt%, 5 wt%) 106
MRP MgAl–CO3 EVA LOI: 32 to 39 (70 phr, 10 phr) 103
MgAl–DS LDPE/EVA LOI: 29 to 36 (5 phr, 5 phr) 65
EG MgAl–CO3 EVA 80.2% (35 wt%, 15 wt%) 105
MgAl–DS LDPE/EVA LOI: 29 to 38 (5 phr, 5 phr) 65
IFR NiAl–DS PP 87.8% (1.5 wt%, 28 wt%) 64 and 104
ZnAl–DS 75.0% (1 wt%, 30 wt%)
MgAl–DS 74.1% (1 wt%, 30 wt%)
CuAl–DS 66.7% (1 wt%, 30 wt%)
CaAl–DS 72.5% (1 wt%, 30 wt%)
MgAl–DBS mEPDM 55.2% (2 wt%, 38 wt%) 81
MgAl–DBS EPDM 59.9% (2 phr, 30 phr) 108
ZnAl–DBS PLA 58.5% (2 wt%, 23 wt%) 114
MgAl–DBS PLA 46.0% (2 wt%, 23 wt%)
SiO2 MgAl–CO3 EVA 67.7% (2 wt%, 48 wt%) 105
Melamine ZnAl–undecenoate PMMA 52% (2.5 wt%, 27.5 wt%) 109
Zinc borate MgAl–MAPK PP 63% (10 wt%, 10 wt%) 59
TPP ZnAl–oleate PE 8% (10 wt%, 10 wt%) 94
RDP ZnAl–oleate PE 14% (10 wt%, 10 wt%) 94
DECA/AO ZnAl–oleate PE 24% (10 wt%, 8 wt%, 2 wt%) 94
a
The rst loading in the bracket is for LDH, and the second loading is for synergistic compounds. MH: magnesium hydroxide, APP: ammonium
polyphosphate, MRP: micro-encapsulated red phosphorus, EG: expandable graphite, IRF: intumescent ame retardant, TPP: triphenol phosphate,
RDP: resorcinol diphosphate, DECA/AO: decabromophenyl oxide/antimony oxide, phr: parts per hundred resin.

LDHs on ame retardant properties have been a major focus of
recent research in this area. In order to improve the re
performance of polymer matrix, various LDHs, including MgAl–
DS, ZnAl–DS, MgFe–DS, have been added to EVA/MH compos-
ites. The addition of LDH instead of the same amount of MH
increases the LOI (insignicantly) from 29 to 31, 32, 32, and 34
at loadings of 2, 5, 10, and 15 phr LDH, respectively; these small
changes should have no effect on re performance. Similarly,
synergistic effects of MgAl, ZnAl, and MgFe LDHs with MH have
also been compared.102 The cone calorimetry data show that all
LDHs led to good ame retardant properties with EVA. The EVA/
MH/MgAl LDH nanocomposites resulted in a remarkable
reduction in PHRR of 59% relative to EVA/MH. One reason that
LDH can act as ame retardant synergistic agent with MH is
that the LDH layers act as a good barrier and can help the
HFMH additive disperse more evenly in the EVA matrix and
thus enhance the ame performance compared with the sample
without LDH.
APP is another important ame retardant additive, with
which LDHs may offer synergy. Studies show that using LDH
together with phosphorus-containing ame retardants can help
to improve the dispersion of these additives within the polymer
matrix.106 ZnAl–CO3, ZnFe–CO3, NiAl–CO3, NiFe–CO3, ZnAl–
oleate, MgAl–DS, and MgAl–undecenoate with APP have been
added to polymers, such as PVA, PE, P(BA-VAc), and PS. For
example, ZnAl–CO3, ZnFe–CO3, NiAl–CO3, and NiFe–CO3 LDH
as synergistic agents were used to improve the ame retardancy
of APP in a PVA matrix.53 When the content of the LDH in PVA is
0.3 wt% and the content of APP is 14.7 wt%, the LOI of PVA
increased from 20 to 31, 33, 34, and 34, respectively. Further-
more, the amount of residue increased in the order: PVA/APP <
PVA/APP/ZnAl < PVA/APP/ZnFe < PVA/APP/NiFe < PVA/APP/NiAl.
Among the PVA/APP/LDH samples, PVA/APP/NiAl showed the
best ame retardant performance. Manzi-Nshuti et al.94
prepared PE/APP/ZnAl–oleate LDH nanocomposites. The
combination of 10% APP and 10% ZnAl led to a 43% reduction
in PHRR, which is a much higher reduction than 10% APP (4%)
and 20% APP (35%) (Fig. 14). The effect of composition of
MgAl–DS and APP on P(BA-VAc) materials with a 15 wt% total
loading was investigated.82 When the contents of MgAl–DS and
APP in BA-VAc were 0.5 and 14.5 wt%, the LOI increased from 20
to 31, and obtained a UL94 V-0 rating. Nyambo et al.106 added
MgAl–undecenoate LDH and APP to PS individually and in
combinations at weight fractions no greater than 10%. Cone

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Fig. 14 HRR curves of PE modified with APP and LDH and the residues
of modified PE systems after the cone experiment (a) PE/APP 20%, (b)
PE/APP 10%/LDH 10%.94 Adapted with permission from ref. 94.
Copyright © 2009, Elsevier.
calorimetry data showed that the PHRR reduction of PS/APP
5%/MgAl 5% was 42%, which was signicantly higher than PS/
MgAl 10% (17%) and PS/APP 10% (27%). The ame retardant
properties can be improved by the synergistic combination of
LDHs with APP. Physical and chemical interactions between
LDH and APP are responsible for the observed synergy in re
performance.106
The exact nature of the interaction between APP and LDH
when dispersed in a polymer is not known.53,94 A possible
origin of this synergistic effect between APP and LDHs was
proposed by Zhao et al.53 During burning, APP rst decom-
poses thermally to form poly(phosphoric acid) (Fig. 15,
Reaction 1) which may undergo a further dehydration in two
traditional ways. The phosphate ester may react with the PVA
chain (Reaction 3) or itself (Reaction 2), and subsequently
may crosslink with the formation of a three-dimensional
network. In addition to the traditional dehydration pathway,
poly(phosphoric acid) may react with the LDH, releasing
water or produce bridges between APP chains (Reaction 4).
The formation of a small number of such bridges will induce a
stabilization of APP and a decrease in the volatility of phos-
phorus, and thus more APP will be available for phosphory-
lation and char formation. The crosslinks will, in effect,
increase the degree of polymerization of poly(phosphoric
acid), which will then increase the viscosity of the melt during
pyrolysis and combustion, and therefore enhance the forma-
tion of compact and dense charred layer.
The IFR is an efficient ame retardant system for polymer
materials. It is halogen-free and has a low toxicity. A typical
This journal is © The Royal Society of Chemistry 2014
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Journal of Materials Chemistry A
IFR system for PP, comprised of APP and pentaerythritol (APP/
PER), has proven to be a highly efficient ame retardant
system.64 When this IFR system is introduced into polymers,
the physical and mechanical properties will sharply decrease
and need to be enhanced by some synergists.64 Recently,
synergy between IFR and LDHs has been shown to be an effi-
cient to improve the ame performance; ZnAl–DS, MgAl–DS,
CuAl–DS, CaAl–DS, ZnAl–DBS, MgAl–DBS LDH have been
added to the polymer/IFR system. For example, Zhang et al.64
studied the effect of LDHs with different divalent metal
cations on the ame retardant, thermal, and mechanical
properties of PP/IFR/LDH nanocomposites. When the
composition of PP/APP/PER/LDH samples was 100 : 20 : 10 : 1
(wt%), the reduction in PHRR followed the order of ZnAl (75%)
> MgAl (74%) > CaAl (73%) > CuAl (67%). The PP/IFR/ZnAl LDH
sample showed the longest combustion time aer ignition.
The PP/IFR/LDH samples with ZnAl and CuAl have high LOIs,
33, and can obtain UL-94 ratings. One reason for this is that Zn
and Cu can catalyze the esterication reactions of APP and
PER IFR system and so promote the formation of char.64,107 PLA
based on ame retardant composites containing APP, PER,
and melamine cyanurate in addition to ZnAl–DBS, MgAl–DBS
LDHs have been prepared.53 At 23 wt% IFR and 2 wt% LDH
loading, the PHRR value of PLA (480 W g
1) was lowered to 273
W g
1, 259 W g
1, 199 W g
1 for PLA/IFR, PLA/IFR/MgAl LDH,
and PLA/IFR/ZnAl LDH nanocomposites which represent a
43%, 46% and 59% reduction, respectively. The synergistic
effect of other re retardant together with MgAl–DBS LDH in
mEPDM/IFR system has been studied.81 Fig. 16 shows the
PHRR data for mEPDM, mEPDM/LDH40, mEPDM/IFR40 and
mEPDM/IFR38/LDH2. The PHRR for mEPDM/IFR40 and
mEPDM/LDH40 are 472 W m
2 and 451 W m
2, 29% and 25%
reductions compared to pure mEPDM. However, the PHRR
reduction of mEPDM/IFR38/LDH2 is 55%, which indicated
that only small amounts of an LDH may have a considerable
effect on this IFR system. Besides, Wang et al.108 synthesized
EPDM/IFR/MgAl–DBS nanocomposites and compared the re
performance with EPDM/IFR/OMMT. They found that EPDM-
IFR30-OLDH2 composite (100 phr EPDM, 30 phr IFR, and 2
phr OLDH) presented the highest tensile strength and could
pass a UL-94 test V-0 rating; while the EPDMIFR30-OMMT2
composite (100 phr EPDM, 30 phr IFR, and 2 phr OMMT)
showed the lowest peak pHRR and THR values, suggesting
different ame-retardant performances should be attributed
to their own characteristics, dispersion state in EPDM matrix,
and the change of structure during burning.
Apart from MH, APP, and IFR, other HFFR materials such
as micro-encapsulated red phosphorus, expandable
graphite, SiO2, melamine, and zinc borate show good synergy
with LDHs in polymers.59,65,103–105,109 Both the physical and
chemical interactions between the LDH and the HFFR
materials are responsible for the observed synergy in re
performance.106 The LDHs are thought to impact char
formation in the polymer/HFFR system. This char is very
effective, making the polymeric substance less prone to
combustion.62
J. Mater. Chem. A

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Fig. 15 A schematic of the possible mechanism of char formation during combustion of the PVA/APP/LDH nanocomposite.53 Reproduced with
permission from ref. 53. Copyright © 2008, Elsevier.
8. Conclusions and future prospects
LDHs may be regarded as a promising new green ame retardant
for polymer applications. In this review, the current state-of-the-
art in ame retardant LDH–polymer nanocomposites is sum-
marised. It is generally believed that the ame retardant mecha-
nism of LDHs is different from that of silicate clay-based
nanocomposites, and can be attributed to the combination of the
following four functions: (1) heat absorption (endotherm), (2)
gaseous dilution, (3) char formation and (4) dispersion. Various
J. Mater. Chem. A
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Application
polymers including PP, PE, EVA, PS, PMMA, PVC, ABS, UP, EP,
PLA, EPDM, and PA 6 have been investigated as ame retardant
polymer–LDH nanocomposites. It has been demonstrated that
LDHs are efficient for all the above mentioned polymers. To
obtain the best ame retardant performance, different polymers
require different types of LDHs. There is still no thorough
understanding of the processes by which the various divalent and
trivalent metals are effective but it is likely that this must be
related to the thermal stability and the dispersion of LDHs.
Among different divalent cations, Zn and Mg seem to give better
ame retardant performance than others. Among the trivalent
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Application
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Fig. 16 HRR curves of mEPDM, mEPDM/LDH, mEPDM/FR, and
mEPDM/FR/LDH nanocomposites.81 Reproduced from ref. 81.
cations (Al, Fe and Cr) studied, no big difference was noticed, and
in most of the cases Al is always the rst choice. The literature also
suggests the use of two or more divalent or trivalent cations in
LDHs for higher ame retardant and smoke suppression effi-
ciencies. The effect of inorganic anions, including carbonate,
borate and phosphate, has also been evaluated with EVA. Borate
and phosphate seems slightly more efficient than carbonate,
particularly in the aspect of smoke suppression. However, the
current studies were only focused on EVA and it is believed that
their performance in other polymer systems, such as PP, PE,
PMMA, should be evaluated as well. In addition, other types of
inorganic anions including Cl
, NO3
, SO42
or HCO3
remain
essentially unexplored. Compared to inorganic anions interca-
lated in LDHs, the organically-modied or intercalated LDHs have
much better compatibility with polymers, and a much lower LDH
loading is required to deliver similar ame retardant perfor-
mance. However, it is important to note that the organic anions
are ammable and thus the loading of such organic modied
LDHs cannot be too high. For the polymer/organo-LDH nano-
composites, currently most of the ame retardant evaluations use
either cone calorimetry or MCC, more LOI and especially UL-94
evaluations are required to evaluate their viability for real appli-
cations. Polymeric compatibilisers, such as PP-g-MA, have been
shown to signicantly increase the interactions between polymers
and LDHs and improve the ame retardant properties of the
composites. LDHs may exhibit synergy with many HFFR agents;
this can not only enhance the ame retardant properties of
polymer–LDH nanocomposites, but also reduce the loading of
HFFR agents in polymer matrix so as to improve the mechanical
properties of polymer nanocomposites. The synergistic function
of LDHs is considered to impact the char formation of polymer/
HFFR agents system.
Acknowledgements
The authors thank the Fundamental Research Funds for the
Central Universities (TD-JC-2013-3 and BLYJ201402), the
Program for New Century Excellent Talents in University (NCET-
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Journal of Materials Chemistry A
12-0787), the Beijing Nova Programme (Z131109000413013), the
National Natural Science Foundation of China (51308045), the
Foundation of State Key Laboratory of Coal Conversion (Grant
no. J14-15-309), Institute of Coal Chemistry, Chinese Academy
of Sciences, and the SCG Chemicals, Thailand for nancial
support.
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