Fire Safety Journal 62 (2013) 281288

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Fire Safety Journal

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Enhanced ame retardancy of natural rubber composite with addition

of microencapsulated ammonium polyphosphate and MCM-41 llers
Na Wang n, Long Mi, Yuxian Wu, Xiangzhou Wang, Qinghong Fang
College of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China

art ic l e i nf o

a b s t r a c t

Article history:
Received 12 December 2012
Received in revised form
25 April 2013
Accepted 3 September 2013
Available online 26 October 2013

Microencapsulated ammonium polyphosphate with melamine-formaldehyde resin (MCMF-APP) prepared by in situ polymerization and characterized by FTIR showed decreased water solubility and particle
size in comparison to bare ammonium polyphosphate. APP was used as additive to natural rubber (NR)
together with mesoporous silica MCM-41 as a synergistic agent to form intumescent ame retardant
composite in this study. The ame retardancies of NR/APP, NR/MCMF-APP and NR/MCMF-APP/MCM-41
composites were studied using limiting oxygen index (LOI) and UL-94 test, and their thermal stability
was evaluated by thermogravimetric analysis (TGA) and dynamic mechanical thermal analysis (DMTA) as
well as physico-mechanical properties. The results indicated that the LOI value of NR/MCMF-APP
composite was higher than those of NR/APP composite and NR. Addition of MCM-41 into NR/MCMF-APP
composite further increased the LOI values and also increased the UL-94 ratings of most ternary
composites to V-0 due to a synergistic effect between MCM-41 and MCMF-APP in NR composites. As the
results showed, the thermal stability and ame retardancy of NR were enhanced.
Crown Copyright & 2013 Published by Elsevier Ltd. All rights reserved.

Keywords:
Intumescent ame retardant
Thermal stability
Synergism
DMTA
Physico-mechanical properties

1. Introduction
Natural rubber (NR) has been increasingly replacing synthetic
rubbers in many applications favored by its unique properties such
as elasticity, exibility and resilience. It has been especially applied
in a wide range of commercial products like tires of aircraft and
automotives where superior properties are required. However,
despite its many superior qualities, its inherent high ammability
prevents NR from being used in some highly demanding applications such as coal mine convey or belts, power cables, aircraft tire
treads, and so on [14].
To prevent complete combustion of NR, ame retardants are
usually added, among which the bromine-containing ame retardants and their synergistic systems have been proven to be the
most effective and also cost-effective ones. However, concerning
the environmental and life safety issues, the use of these ame
retardants have been limited. Metal hydroxides, such as aluminum
hydroxide and magnesium hydroxide, are other effective ame
retardants in NR. But usually high loading of these metal hydroxides are required to obtain satised re resistance, which
however greatly destroys the mechanical properties of NR. Intumescent ame retardants (IFR) with little smoke release and low
toxicity are preferable additives in NR. As a traditional IFR,
ammonium polyphosphate (APP)pentaerythritol (PER)melamine system was rst used in re retardant intumescent coatings

Corresponding author. Tel.: 86 13840257976; fax: 86 24 89388153.

E-mail address: iamwangna@sina.com (N. Wang).

[5]. But due to its high water solubility and low compatibility
with organic materials, the IFR system is not durable. For instance,
APP, a well known component of the IFR system, is easily attacked
by moisture. It will then migrate to the surface, not only leading
to decrease of the ame retardancy, but also degrading some
other properties of the polymers [69]. To overcome these
problems, microencapsulation of IFR system has been regarded
as an effective strategy. Hu Yuan et al. [10,11] successfully microencapsulated APP with polyurethane (PU), ureamelamine-formaldehyde (UMF) resin and PVAmelamine-formaldehyde (VMF)
resin shell. Specos [12] developed a novel approach to synthesize
microcapsules and cotton fabrics by means of microencapsulation
technique. Nevertheless, the commercially available intumescent
formulations could contain any of the following llers: titaniumdioxide, resin binder, plasticizers, and alumino-silicate clay materials. These llers may act as synergistic agents in intumescent
ame retardant formulations. Among the possible alumino-silicate
llers, Wang et al. [13] reported that the 4A zeolite could be an
effective ller for improving the mechanical and FR properties of
NR composites. IFR/NR systems, the 4A zeolite/IFR/NR composite
showed lower mass loss ratio, higher LOI value and higher thermal
stability. Wei et al. [14] studied the effect of 4A zeolite on the
thermal degradation and charring of intumescent APP/PER system
by X-ray photoelectron spectroscopy and thermogravimetric analysis. They veried that the thermal degradation and charring
processes of the APP/PER system with zeolite was related to the
type of zeolites. Synergism has also been found between intumescent ame retardants and MCM-41 or SBA-15 in polypropylene
composites (PP-IFR) in our previous work [15]. The synergistic

0379-7112/$ - see front matter Crown Copyright & 2013 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.resaf.2013.09.008

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N. Wang et al. / Fire Safety Journal 62 (2013) 281288

2.2. Preparation of microencapsulated APP

Table 1
Formulations of NR ame retardant nano-composites.
No.

NR
(phr)

MCM-41
(phr)

APP
(phr)

MCMF-APP
(phr)

PER
(phr)

MEL
(phr)

0#
1#
2#
3#
4#
5#
6#
7#
8#
9#
10#
11#
12#
13#
14#
15#

100
100
100
100
100
100
100
100
100
100
100
100
100
100
100
100

0
0
0
0
0
1.5
3
5
0
1.5
3
5
0
1.5
3
5

0
35
45
55
0
0
0
0
0
0
0
0
0
0
0
0

0
0
0
0
35
35
35
35
45
45
45
45
55
55
55
55

0
11.7
15
18.3
11.7
11.7
11.7
11.7
15
15
15
15
18.3
18.3
18.3
18.3

0
11.7
15
18.3
11.7
11.7
11.7
11.7
15
15
15
15
18.3
18.3
18.3
18.3

systems of PP with mesoporous silica MCM-41 or SBA-15 not only

showed good ame retardancy but also possessed remarkably
good mechanical properties as compared to the PP/PP-g-MA/IFR
system.
The use of intumescent additives allows for optimization of
both the re properties and mechanical behavior of the materials
[15,16]. However, little work has been done concerning the
synergistic effect between the ame retardants and MCM-41 in
NR composites. In this work, the effects of incorporation of
microencapsulated ammonium polyphosphate with a melamineformaldehyde resin (MCMF-APP) combined with MCM-41 into NR
composites on their ame retardancy and mechanical properties
were studied. In addition to TG and other ame retardancy tests, a
detailed dynamic mechanical thermal analysis (DMTA) that was
useful for studying the composite structure and performance was
employed in this study. This method was commonly used to
determine the glass transition temperature of polymeric materials
from the peak of loss angle tangent, morphology of crystalline
polymers and damping (heat dissipation) [17,18].

2. Experimental details
2.1. Materials
Nano-sized mono-disperse mesoporous MCM-41 particles with
uniform diameters in the range of 80100 nm and with a spherical
shape were prepared in our laboratory following a literature
method [19]. The particle size and its distribution were measured
by a particle size analyzer and transmission electron microscope
(TEM). Infrared radiation (IR) analysis of the synthesized nanosized mesoporous MCM-41 particles has been reported in our
previous paper [18]. The (BET) surface area and specic pore
volume of the MCM-41 particles were 732 m2/g and 0.9 cm3/g,
respectively. A narrow pore size distribution of 3.6 nm was
measured from the as-prepared MCM-41 particles [19].
The NR SMR-20 was supplied by Petrochemical Co. Jilin.
Analytical grade zinc oxide (ZnO), stearic acid, sulfur and other
chemicals were used as received. APP with an average degree of
polymerization n 41000, a solubility of 0.5 g/ml in H2O at 25 1C
and phosphorous content of 431 wt% was supplied by Changfeng
Chemical Corporation, China. Pentaerythrite (PER) and Melamine
(MEL) were purchased from Sinopharm Chemical Reagent Co. Ltd.
Here the formulation of IFR was APP, PER and MEL (APP: PER:
MEL 3:1:1), whereas the formulation of MCMF-IFR was MCMFAPP, PER and MEL.

Pre-polymer synthesis: 15 g of MEL and 37 wt% formaldehyde

solution were put into a three-neck bottle and magnetically
stirred. The pH value of the mixture was adjusted to 89 by
10 wt% Na2CO3 solution. The mixed solution was heated to about
70 1C and kept at that temperature for 2 h. After that, MF prepolymer solution was prepared and ready for microencapsulation
of APP.
Preparation of microencapsulated APP: 60 g of APP was rst
dispersed in 150 ml ethanol within a three-neck bottle, following
by addition of 6.54 g MF pre-polymer solution under stirring. The
pH of the mixture was adjusted to 45 with sulfuric acid. The
mixture was then heated to 70 1C and held for 2 h. After that,
the mixture was cooled to room temperature, ltered, washed
with distilled water, and dried at 95 1C. By this process, microencapsulated ammonium polyphosphate with melamineformaldehyde (MCMF-APP) resin was obtained.
Preparation of ame retarded NR composites: to obtain vulcanisates, nano-compounds were mixed with the change of the
amount of IFR agents and MCM-41 according to the recipe in
Table 1 by a laboratory two-roll mill. The recipes of NR compounds
include carbon soot, ZnO, stearic acid, sulfur, accelerant CZ, age
inhibitor 4010 were 30, 5, 3, 1, 2.8, 1, respectively as a xed value.
All the rubber compounds were vulcanized at 150 1C in a hot press
for the optimum cure time t90 determined by a GT-M2000-A
rheometer (GaoTie Limited Co., Taiwan). All the specimens were
then cut from the vulcanized sheets and subjected to conditioning
at 20 1C for 24 h before testing.
2.3. Characterization
Infrared spectra of the APP and MCMF-APP were performed on
Nicolet MNGNA-IR 560 with 4 cm  1 resolution. The water solubility
of APP or MCMF-APP at 20 1C and 80 1C was obtained by adding
10 g of them into 100 ml distilled water and stirred at 20 1C and
80 1C for 60 min before the suspension was ltered out. 50 ml of the
ltrate was then taken out and dried to constant weight at 105 1C.
Solubility of the samples in water was calculated. The particle size
and particle size distribution of each sample was determined by a
laser particle size analyzer (Rise-2008, Shandong, China). To prevent
reuniting of the sample, the suspension was ultrasonically vibrated
for 10 min to improve before the measurements. Scanning electron
microscope (JEOL JSM-6360LV) with an accelerating voltage of
15 kV was employed to observe the morphology of the fractured
surfaces of ame retarded NR composites.
The ame retardancy of all the samples was characterized
by limiting oxygen index (LOI) and UL-94 methods. LOI data was
obtained at room temperature on an oxygen index instrument
(JF-3) produced by Jiangning Analysis Instrument Company, China,
according to ISO4589-1984 standard. The dimensions of the
samples were 126 mm  6.5 mm  3 mm. LOI is a parameter to
evaluate the ame retardancy and ammability of polymeric
materials in the same condition. It denotes the lowest volume
concentration of oxygen sustaining candle burning of materials in
nitrogen and oxygen mixed gases.
The vertical test was carried out on a CFZ-2 type instrument
(Jiangning Analysis Instrument Company, China) according to the UL94 test standard. The specimens were of 126 mm  13 mm  3 mm
according to UL-94 standard. The UL-94 test results were classied by
burning ratings V-0, V-1, or V-2 with V-0 rating presenting the best
ame retardancy of polymeric materials. The thermal stability of NR
composites was examined by thermogravimetry analysis (TGA) using
a Perkin-Elmer TGA 7 thermal analyzer at a heating rate of 10 1C/min
from room temperature to 600 1C. Nitrogen was used as a carrier gas
with a constant ow rate during the analysis. The thermal

N. Wang et al. / Fire Safety Journal 62 (2013) 281288

283

Fig. 1. FTIR spectra of APP and MCMF-APP.

degradation data was obtained from TG and DTG curves. Room

temperature tensile test of the composites was done following GB/
T528-1998 on an Instron 1211 testing machine at a crosshead speed
of 500 mm/min. The measurements were repeated for specimens for
each type of sample and the average value was calculated. Dynamic
mechanical properties of pure NR and NR composites were measured
using a dynamic mechanical thermal analyzer (DMTA V, Rheometrics
Science Corp.) at a xed frequency of 1 Hz with 3 1C/min heating rate
using liquid nitrogen as shielding gas. Storage modulus (E) and loss
factors (tan ) were obtained by rectangular tension mode in the
temperature range of  100 to 100 1C in all the experiments.

3. Results and discussion

3.1. Characterization of MCMF-APP by FTIR
The FTIR spectra of APP and MCMF-APP are shown in Fig. 1. The
typical absorption peaks of APP include 3200 (NH), 1256 (P O),
1075 (PO symmetric vibration), 1020 (symmetric vibration of
PO2), 880 (PO asymmetric stretching vibration), and 800 cm  1.
For MCMF-APP, the main absorption peaks appear at 3285, 1560,
1256, 1063, 880 and 798 cm  1. The absorptions of 1560 cm  1 is
due to the ring vibration of MEL from the MF resin and the
1063 cm  1 band is representative of symmetric COC between
melamine groups. As a result, the spectrum of MCMF-APP reveals
not only the characteristic bands of APP, but also the well-dened
absorption peaks of MF resin, indicating that MF resin exists in the
structure of MCMF-APP.

Fig. 2. The solubility of APP microencapsulated with different percentages of resin.

similar to our previous results of microencapsulated APP with

PVAmelamine-formaldehyde resin (VMFAPP) or ureamelamineformaldehyde (UMF) resin [20]. Comparing this result to our
previous work in which APP was microencapsulated with EP resin
[16], the solubility is decreased more greatly in present study. This
proves that the solubility of microencapsulated APP is related to
different coating materials.
The particle size distributions of APP and MCMF-APP are shown
in Fig. 3 and Table 2. Clearly, the average diameter of MCMF-APP is
lower than that of APP. Also, with the increase of MF content
coated onto MCMF-APP, the mean size of MCMF-APP decreases
rstly and then increases slightly. The average diameter of MCMFAPP is about 816.6 nm, smaller than that of APP (3408 nm) when
the content of MF coated on MCMF-APP is 10.9%. It had been
reported by Wang et al. [21] that the average diameter of MC-APP
is about 2800 nm when ammonium polyphosphate is microencapsulated with melamine-formaldehyde (MF) resin by the in situ
polymerization method. The particle size is much smaller than
that of microencapsulated ammonium polyphosphate with an EP
resin coating layer prepared by in situ polymerization by our
group [16]. As smaller size microcapsules is recommended to
make coatings with good homogeneity and acceptable mechanical
properties, it is expected that the MCMF-APP prepared here may
have better dispersion in NR than APP when it is blended with NR
because of its smaller average diameter and narrow particle size
distribution, which may lead to MCMF-APP/NR composites with
better ame retardancy and mechanical properties.

3.2. Water solubility and particle size distribution of MCMF-APP

3.3. Flame retardancy
Fig. 2 shows the variations of water solubility of APP and
MCMF-APP with different percentages of MF resin. The solubility
of APP at 20 1C and 80 1C are 0.601 and 9.728 g/100 ml H2O,
respectively, indicating that APP can be easily attacked by moisture or water, especially at high temperature. After the microencapsulation of APP with MF resin, however, the solubility of
MCMF-APP is decreased to 0.194% at 20 1C and 0.537% at 80 1C
when the content of MF resin is 10.9%. At both 20 1C and 80 1C, the
solubility of MCMF-APP show little change as the content of MF
resin increases. Also, unlike the large difference of solubility of APP
at 20 1C and 80 1C, the solubility of MCMF-APP at 20 1C and 80 1C is
very similar. This is due to the MF resin coating induced hydrophobic surface at the outside of APP, which leads to the decreased
solubility of APP at even higher temperature. This trend is very

In this research, MCMF-APP was mixed with PER and MEL to

produce a novel IFR. Meanwhile, the ame synergistic agent MCM41 was compounded with NR by different weight ratios to obtain
NR/MCMF-APP systems. Table 3 gives the UL-94 ratings and LOI
values for the formulations with/without microencapsulation and
MCM-41 on ammability of NR. As can be seen, with its LOI value
of only 16, NR was obviously an easy ammable polymeric
material. When 55 wt% APP was added, the LOI value of the NR/
IFR system was increased to 28.8. But it failed in vertical burning
test. The LOI value of the NR/MCMF-APP system was greatly
increased to 29.1% and the UL-94 V-1 rating was surpassed after
microencapsulation of APP with MF resin. It was believed that
smaller size microcapsules have been obtained with a good

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N. Wang et al. / Fire Safety Journal 62 (2013) 281288

Fig. 3. Size distribution of APP and MCMF-APP. (a) APP; (b) MCMF-APP (the content of MF 5%);(c) MCMF-APP (the content of MF 10.9%); and (d) MCMF-APP (the content
of MF 22.5%).

Table 2
Statistics of particle distribution of MCMF-APP.

Table 3
Effect of microcapsule and MCM-41 on ame retardancy of composites.

The content of
MF coated on MCMF-APP (%)

Mean size (nm)

0
5
10.9
22.5

3408.5
1153.8
816.6
1204.6

homogeneity and dispersion in NR matrix and the MF resin on the

outer surface of the microcapsules had improved the interface
adhesion between NR matrix and APP. As a result, acceptable re
resistance property was obtained for this formulation.
To get better ame retardancy, MCM-41 was further added to
the NR/MCMF-APP systems as a synergistic agent. As can be seen,
the LOI values of such composites were higher in comparison to
that without MCM-41 loadings even at MCM-41 content as low as
1.5 wt%. Synergism between MCM-41 and the ame retardant
additives can be easily observed at low MCM-41 loading. The UL-94
ratings and LOI results listed in Table 3 further demonstrated that
MCM-41 was an effective synergistic agent in NR. The composite
with 5 wt% MCM-41 and 55% MCMF-APP showed the maximum
LOI value of 30.2% among all the ame retardants added NR
composites and also reached V-0 rating in the UL-94 test. We
believed that MCM-41 might have played an important synergistic
role to catalyze the reaction between APP, PER and MEL, which
made char formation much more stronger and therefore led to a
better ame retardant performance for NR. The present results
were coincided with our previous study on retardant polypropylene
composites where MCM-41 had also played a good synergistic
role [16].
3.4. Dynamic mechanical properties
Dynamic mechanical properties were measured to examine the
degree of ller-matrix or llerller interactions of NR composites.

Flame retardant composite

NR0(NR)
NR1(NR/APP)
NR2(NR/APP)
NR3(NR/APP)
NR4(NR/MCMF-APP)
NR5(NR/MCMF-APP/MCM-41)
NR6(NR/MCMF-APP/MCM-41)
NR7(NR/MCMF-APP/MCM-41)
NR8(NR/MCMF-APP)
NR9(NR/MCMF-APP/MCM-41)
NR10(NR/MCMF-APP/MCM-41)
NR11(NR/MCMF-APP/MCM-41)
NR12(NR/MCMF-APP)
NR13(NR/MCMF-APP/MCM-41)
NR14(NR/MCMF-APP/MCM-41)
NR15(NR/MCMF-APP/MCM-41)

Components (phr)

100
100/35
100/45
100/55
100/35
100/35/1.5
100/35/3
100/35/5
100/45
100/45/1.5
100/45/3
100/45/5
100/55
100/55/1.5
100/55/3
100/55/5

Flame retardancy
LOI (%)

UL-94

16
25.7
27.2
28.8
25.8
25.9
26.1
26.5
27.3
27.4
27.6
28
29.1
29.8
30
30.2

Burning
Burning
Burning
V-1
Burning
V-1
Burning
Burning
V-1
V-0
V-1
V-1
V-1
V-0
V-0
V-0

The storage modulus (E) and loss factors tan() of the standard
composite (NR), NR/APP, NR/MCMF-APP and NR/MCMF-APP/MCM41 composites versus temperature are depicted in Figs. 4 and 5,
respectively. The data was summarized in Table 4.
As shown in Fig. 4, the composites exhibited a strong enhancement of the storage modulus in the following order: NR/MCMFAPP/MCM-41 4NR/MCMF-APP4 NR/APP, under all temperature
regions. The improvement of E0 was smaller below the glass
transition temperature (Tg) than that above Tg. A shift of rapid
decreasing region of E0 towards higher temperature can be seen
for NR/MCMF-APP and NR/MCMF-APP/MCM-41 composites. The
highest E0 value was obtained in the composite with addition of
both synergistic agent MCM-41 and MCMF-APP. The storage
modulus measured the recoverable strain energy in a deformed
specimen, so it reected the elastic modulus of rubber materials.
The evident E0 reinforcement in NR/MCMF-APP/MCM-41 could be

N. Wang et al. / Fire Safety Journal 62 (2013) 281288

285

Table 4
Data of DMTA analysis of NR and ame retardant NR composites.
Sample

NR3(NR/
APP)

NR12(NR/MCMFAPP)

NR15(NR/MCMF-APP/
MCM-41)

Tg (1C)
Tan of peak
position

 47.81
1.06

 47.26
0.79

 47.19
0.77

Table 5
TGA data of the NR ame retardant nano-composites.
Sample

T10%/(1C)a T20%/(1C)b T50%(1C)c Residue(%) at

560 1C

NR0(NR)
NR3(NR/APP)
NR12(NR/MCMF-APP)
NR15(NR/MCMF-APP/MCM-41)

335
300
314
306

a
b
c

360
354
360
355

394
404
416
413

26
35.36
37.62
40.63

Temperature at 10% weight loss.

Temperature at 20% weight loss.
Temperature at 50% weight loss.

Fig. 4. The temperature dependence of the storage modulus of NR ame retardant

composites.

Fig.6. TG of NR and NR ame retardant composites.

Fig. 5. The temperature dependence of tan of NR ame retardant composites.

ascribed to a higher homogeneity in the NR matrix resulted from

the lower size of the added microcapsules. The storage modulus of
the system with IFR addition was increased, leading to a lower
tan as compared to the system without IFR [22].
The glass transition temperatures of the NR composites determined from the peaks of the loss factor tan were as follows:
NR/APP (  47.81 1C), NR/MCMF-APP (  47.26 1C), NR/MCMF-APP/
MCM-41(  47.19 1C). A slight increase of the glass transition
temperature and the lower tan peak value was observed in the
NR/MCMF-APP/MCM-41 composite. The Tg increase was probably
caused by the better dispersion of microcapsules with small sizes
and nano-sized MCM-41 ller in the NR matrix, which would lead
to strong interaction between the llers and rubber molecules,
restricting the movement of polymer segments near the ller
surface and then resulting in increase of the glass transition
temperature of the matrix. The reduced chain mobility owing to

the physical and chemical adsorption of the NR molecules onto the

ller surface also caused a height reduction of tan peak during
dynamic mechanical deformation [23]. A similar result was
reported by alkov et al. in Ref. [24] in which the addition of
different kinds of montmorillonite into NR matrix had also slightly
increased the glass transition temperature and led to an evident E0
reinforcement.
3.5. Thermal stability
The TG data of all the composites are listed in Table 5. Selected
TG curves are shown in Fig. 6. The labels, T10%, T20% and T50%,
denote the temperatures at which 10%, 20% and 50% weight loss of
the samples are recorded. The addition of IFR into NR decreased
T10%, T20% and T50% values as compared to pure NR, which meant
that signicant enhancements of the thermal stability had been
achieved by adding MCMF-APP and MCMF-APP/MCM-41 into NR.
For example, the NR/MCMF-APP composite showed T10% and
T50% of 300 1C and 416 1C, which were increased 14 1C and 12 1C
respectively as compared to that of NR/APP. The char residue of

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N. Wang et al. / Fire Safety Journal 62 (2013) 281288

NR/MCMF-APP system was 37.62% at 560 1C, higher than that of

NR and NR/APP. The increased weight residue at high temperature
should be due to the formation of thermally more stable carbonaceous char [16].
As seen from Fig. 6, the decomposition processes of the NR/
MCMF-APP and NR/MCMF-APP/MCM-41 composites were similar
but with small decrease of the T10%, T20% and T50% in the latter,
indicative of some interactions between MCM-41 and MCMF-APP.
The char residue of NR/MCMF-APP/MCM-41 composite was
40.63% at 560 1C, which was higher than that of NR, NR/APP
and NR/MCMF-APP. This demonstrated that MCM-41 had further
promoted char formation of IFR system. We supposed that the
MCM-41 dispersed in the nanocomposite possessed high thermal
stability and good barrier properties, which might be able to
slowdown the heat transmission to the polymer, consequently

Table 6
Mechanical properties of NR and ame retardant NR composites.
Sample code

Components
(%)

Tensile strength
(MPa)

Elongation at
break (%)

NR0(NR)
NR3(NR/APP)
NR12(NR/MCMF-APP)
NR13(NR/MCMF-APP/
MCM-41)
NR14(NR/MCMF-APP/
MCM-41)
NR15(NR/MCMF-APP/
MCM-41)

100
100/55
100/55
100/55/1.5

22.7
7.3
7.8
8.0

432.4
187
242
276

100/55/3

8.2

280

100/55/5

9.3

288

delay the decomposition of the nanocomposite [25].The enhancement of char residue at 560 1C could be connected to the improved
anti-ammability of the polymer composites. Some difference was
obtained with the microencapsulation of EP resin with APP and its
application in PP in our previous study [16]. The results of TG
analysis of the NR composites were affected by the type of chosen
matrix and the type of interaction between matrix and used ller,
mainly including the microencapsulated resin.
3.6. Mechanical properties
The mechanical properties of NR and ame retardant NR composites are shown in Table 6. The tensile strength of pure NR was around
22.7 MPa, which was 67% higher than that of the ame retardant NR
composites reinforced by 55 wt% IFR ller. This proved that addition
of IFR ller had greatly decreased the mechanical properties of the
composites. However, after microencapsulation of ammonium polyphosphate with melamine-formaldehyde resin, elongations of
NR/MCMF-APP system at break was 242%, 29% higher than that of
NR/APP system. The tensile strength was 7.8 MPa for NR/MCMF-APP.
We believe that the interface interaction between MCMF-APP and NR
was strengthened after the microencapsulation of APP with MF resin,
indicating that the interface at the surface of particle inclusions has
played a key role in the structureproperty relationship.
After addition of synergistic agent MCM-41, the tensile strength
and elongation at break of the composites were all increased as
compared to NR/MCMF-APP. For example, for the composite with
5% MCM-41, the tensile strength and elongation at break of the
NR/MCMF-APP/MCM-41 system reached the maximum values of
9.3 MPa and 288%, which were 27.4% and 54% higher than those of

Fig. 7. SEM micrograph of ame retardant composites (a), (b) NR3(NR/APP); (c) NR12(NR/MCMF-APP); and (d) NR15 [NR/MCMF-APP/MCM-41(5%)].

N. Wang et al. / Fire Safety Journal 62 (2013) 281288

NR/MCMF-APP system, respectively. It is assumed that the stiffness of the MCM-41 ller particles has resulted in the reinforcement of the composite, the soft interlayer was formed between MF
resin and NR matrix. Such an effect has been veried in our
previous reports [2529] although it is contradict to the other
nano-synergistic systems [3032]. The difference may be due to
the higher surface area of the MCM-41 use in our study. Our
results demonstrated that microencapsulation of APP with MF
resin together with the addition of MCM-41 synergistic agent can
improve the mechanical properties of the composite effectively.
3.7. Morphology of burnt composites
Fig. 7 showed the SEM micrographs of (a, b) burnt NR/APP,
(c) NR/MCMF-APP and (d) NR/MCMF-APP/MCM-41 composites,
respectively. Relative loose structure including cracks and cavities
and some incomplete hollow fractured char could be seen on the
surface of char residue in NR/APP (Fig. 7a and b). Therefore, during
burning, heat and ammable volatiles could easily penetrate the
char layer into the ame zone. After microencapsulation of APP
with MF resin, the interface between NR and MCMF-APP was
blurrier and no obvious cavities can be observed, suggesting a
good interfacial interaction between the MCMF-APP and NR
matrix (Fig. 7c). The microstructure of char residue containing
MCM-41 displayed more homogenous and compact structure than
the samples without MCM-41 (Fig. 7d). This indicated that MCM41 was effective in retarding the degradation of underlying
materials and thus effectively stopped the transfer of heat and
ammable volatiles, which led to good ame retardancy. Moreover, the fractured surfaces were full of extensive matrix brils
which suggested plastic deformation of the matrix (Fig. 7d), which
were coincided with the mechanical results as aforementioned.
It showed that microencapsulation of APP with MF resin together
with use of MCM-41 as synergistic agent had effectively improved
the char structure and quality. As a result, improved ame
retardancy of natural rubber was obtained.

4. Conclusions
Microencapsulation of ammonium polyphosphate with melamineformaldehyde resin by an in situ polymerization method resulted in
decrease of the size and water solubility of MCMF-APP microcapsules, which were thought important to improve the homogeneity
and thermal stability of the natural rubber composite when they
were used as ame retardants. The LOI values of NR/MCMF-APP
composites were enhanced as compared to that of the NR/APP
composites at the same loading. When MCM-41 was further added
into the NR/MCMF-APP composite, a remarkable improvement of
ame retardancy was achieved, which was presented not only by
the increased LOI values, but also by the UL-94 V-0 ratings reached
by some of the NR/MCMF-APP composites. A slight increase of
the glass transition temperature, lowered tan peak value together
with the highest E0 value of natural rubber composites were
obtained with the addition of synergistic agent MCM-41 and
MCMF-APP. The addition of MCM-41 not only effectively enhanced
the ame retardancy of NR composites by acting as a synergistic
agent, but also remarkably improved the mechanical and thermal
properties of the composites in comparison to the NR/MCMF-APP
system.

Acknowledgments
The Authors gratefully acknowledge the nancial support of
the National Natural Science Foundation of China (Grant nos.

287

51103086 and 51173110), the Distinguished Young Scholars of

Liaoning Province Higher Growth Plans, China (Grant no.
LJQ2011040) and the China Postdoctoral Science Foundation
(Grant no. 2012M510922).

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