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The Flame Retardant Behaviors and Synergistic

Effect of Expandable Graphite and Dimethyl
Methylphosphonate in...

Article in Polymer Composites · February 2014

DOI: 10.1002/pc.22662

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The Flame Retardant Behaviors and Synergistic
Effect of Expandable Graphite and Dimethyl
Methylphosphonate in Rigid Polyurethane Foams
Fafei Feng, Lijun Qian
Department of Materials Science and Engineering, Beijing Technology and Business University, Beijing
100048, China
A series of flame-retardant rigid polyurethane foams
(RPUFs) containing dimethyl methylphosphonate
(DMMP) and expandable graphite (EG) were prepared
by box-foaming. The RPUFs were characterized by ther-
mogravimetric analysis (TGA), the limiting oxygen index
(LOI), cone calorimeter, and scanning electron micro-
scope (SEM). The decomposition process of DMMP
was investigated by Pyrolysis-Gas Chromatography/
Mass Spectroscopy (Py-GC/MS). Accordingly, their
flame retardant behaviors and mechanism were also
discussed. The results show that the DMMP/EG system
can linearly enhance the LOI value from 19.2% of the
pure RPUF to 33.0% of RPUFs containing 16 wt% flame
retardant. In addition, the DMMP/EG system also
remarkably increases yields of the residual char and
drastically decreases the peak value of heat release
rate (PHRR), heat release rate (HRR), total heat release
(THR), total smoke release (TSR), and the yields of CO
(COY). In the flame retardant RPUFs, when the matrix is
ignited, the flame retardant DMMP should be decom-
posed to gaseous PO2 fragments, which can inhibit free
radical chain reaction of flammable alkyl free radical
from the decomposed matrix; whereas the flame retard-
ant EG can rapidly expand and form loose and worm-
like expanding graphite char layer accordingly, which
can hinder the heat transmission to the inner matrix
and reduce decomposing velocity of matrix. After the
combination of the two flame retardant effects, the
DMMP/EG flame retardant system provides the matrix
with better flame retardant effects than one of them
does. Namely, it shows excellent gas-condensed bi-
phase synergistic effect. POLYM. COMPOS., 00:000–000,
2013. VC 2013 Society of Plastics Engineers
Correspondence to: Lijun Qian; e-mail: qianlj@th.btbu.edu.cn
Contract grant sponsor: Importation and Development of High-Caliber
Talents Project of Beijing Municipal Institutions; contract grant number:
CIT&TCD201304028.
Additional Supporting Information may be found in the online version
of this article.
DOI 10.1002/pc.22662
Published online in Wiley Online Library (wileyonlinelibrary.com).
C 2013 Society of Plastics Engineers
V flame retardant systems for polyurethane foams have been
POLYMER COMPOSITES—2013
INTRODUCTION
Polyurethane, made by the reaction between di-
isocyanates or polyisocyanates and diols or polyols, has
already been one of the most important polymers, which
has a wide range of applications such as coatings, flexible
or rigid foams, adhesives, sealants, synthetic leathers,
membranes, and elastomers in both industry and daily life
[1, 2]. Typically, rigid polyurethane foams (RPUFs) are
extensively used as thermal insulation materials due to
lower thermal conductivity and better physical and
mechanical properties than those of polystyrene foams.
However, the application of RPUFs is restricted in the
construction industry because of the high flammability,
where the stringent standards on the flammability of
materials are imposed [3].
The flammability of flexible or rigid polyurethane
foams is caused by their porous cellular structure full of
gases. In the past years, considerable efforts have been
made to enhance the flame retardancy of RPUFs from both
academy and industry. So far, inorganic fire-retardants,
e.g., alumina trihydrate (ATH) [4], expandable graphite
(EG) [5, 6], and ammonium polyphosphate (APP) [7–9],
and organic ones [10, 11], e.g., triethylphosphate (TEP)
[12], dimethyl methylphosphonate (DMMP), tris-(2-chloro-
propyl)-phosphate (TCPP) [13], and tris-(2-chloroethyl)-
phosphate (TCEP) all have been incorporated into RPUFs
to investigate the flame retardant effects, respectively.
Expandable graphite (EG) is a kind of effective inor-
ganic intumescent halogen-free flame retardant for most of
polymeric materials, and has been widely used in the
RPUFs in recent years. Several groups have researched the
flame retardant effects of different-sized expandable graph-
ite particles and different addition amount in rigid polyur-
ethane foams [14–16]. It discloses that sulfuric acid
intercalated between layers of graphite boils and releases
vapors when EG is rapidly heated, which results in exfolia-
tion and expansion of the graphite slice. Furthermore, EG
and other constituents (e.g., hollow glass microsphere [17],
whisker silicon oxide [18], organic phosphate [19]) as
 TABLE 1. The basic formula of RPUFs.
Component A
Component B
450L KAc Am-1 DMCHA 141b Water Stabilizer
(g) (g) (g) (g) (g) (g) (g)
72.00 0.36 0.36 1.44 14.40 0.90 2.70
reported in a few literatures. However, a large amount of
EG is incorporated into RPUFs for obtaining better flame
retardancy of the matrix, which not only makes foaming
process harder but also sacrifices the mechanical properties
and the thermal conductivity of the materials.
In this study, we introduce another liquid flame retard-
ant dimethyl methylphosphonate (DMMP) into the matrix
in order to explore the high-efficiency flame retardant
way. The flame retardancy and physical properties of the
bi-component flame-retardant RPUFs are systematically
researched and the flame retardant synergistic effect of
DMMP/EG is also discussed.
EXPERIMENTAL
Materials
(1) Polyether polyol, DSU-450L, was supplied by Dexin
Lianbang Chemical Industry Co., Shandong, China. The
main properties are as follows: typical hydroxyl value
(450 6 10) mg potassium hydroxide (KOH) equiv g21;
water content, not more than 0.1 wt%; viscosity (25 C),
6000–10000 mPa
s; potassium ion (K1), not more than 8
mg kg21; colority GD, not more than 8; pH, 4–6. (2) About
30% potassium acetate solution (KAc), colorless to pale
yellow transparent liquid used as catalyst, was purchased
from Liyang Yutian Chemical Co., Jiangsu, China. (3) Pen-
tamethyldiethylenetriamine (Am-1), an effective catalyst for
RPUFs, was obtained from Liyang Yutian Chemical Co.,
Jiangsu, China. (4) N,N-Dimethylcyclohexylamine
(DMCHA), another catalyst, colorless liquid, was also pur-
chased from Liyang Yutian Chemical Co., Jiangsu, China.
(5) 1,1-Dichloro-1-fluoroethane (141b), blowing agent, was
supplied by Hangzhou Fushite Chemical Industry Co., Zhe-
jiang, China. (6) Distilled water (H2O), blowing agent, was
prepared in our laboratory. (7) AK-8803, with good nuclea-
tion and liquid flowability, PU Foam Stabilizer AK Series,
was bought from Jiangsu Maysta Chemical Co., China. (8)
Dimethyl methylphosphonate (DMMP), was supplied by
Beijing Donghua Rio Tinto Technology Development Co.,
China. Purity is 99%. (9) Expandable graphite (EG), ADT
350, was produced by Shijiazhuang ADT Carbonic Material
TABLE 2. The formulas of flame retardants in RPUFs.
Samples F0 F1 F2
FR content (%) 0 8 10
DMMP (g) 0 3.49 4.46
EG (g) 0 13.97 17.86
2 POLYMER COMPOSITES—2013
Factory, Hebei, China. Main properties are: moisture,
0.56%; pH value, 7.0; expansion rate, 350 mL g21; volatile,
17.1%; ash, 4.8%; particle size (not less than 300 lm),
PAPI 83%; purity, not less than 95%. (10) Isocyanate, 44V20,
(g) PAPI, was purchased from German Bayer Company. Main
108.00
performance indices are as follows: –NCO weight percent,
30%; monomer MDI content, 52%. All of the chemicals
were used as received.
Preparation of Rigid Polyurethane Foams
Pure RPUF and DMMP/EG-filled RPUFs were prepared
by box-foaming in our laboratory according to the follow-
ing formula listed in Tables 1 and 2. Take the preparation
of pure RPUF for example. First, all the items of compo-
nent A in Table 1 were mixed and stirred with an electric
stirrer until a uniform mixture was achieved. Then compo-
nent B was added into the above mixture and was stirred
again for an additional 20 s at elevated stir speed and then
the mixture was quickly poured into an open paper mold
(250 3 250 3 60 mm3) in order to obtain free-rise foam.
The polymerization reaction was quickly initiated among
the distilled water, ployether polyol, and PAPI, and the
resulting foam fleetly formed and expanded simultane-
ously. Finally, the foams were put in an oven for 30 min
at 70 C to accelerate the curing process. DMMP/EG-filled
RPUFs were prepared with the same method. The only dif-
ference was that DMMP and EG were firstly incorporated
into component A with the ratio of flame retardant ingre-
dients in Table 2 before foaming. After foaming, the prod-
ucts were taken out from the paper mold. The samples
were cut into desired shapes and sizes according to the
corresponding standards for the evaluation of different
properties. The total adding amounts of DMMP and EG in
the composites ranged from 0 to 16 wt%, namely, 0, 8, 10,
12, 14, and 16 wt% in sequence. In addition, the ratio of
DMMP to EG in bi-component flame-retardant RPUFs
was 1:4 by weight, which has been determined as an opti-
mized ratio by the previous work as seen in supporting
information. Moreover, 10 wt% DMMP-filled RPUF as
sample Fa, 10 wt% EG-filled RPUF as sample Fb, 12 wt%
DMMP-filled RPUF as sample Fc and 12 wt% EG-filled
RPUF as sample Fd were also prepared, respectively, in
order to further illuminate the synergistic effect between
DMMP and EG in RPUFs.
Characterizations
Thermogravimetric Analysis. TGA of samples was
performed on TA instrument Q5000IR thermal
F3 F4 F5 Fa Fb Fc Fd
12 14 16 10 10 12 12
5.47 6.52 7.63 22.32 0 27.36 0
21.89 26.06 30.53 0 22.32 0 27.36
DOI 10.1002/pc
gravimetric analyzer with a heating rate of 10 C min21
from 30 to 700 C under N2 atmosphere. All the samples
were tested with a gas flow rate of 30 mL min21.
Limiting Oxygen Index (LOI) Test. The LOI values
were obtained on a FTT (Fire Testing Technology, UK)
Dynisco LOI instrument according to ASTM D 2863-97
with sheet dimension 100 3 10 3 10 mm3.
Cone Calorimeter Test. The fire behavior was charac-
terized on a FTT cone calorimeter according to ISO5660
under an external heat flux of 50 kW m22. The dimension
of samples was 100 3 100 3 30 mm3. Heat release rate
(HRR), total heat release (THR), total smoke release
(TSR), and other parameters were recorded simultaneously.
Pyrolysis-Gas Chromatography/Mass Spectroscopy
(Py-GC/MS) Test. Pyrolysis-Gas Chromatography/Mass
Spectroscopy (Py-GC/MS) analyses were performed on a
Shimadzu Model GC-17A-GCMS-QP5050A under below
conditions: the injector temperature was 250 C and the
interface temperature of GC/MS was kept at 280 C; the
temperature program started at 50 C, held for 1 min, and
then increased to 280 C at the rate of 8 C min21; the
cracker temperature was 500 C.
Scanning Electron Microscope (SEM). The micro-
morphology of the residual char after combustion with a
conductive gold layer was observed using a FP 2032/14
Quanta 250 FEG scanning electron microscope (SEM)
under high vacuum with voltage of 15 kV.
Thermal Conductivity. The thermal conductivity of
samples was performed on a thermal conductivity tester
EKO instruments according to ASTM C 518-04. The tem-
peratures of upper plate and lower plate were set at 16 C,
34 C respectively, which kept the sample at an average
temperature of 25 C. The dimension of the specimens
was 200 3 200 3 40 mm3.
Open and Closed Cell. Average open and closed cell
values were measured on an Ultrafoam 1200e V4.01
instrument according to ASTM D 6226-05. The size of
samples was 25 3 25 3 25 mm3.
Apparent Density. Apparent density of samples was
calculated according to ISO 845:2006. The dimension of
the specimen was 30 3 30 3 30 mm3.
RESULTS AND DISCUSSION
Thermal Stability
Figure 1 shows the corresponding TG curves of the
investigated samples. The sample F0 without flame
retardant has three visible degradation stages. As we see,
there should be some mass loss, 1.7 wt% or so, in the
DOI 10.1002/pc
FIG. 1. The TGA curves of the samples F0–F5. [Color figure can be
viewed in the online issue, which is available at wileyonlinelibrary.com.]
first stage between 100 and 110 C because of the evapo-
ration of water from the sample. It is obvious that the
second thermal degradation process occurs from 120 to
250 C and has about 6.5 wt% mass loss, probably corre-
sponding to the cleavage of the urethane bond, and the
third degradation stage is mainly decomposing process
from 250 to 550 C, which has a maximum mass loss rate
at about 320 C and has about 79.0 wt% mass loss due to
the thermal depolymerization reaction of polyisocyanates
and polyols, releasing some gaseous products [12, 20].
And then F0 exhibits a slow degradation rate in the range
of 550 to 700 C. Finally, only 12.8 wt% residual char
remains at 700 C.
Compared with the sample F0, the other samples F1–
F5 have a significantly similar decomposing trend. But
three differences also can be observed between F0 and
F1–F5. The first difference is that F1–F5 have more mass
loss during the first degradation stage from 120 to 250 C,
which is attributed to the volatilization and thermal pyrol-
ysis of the flame retardant DMMP because its boiling
temperature is just 181 C and it is easily volatile [21]. As
a consequence, the phosphorus-containing fragments are
released by DMMP and act effectively in gas phase.
Meanwhile, the remaining DMMP may still exist in the
matrix and subsequently exert a little flame retardant
effect in condensed phase. The second difference lies in
the decomposition velocity in the temperature range of
250 to 550 C. Obviously, in this degradation step the
decomposition velocity of samples F1–F5 is slower than
that of virgin F0, which is caused by the comprehensive
degrading behavior of the flame retardants DMMP and
EG, including the vaporization or decomposition of
DMMP and high thermal stability of EG. Some investiga-
tors think that the phenomenon should be ascribed to the
formation of thermally stable intermediates composed of
phosphoric acid derivatives produced by DMMP at ele-
vated temperature [[22]]. The third difference is that the
char yields at 700 C gradually raise with the increase of
POLYMER COMPOSITES—2013 3

FIG. 2. The LOI values and their fitting curve of the RPUFs.
DMMP/EG amount. Of course, the increase of EG in
matrix is the main reason which leads to the increase of
residue char yields. As we know, EG is thermal stable
material and hardly reduces its weight below 700 C, and
it will only turn into the expansive worm-like char [[23]],
which serves as an effective carbonaceous heat-insulation
barrier layer, preventing the heat and air from penetrating
the underlying substrate. Basically, the char yield raises
with the increase of flame retardants DMMP/EG. But EG
has a relative bigger particle size, which leads to the
microscopic dispersion heterogeneity of the EG in matrix.
Therefore, there is some acceptable fluctuation in the
yields of residual char of F3–F5.
LOI Test
LOI test is a kind of simple yet important method to
evaluate the flame retardancy of polymeric materials.
Therefore, the LOI values of the RPUF specimens with
different total adding amounts of flame retardants
DMMP/EG were measured so as to research the influence
of DMMP/EG on the fire-resistant behaviors of the
RPUFs.
The LOI values of the RPUFs with different DMMP/
EG amounts are illustrated in Fig. 2. It is noteworthy that
the LOI value increases drastically from 19.2% of F0
without flame retardant to 27.0% of F1 containing 8 wt%
DMMP/EG. Subsequently, the LOI values of the samples
F1–F5 continue increasing up to 33.0% with the increase
of flame retardants in matrix. The linear correlation has
also been observed between LOI values and the adding
amounts of flame retardants in matrix. It implies that
addition of flame retardants is the only factor influencing
on flame retardancy of the samples and there isn’t a syn-
ergistic effect between FR and matrix.
Furthermore, we choose the DMMP/EG flame retard-
ants with certain 1/4 weight ratio. The reason is that we
determine there is a synergistic effect between DMMP
4 POLYMER COMPOSITES—2013
and EG and this ratio is an optimal one which can show
remarkable synergistic effect. For clearly explaining it,
we mark the LOI values of two groups of specimens. One
group includes F2 containing 10 wt% DMMP/EG (1/4 by
weight) flame retardant, the sample Fa with 10 wt%
DMMP and the sample Fb with 10 wt% EG, and the
other group includes F3 containing 12 wt% DMMP/EG,
the sample Fc with 12 wt% DMMP and the sample Fd
with 12 wt% EG, as showed in Fig. 2. Obviously, the cor-
responding LOI values of Fa and Fb are 24.6% and
27.2%, which are obviously lower than that of F2 with 10
wt% DMMP/EG. Meanwhile, 24.9% of Fc and 28.6% of
Fd are also lower than that of F3. Therefore, we confirm
that the flame retardants DMMP and EG have a synergis-
tic effect in RPUF. When they are used in matrix simulta-
neously with a certain ratio, at least the matrix can
possess higher LOI value.
Additionally, as mentioned above, DMMP can release
gaseous phosphorus-containing fragments due to the fact
that it has about 181 C temperature of vaporization or
decomposition, and the fragments inhibit the intensity of
flame, which exhibits a mechanism of gas-phase action.
Whereas EG can promote the formation of larger-volume
residual char of RPUFs and it shows a condensed-phase
action. Therefore, we conclude that the high LOI value of
RPUFs is attributed to the synergistic effect, composed of
the gas-phase flame retardant effect from DMMP and the
condensed-phase flame retardant effect from EG and the
probable condensed-phase flame retardant effect from
DMMP.
Herein, in order to avoid the repeated discussion and
simplify the analytical process, we take the samples Fa
and Fb to explain the synergistic effect of DMMP and
EG, and do not mention the samples Fc and Fd any
longer.
Cone Calorimeter Test
As we know, the cone calorimeter test usually gives
several combustion parameters which are used to assess
fire safety, including time to ignition (TTI), the heat
release rate (HRR), total heat release (THR), total smoke
release (TSR), yield of CO (COY), and so on [24]. These
parameters of RPUFs were also tested by cone calorime-
ter, as partially illustrated in Fig. 3 and listed in Table 3.
Herein, in order to make the HRR curves more clear,
we choose the samples F0, F1, and F5 as the representa-
tion of all the samples. From Fig. 3, it is not hard to see
that the TTIs of the specimens are rather short and their
heat release rates rapidly rise to the maximum value after
burning because the porous cellular structure of the
RPUFs increases the contact area between the substrate
and oxygen. But more importantly, we observe a remark-
able decrease of the peak value of heat release rate
(PHRR) in sequence from F0 to F5 with the increase of
DMMP/EG in RPUFs. When the adding amounts of
DMMP/EG reach 16 wt% in F5, the PHRR has
DOI 10.1002/pc

FIG. 3. The HRR curves of the samples F0, F1, and F5 and the fitting
PHRR curve of F0–F5.
been reduced by 64.9% than that of F0. Accordingly, the
Av-HRR (between 1 and 300 s) and THR values have
also been drastically reduced by 67.4 and 57.8%, respec-
tively, in Table 3. Combining with the results from LOI
and TGA, we can deduce the reasons why DMMP and
EG can reduce the PHRR, HRR, and THR of RPUFs. On
the one hand, DMMP can volatilize or degrade prior to
burning, and produce PO2 free radicals which can quench
the flammable alkyl and hydroxyl free radicals from the
decomposition of the matrix in gas phase. As a result, the
DMMP can restrain the drastic intensity of combustion to
some extent in gas phase. It is a critical factor in reduc-
tion of PHRR, HRR, and THR of RPUFs. On the other
hand, the volume of EG dramatically increases after ther-
mal expansion. At the beginning of burning of the matrix,
the loose porous worm-like char can not only serve as an
excellent barrier to heat but also inhibit production of
combustible gases from thermal decomposition of foams,
which can effectively control further thermo-oxidative
degradation of RPUFs. It is another critical factor in
reduction of HRR. All these disclose that DMMP/EG sys-
tem inhibits the heat release of combustion, weaken the
thermal degradation intensity of combustion of RPUFs,
and thus bring excellent flame retardant effect on RPUF
matrix.
Then, as a potential construction material, TSR and
COY of the RPUFs are also important factors to evaluate
the anti-fire performance. The more inspiring results are
that the values of TSR and COY all have outstandingly
decreased due to the existence of DMMP/EG, as listed in
Table 3. The reason is that the flame retardant DMMP
can promote charring of the larger decomposed frag-
ments, which is the main content of smoke, and the resi-
due formed by the expanded graphite can filtrate or
absorb the charred fragments, and thus the TSR is dra-
matically reduced. Accordingly, the more decomposed
fragments were reserved in the residue, the less fragments
were burned in fire and the less CO was released. That’s
why the COY value can be reduced. In addition, the TSR
gradually reduces from F0 to F4, but the sample F5’ TSR
suddenly increases. We deduce that the more DMMP in
matrix prevents from the combustion of the gas contain-
ing fragments of decomposed matrix, accordingly the
decomposed fragments undergoing incomplete burning,
and thus the higher smoke concentration forms in gas
phase. Of course, the TSR of F5 is still far lower than
that of F0. Smoke and CO are both dangerous fire factors
in people’s life. Therefore, their reductions are extremely
important improvement on flame retardancy of materials.
Furthermore, in order to disclose the flame retardant
synergistic effect of DMMP and EG in RPUFs during
combustion, the cone calorimeter tests of Fa, Fb, and F2
were also carried out and the corresponding HRR curves
are illustrated in Fig. 4. As we see, although the flame
retardants in samples have the same total amounts, the
PHRRs of Fa and Fb are higher than that of F2, but is far
lower than that of the virgin F0. Therefore, we consider
that the DMMP and EG can effectively amend the defects
of each other during the combustion of flame retardant
PU. Especially, when the flame retardant effects in gas
phase from DMMP and in condensed phase from EG are
combined with a certain ratio, the DMMP/EG system will
show an obvious bi-phase synergistic effect, which has
also been observed in LOI result.

TABLE 3. The parameters of RPUFs investigated by the cone calorim-

eter test.

PHRR Av-HRR THR TSR COY

Samples (kW
m22) (kW
m22) (MJ
m22) (m2
m22) (kg
kg21)

F0 317 84.9 25.1 955 87.9

F1 168 60.9 21.2 540 16.7
F2 146 57.3 21.5 437 20.6
F3 134 55.5 20.5 390 22.6
F4 119 49.4 18.0 287 24.6
F5 111 27.7 10.6 581 21.0
Fa 230 73.0 21.8 1169 27.6
Fb 169 58.4 22.8 288 19.2
FIG. 4. The HRR curves of the samples Fa, Fb, and F2.

DOI 10.1002/pc POLYMER COMPOSITES—2013 5


FIG. 5. The Py-GC/MS spectrum of DMMP and the deduced structure
of typical m/z peaks.
The Py-GC/MS analysis of DMMP
The decomposition process of DMMP was investigated
by Pyrolysis-Gas Chromatography/Mass Spectroscopy
(Py-GC/MS) to make the action mechanism of DMMP
clarify. The pyrolysis temperature is set at 500 C where
DMMP has been broken completely. We select a typical
fragment flow with some characteristic ionic peaks as
illustrated in Fig. 5. According to the structure of
DMMP, it is not hard to deduce the corresponding struc-
tures of each fragment. First, the peak at m/z 124 should
be the molecular ionic peak of DMMP because the
molecular weight of DMMP is 124. Second, the m/z of
fragments at 124, 109, 94, and 79 with an interval 15 are
formed due to the dissociation of methyl step by step.
Finally, two distinctive characteristic ionic peaks are
observed at m/z 63 and 47, which correspond to PO2 and
PO free radicals, respectively. According to the above
analysis, the decomposition route of DMMP is elucidated
in Fig. 6. Therefore, it can be powerfully demonstrated
that DMMP plays an important role in gas phase during
combustion based on the fact that PO2 and PO free radi-
cals produced by DMMP can quench the flammable
active free radicals from the matrix and inhibit the burn-
ing intensity of the matrix.
FIG. 6. The decomposition route of DMMP.
6 POLYMER COMPOSITES—2013
The Analysis of Residual Char Photos
Residual char photos of all the samples after the cone
calorimeter test and the original F2 photo are shown in
Fig. 7. The original F2 photo expresses that the sample is
homogenous and uniform on the whole. Namely, EG
blends well with the RPUFs. From Fig. 7, only a little
curly residual char remains of the sample F0 and Fa,
which means the pure RPUF will fully degrade under
higher temperature and DMMP has not obviously pro-
moted charring effect yet, and thus it mainly exert its
effect in gas phase [25]. But the residues from F1 to F5
and Fb are very different and a lot of residue is reserved,
which confirms that EG in RPUF results in the formation
of loose and worm-like expanding graphite char layer.
The char layer can effectively inhibit heat spreading so
that some original matrix still remains in the residues of
F4 and F5.
In order to further testify the inference above, SEM
photos of residual char obtained from samples F0, F2, Fa,
and Fb are also illustrated in Fig. 8. Conspicuously, we
can observe some distinct morphological discrepancies.
With respect to the virgin F0, the char residue formed
during combustion is compact but rather thin, which can-
not hamper the heat and mass transfer effectively. For
sample Fa only containing DMMP, a thick and holey car-
bonaceous layer is generated because of the formation of
phosphoric acid analogues and the emission of gaseous
products through vaporization or decomposition of flame
retardant DMMP. Such layer can serve as an insulation
barrier to some extent. In the case of only EG-containing
sample Fb, it is markedly found that the gaps of worm-
like expandable graphite are filled with amount of incom-
plete and lamellar residual char. In fact, good flame
retardancy of sample Fb should be mainly ascribed to the
barrier effect of EG to the heat and oxygen on the surface
of the matrix. In comparison with residual char of sam-
ples F0, Fa, Fb, the char layer of sample F2 consists of
worm-like graphite and complete compact char superior
to that of sample Fb. In other words, the char layer of
sample F2 offsets the deficiencies of samples Fa and Fb
in the condensed phase.
Therefore, in combination with results from TGA, LOI
test, and cone calorimeter test, we conclude that DMMP
DOI 10.1002/pc
 FIG. 7. Residual char photos of all the samples and original F2 photo. [Color figure can be viewed in the
online issue, which is available at wileyonlinelibrary.com.]

FIG. 8. SEM photos of the samples F0, F2, Fa, and Fb after combustion.

DOI 10.1002/pc POLYMER COMPOSITES—2013 7

 reduces the burning intensity but also inhibits the thermal
feedback to the matrix and further decreases the decom-
position velocity of matrix. All the flame retardant effects
are combined together to produce better flame retardant
behaviors. Therefore, we are certain that DMMP and EG
flame retardant system has a gas-condensed bi-phase syn-
ergistic effect.

Physical Properties
As the essential parameters, the physical properties of
the samples, such as thermal conductivity, the ratio of
open and closed cell and apparent density, are also
detected and the results are listed in Table 4.
From the data in Table 4, the incorporation of the
FIG. 9. The bi-phase synergistic flame retardant mechanism of DMMP DMMP/EG leads to the slight enhancement of thermal
and EG. [Color figure can be viewed in the online issue, which is avail-
conductivity of the matrix, but we also observe that the
able at wileyonlinelibrary.com.]
thermal conductivity of the samples increases by less than
10 wt%, which is probably attributed to the higher ther-
and EG produce the flame retardant effect in gas phase
mal conductivity of DMMP/EG than that of matrix.
and condensed phase respectively, but the flame retardant
The ratio of open and closed cell is also an important
effect will be maximized when the gas-phase effect of
parameter to characterize the cell structure that has a pro-
DMMP and the condensed-phase effect of EG are
found influence on the usability of the RPUFs. It not only
adjusted to the appropriate ratio.
can disclose foaming performance, but also is used to
evaluate the thermal insulation and water absorption prop-
The Bi-phase Synergistic Flame Retardant Mechanism of erties. With addition of DMMP/EG, the closed cell con-
DMMP and EG tent of the fire-retardant samples F1–F5 only has a subtle
increase in comparison with that of F0, which means that
The flame retardant mechanism is illustrated in Fig. 9. the flame retardant system would not disturb the foaming
As we mentioned, when the flame retardant RPUFs are process. It is very critical to reserve the processability
ignited or heated to decompose, the DMMP in the sam- and usability of RPUF.
ples will be volatile and decompose to form gaseous PO2 Apparent density is a very important factor in the
fragments. At the same time, the PU matrix also begins usability of the RPUFs. In general, the foam density
to decompose and release the ignitable alkyl free radicals. depends on foaming rate [26]. During the preparation of
If there is no flame retardant added, the matrix will com- the RPUFs, the EG is the only solid filler, which certainly
bust drastically. But due to the existence of DMMP, increases the density of foaming. Of course, all the appa-
whose decomposition products PO2 fragments are excel- rent densities of flame retardant samples are lower than
lent quencher of ignited free radicals, the intensity of 47.2 kg
m23. Undoubtedly, the effect of flame retardants
combustion will be inhibited rapidly in a lower level. Of on the RPUF foaming is relatively less and would not
course, the DMMP perhaps produces some phosphorus hinder researches or even application.
acid to promote charring, but its main flame retardant
effects should be exerted in gas phase. In addition, the
heated EG begins to expand to fill in the space formed by CONCLUSIONS
the decomposed matrix. Accordingly, EG absorbs some A high efficiency halogen-free flame retardant RPUFs
energy from combustion. Further, the EG forms loose and based on DMMP/EG system were prepared and
worm-like expanding graphite char layer, which has
excellent heat-insulation property and inhibits the heat TABLE 4. The physical properties of the samples.
transmission from fire and heat conduction, further keeps
the matrix from heat and reduces or prevents from degra- Coefficient of Average Apparent
dation of the matrix. The loose and expanding graphite thermal conductivity closed density
Samples (W
m21
K21) cell (%) (kg
m23)
char also has capability to filtrate or absorb larger frag-
ments and thus reduces the amount of flammable sub- F0 0.020 85.4 36.0
stance and further decreases the burning intensity. F1 0.021 85.6 39.1
Furthermore, the combined flame retardant effects are F2 0.021 87.2 41.0
obviously superior to DMMP or EG alone according to F3 0.022 87.4 47.2
F4 0.021 86.3 43.6
the results of LOI, the cone calorimeter and the char pho- F5 0.022 87.5 46.3
tos. The DMMP/EG flame retardant system not only

8 POLYMER COMPOSITES—2013 DOI 10.1002/pc

 investigated. The DMMP/EG system can linearly enhance
the LOI value from 19.2% of the pure RPUF to 33.0% of
RPUFs with 16 wt% flame retardants. The DMMP/EG
system also remarkably increases yields of the residual
char and drastically decreases the PHRR, HRR, THR,
TSR, and COY. All these performances were ascribed to
the flame retardant synergistic effect of EG and DMMP.
The flame retardant DMMP mainly decomposes to gase-
ous PO2 fragments which can inhibit the free radical
chain reaction of flammable alkyl free radical from
decomposed matrix. And thus DMMP shows better flame
retardant effect in gas phase. During the process of initial
combustion, the flame retardant EG rapidly expands and
forms loose and worm-like expanding graphite char layer
accordingly which can hinder the heat transmission to the
inner matrix and reduce decomposing velocity of matrix.
Undoubtedly, EG shows excellent flame retardant effect
in condensed phase. Through the combination of the two
flame retardant effects with a certain ratio, the DMMP/
EG system exerts more excellent fire-resistance effect
than DMMP or EG does alone. In a word, we are certain
that the DMMP/EG system has gas-condensed bi-phase
synergistic effect.
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