Journal of Thermoplastic Composite Materials OnlineFirst, published on June 19, 2009 as

doi:10.1177/0892705709093502

Study on Thermal Decomposition of

Intumescent Fire-Retardant Polypropylene
by TG/Fourier Transform Infrared

FENG ZHANG, JUN ZHANG* AND DAOXING SUN

Key Laboratory of Rubber-Plastics for Ministry of Education, Qingdao
University of Science and Technology, 53 Zheng Zhou Road
Qingdao 266042, P.R. China

ABSTRACT: The thermal decomposition processes of polypropylene formulations

containing intumescent flame-retardant additives as well as the individual
components in the composites have been studied using thermogravimetric analysis
and real time Fourier transform infrared in both air and nitrogen atmospheres.
The results show that the thermal decomposition processes of pure polypropylene
(PP), polyamide, pentaerythritol, and intumecent flame-retarded PP (IFR-PP)
composites in air are significantly different from that in nitrogen atmosphere. The
existence of oxygen promotes the decomposition of the above materials. However,
oxygen has little influence on the thermal decomposition of ammonium polyphos-
phate and zinc borate both in air and nitrogen atmospheres. All IFR-PP composites
show an earlier onset of decomposition in comparison with pure PP both in nitrogen
and air atmospheres. Accordingly, the initial release gases such as NH3 or H2O help
to swell the melted PP polymer and improve the flame retardancy of IFR-PP
composite. At temperature higher than 2908C in air and 4408C in nitrogen, the IFR-
PP composites are more thermally stable than PP because of the incorporation of
intumescent flame additives. The decomposition mechanisms of these materials are
discussed based on the analysis of the results of TG/FTIR.

KEY WORDS: thermal decomposition, polypropylene, intumescent fire-retardant,

TG, FTIR.

INTRODUCTION

OLYPROPYLENE (PP) IS widely used in many fields such as housing

P materials, transport, and electrical engineering applications. This poly-
mer is inherently flammable due to its chemical constitution and flame

*Author to whom correspondence should be addressed. E-mail: [email protected]

Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 00—Month 2009 1

0892-7057/09/00 0001–21 $10.00/0 DOI: 10.1177/0892705708093502
ß SAGE Publications 2009
Los Angeles, London, New Delhi and Singapore

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2 F. ZHANG ET AL.

retardancy is usually required in its applications. Although halogen-

containing fire-retardants are effective for PP, the environmental problems
associated with these flame retardants are concerned nowadays, which has
limited their use in many occasions. As an alternative way to improve the
polymer’s fire-resistance, the use of intumescent fire-retardant systems is
growing rapidly [1–4].
Flame retardant intumescent materials are halogen-free, which provide
flame-retardant properties by developing a carbonaceous shield (char) on
the surface protecting the underlying material from the action of the incident
heat flux. The resulting char reduces the heat transfer to the substrate. The
intumescence concept allows a balance between the fire properties and the
level of additives in the material [5–7]. In recent years, intumescent flame-
retardant additives have been widely used in the flame-retarded PP.
Generally, intumescent formulations include three major components [8–10]:
(1) acid source such as phosphate, (2) carbonific agent such as polyol,
(3) blowing agent such as melamine. When exposed to the heat flux from
a fire, the temperature within these materials rises, causing the thermoplastic
to melt. At a critical temperature, an endothermal chemical reaction releases
volatiles, resulting in swelling of the intumescent layer as many times as
its original thickness. There are several reactions occurring almost
simultaneously, but in a proper sequence during swelling. First, the acid
source must decompose to yield an inorganic acid. Then, it takes part in
the dehydration of the carbon source to yield the carbonaceous char.
Finally, the blowing agent decomposes to yield gaseous products that cause
the char to swell, and hence provide the thermal barriers to protect the
underlying materials.
Camino et al. [11] have reviewed the developments of intumescent and
chemical–physical mechanisms of intumescent fire-retardant systems. Bras
and Bourbigot [12] have done extensive studies on ammonium polyphos-
phate/pentaerythritol/melamine (APP/PER/MEL) system and completed a
review about fire-retarded intumescent thermoplastics formulations,
synergy, and synergistic agents. In particular, intumescent mixtures of the
additives APP and Polyamide-6 (PA6) have been developed for use in PP
and ethylene–vinyl acetate copolymer [9].
The thermal decomposition processes of PP formulations have been
extensively studied regarding the condensed phase, whereas low attention
has been paid to the gas phase. In this work, TG/FTIR technique with both
air and nitrogen atmospheres was used to investigate the decomposition
processes of intumecent flame-retarded PP composites (IFR-PP) containing
intumescent flame-retardant additives by analyzing volatiles under different
conditions.

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Study on Thermal Decomposition of IFR-PP 3

EXPERIMENTAL

Materials

Polypropylene (PP from Dalian Petrochemical Corporation, MFI ¼ 2.1–

3.9 g/10 min, the type is iPP) was used in the present work; pentaerythritol
(PER) was supplied by Tianjin BoDi; ammonium polyphosphate (APP,
crystalline form is II, n41000) was made by Haida Chemical; zinc borate
(ZB, the formula is 2ZnO  3B2O3  3  5H2O) was supplied by Zhenjiang
Sulfuric Acid Corporation; polyamide-6 (PA6, grade is Reinforced) was
manufactured by Shanghai Plastics Corporation; a sodium-based mont-
morillonite (MMT) was provided by Zhejiang Fenghong company; zeolite
(ZEO, Particle size: 2–4 mm) was prepared in our laboratory.
MMT was used to prepare organic montmorillonite (OMMT) according
to the literature [13]. An aqueous solution of cetyltrimethylammonium
bromide was selected as intercalant. PA6nano was prepared by extruding
the mixture of PA6 and OMMT. The exfoliated structure of PA6nano
composites was examined by the TEM technique (The JEOL-2000EX
transmission electron microscope, Japan Electron Co.). As shown in
Figure 1, the micrograph of PA6nano composites containing 5 phr of
organic montmorillonite reveals exfoliated silicate layer structures.

Figure 1. TEM micrographs of PA6nano composite.

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4 F. ZHANG ET AL.

Table 1. Formulations of intumescent flame-retarded PP composites.

Sample
code PP (phr) PA6nano (phr) APP (phr) PER (phr) ZB (phr) ZEO (phr)
IFR-PP1 100 10 10 10 2 2
IFR-PP2 100 10 20 5 2 2

1800

1600

1400

1200 PP
HRR (kW/m2)

IFR-PP1
1000

800

600

400

200

0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
Time (s)
Figure 2. Heat release rates curves of PP and IFR-PP1 at incident heat flux of 50 kW/m2.

The formulations of intumescent flame-retarded PP composites are given

in Table 1.
The burning behaviors of the intumescent fire-retardant PP were studied
by the cone calorimeter (Fire Testing Technology Ltd, UK) at heat flux level
of 50 kW/m2. Figure 2 shows the heat release rates curves of PP and IFR-PP1.
It can be seen clearly that the fire-retardant performance of the system
was improved greatly due to the addition of intumescent fire-retardant.

Sample Preparation

The materials used to prepare IFR-PP composites include PP, PER, APP,
PA6nano, ZB, and ZEO. The above intumescent flame-retardant additives
were mixed with the PP polymer using a laboratory-scale two-roll mill at a
temperature range of 180–1858C to obtain the IFR-PP compounds based on
the different formulations and then each of the compounds was pressed at
1858C under 10 MPa for 30 min to obtain a sheet of specimen with
dimensions of 100 mm  100 mm  10 mm for testing.

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Study on Thermal Decomposition of IFR-PP 5

Table 2. Assignments of the FTIR characteristic

peaks of the main pyrolysis gases.

Wavenumber
(cmR1) Assignment References
3733 H2O [16,17]
2900 alkanes, alkenes [16]
2330 CO2 [17]
1673 H2O [16,17]
1508 H2O [16]

Measurements

About 10 mg of material was cut from the each sample and then pyrolyzed
in a nitrogen atmosphere (the content of N2499.999%) and an air atmo-
sphere using a TGA Netzsch TG209 at a heating rate of 108C/min. The
instrument temperature was calibrated using the Curie-point transition of
the standard metals. The Bruker Vertex 70 FTIR spectrometer (Germany)
was used to examine the gases evolved in the TGA. Dynamic FTIR spectra
were obtained during the thermal decomposition of the polymer and its
composites.
Listed in Table 2 are the assignments of the FTIR characteristic peaks of
the main pyrolysis gases evolved from the materials tested.

RESULTS AND DISCUSSION

Thermal Decomposition of PP in Different Atmospheres

The thermogravimetric (TG) and derivative thermogravimetric (DTG)

traces for PP performed in nitrogen and air atmosphere at heating rates of
108C/min are presented in Figure 3. As shown in the figure, all the samples
exhibit single step decomposition both in nitrogen and air atmospheres over
a relatively small temperature range. The temperatures at which the 5%
weight loss for PP in air and nitrogen atmosphere are 272 and 3988C,
respectively. The temperatures for the maximum loss of PP in air and
nitrogen atmosphere are 329 and 4558C, respectively. It can be seen that the
decomposition of PP occurs at much lower temperature in air than that in
nitrogen atmosphere. This indicates that oxygen promotes the thermal
decomposition of PP.
It is known that, in the absence of oxygen, PP decomposes without residue
to produce large amounts of aliphatic compounds, including alkanes,

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6 F. ZHANG ET AL.

120 0.5
Nitrogen
100 0
Mass retention (%)

Air
0 200 400 600 800 1000
−0.5

DTG (% / °C)
80
60 −1

40 −1.5
−2
20
−2.5 Nitrogen
0 Air
0 200 400 600 800 1000 −3
Temperature (°C) Temperature (°C)

Figure 3. TG and DTG of PP at heating rate of 108C/min in different atmospheres.

alkenes, and dienes [14]. The primary thermal decomposition of the

polymeric chains involves scission of the weakest bonds. Oxygen chemi-
sorbed on the polymer surface initiates radical formation, mainly peroxy
radicals. This can be validated with real time FTIR spectra. Figure 4 shows
the changes of the dynamic FTIR spectra obtained from the degradation
gases evolved from PP in both air and nitrogen atmospheres. It is hard to
find out the relative characteristic peak below 3808C in nitrogen atmo-
sphere, which indicates no decomposition of PP occurring. After that the
relative absorption peaks at about 2960, 1635, 1454, and 1373 cm1 appear
and respectively attributed to alkanes, alkenes, and dienes evolved when PP
degrades. The relative absorption peaks at about 1720 cm1 under air
appear at about 2538C and the intensity continues to increase till the
temperature of 3408C, in which the peak might correspond to methanal or
aldehyde gases evolved in the oxidized PP. It can also be seen from Figure 4
(in air atmosphere) that the relative absorption peaks appear at 2828C
(except the absorption peak at 2330 cm1 corresponding to CO2 existed in
air, the weak peak at 2330 cm1 can be found under nitrogen might be CO2
evolved in PP which was processed into sample PP in air). At that time,
the relative intensity of C–H absorption peaks around 2930 cm1 increases
greatly, which could be the increased amounts of degradation gases
evolved in PP. With the increase of degradation time or temperature, the
relative intensity of the absorption peaks continues to increase. At 5778C,
vanishing of almost all characteristic peaks indicates that PP decomposes
completely.
Usually, the peroxy radicals are formed at the beginning of polymer
degradation in the presence of oxygen [14]:

RH þ O2 ! R þ HO2
 R þ O2 ! ROO

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Study on Thermal Decomposition of IFR-PP 7
2960

In nitrogen 887
1635
2329
1454
548°C
1373

484°C
455°C
473°C
421°C
380°C
346°C
294°C
219°C

3500 2500 1500 500

Wavenumber (cm−1)

In air 2330 1720

1350
2930 1450 1145
577°C

513°C
421°C

386°C

352°C
340°C

305°C
282°C

253°C
230°C
167°C
80°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
Figure 4. FTIR spectra of the degradation gases evolved in PP during the TG experiment in
nitrogen and air atmospheres.

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8 F. ZHANG ET AL.

After the formation of peroxy radicals, they begin to attack the backbone
of PP:

CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

+
HOO
*
O2 + H

Macroradical rearrangement leading to chain scission:

CH3 CH3 CH3 CH3 CH3 CH3 CH3 CH3

¦Â-scission +
¦Â ¦Â
*
¦Á * ¦Á

This reaction pathway will continue and initiate the degradation of PP,
generating a lot of low molecular gases, consequently leading to the rapid
weight loss of PP.

Thermal Decomposition of IFR-PP and its Individual Components in Different

Atmospheres

In order to understand thermal decomposition of the IFR-PP composites

in different atmospheres, it is worthwhile to analyze in detail the TG curves
and characteristic spectra of decomposition gases evolved in IFR additives.
Figure 5 shows the TG and DTG curves of the PA6. It is clearly seen that
similar weight loss curves for air and nitrogen atmospheres appear before
the temperature reaches 4558C. After that, the rapid weight loss of PA6 in
nitrogen is continuing until the almost completely weight loss while the

120 0.5
Nitrogen
100 Air 0
Mass retention (%)

0 200 400 600 800 1000

DTG (% / °C)

80 −0.5
60 −1
40
−1.5
20
−2 Nitrogen
0 Air
0 200 400 600 800 1000 −2.5
Temperature (°C) Temperature (°C)
Figure 5. TG and DTG of PA6 at heating rate of 108C/min in different atmospheres.

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Study on Thermal Decomposition of IFR-PP 9

weight loss in air begins to decrease. This can be interpreted with FTIR
spectra of the degradation gases evolved in PA6. From Figure 6, the relative
intensity of C–H absorption peaks around 2930 cm1 in air after
4558C begins to decrease while the intensity of absorption peaks around
2930 cm1 in nitrogen is still very high. This indicates that the amounts of
degradation gases evolved in PA6 would be still high, and hence pyrolysis
rate of PA6 could be still high after 4558C in nitrogen. The difference for the
degradation of PA6 after 4558C indicates oxygen have a great influence
on PA6 at higher temperatures.
Figure 7 shows the TG and DTG curves of the APP. Figure 8 shows
the changes of the dynamic FTIR spectra obtained from the degradation
gases evolved from APP in air and nitrogen atmospheres. From these
figures, it is clear that the oxygen has little influence on the degradation
of APP.
The temperatures at which the 5% weight loss for APP in air and nitrogen
atmospheres are about 2018C. From Figure 8, it can be seen that the
absorption peaks of degradation gases starts to appear at about 1808C,
such as 3324 and 1616 cm1 indicating that APP begins to decompose.
Usually APP decomposes following the reactions as given subsequently [15]:

ðNH4 Þnþ2 Pn O3nþ1 ! H3 PO4 ! H3 P3 O9 ! ðHPO3 Þn

ðNH4 Þnþ2 Pn O3nþ1 ! nH3 PO4 þ NH3 "
3H3 PO4 ! H3 P3 O9 þ 3H2 O #
n=3H3 P3 O9 ! ðHPO3 Þn

The phosphoric acid units can be bonded together in rings (cyclic structures)
forming metaphosphoric acid molecules. The simplest such a compound
is trimetaphosphoric acid or cyclo-triphosphoric acid with the formula
H3P3O9. Its structure is shown as follows:
O OH

P
O O
OH
O
P P
O
O
OH
Trimetaphosphoric acid

A more general formula for such cyclic structure compounds can be

represented with (HPO3)n where n ¼ number of phosphoric units in the
molecule.

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10 F. ZHANG ET AL.

3729 2931 1704

In nitrogen 2352 1504
841°C 956

513 °C
484°C
467°C
455°C
444°C
426°C
366°C
276°C
144°C
86°C
63°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)

2310
929
In air

2930 1700
784°C
692°C
611°C
542°C
484°C
467°C
455°C
444°C
432°C
415°C
398°C
380°C

357°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
Figure 6. FTIR spectra of the degradation gases evolved in PA6 during the TG experiment
in nitrogen and air atmospheres.

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Study on Thermal Decomposition of IFR-PP 11
120 0.05
Nitrogen 0
100
Mass retention (%)

Air
−0.05 0 200 400 600 800 1000
80 −01.

DTG(%/°C)
60 −0.15
−0.2
40
−0.25
20 −0.3 Nitrogen
0 −0.35 Air
0 200 400 600 800 1000 −0.4
Temperature (°C) Temperature (°C)
Figure 7. TG and DTG of APP at heating rate of 108C/min in different atmospheres.

However, if APP is blended with PER and heated, APP will react with
PER and the resulting reaction equation can be formulated as follows [6]:
O O O
HO CH2 CH2 OH
O P O P O P C
HO CH2 CH2 OH
ONH4 ONH4 ONH4
O
HO CH2 CH2 OH
O O
O P OH C
HO CH2 CH2 O P O P
ONH4
ONH4 ONH4

Figure 9 shows the TG and DTG curves of the PER. Figure 10 shows the
changes of the dynamic FTIR spectra obtained from the degradation gases
evolved from PER in air and nitrogen atmosphere. As shown in Figure 9,
all the samples exhibit single step decomposition in nitrogen and air
atmospheres over a relatively small temperature range. The temperatures for
the 5% weight loss of PER in air and nitrogen atmospheres are 223 and
2358C, respectively. The temperature for the maximum loss of PER in air
and nitrogen atmospheres are 270 and 2888C, respectively. It can be seen
that PER decomposition occurs at much lower temperatures in air than in
nitrogen, which indicates that oxygen promotes the thermal decomposition
of PER. This could be verified by the increase of intensity of the 3733 cm1
(–OH) and 1508 or 1673 cm1 (–OH) peaks at about 2308C in Figure 10
(in air). That is, the amounts of the water vapor evolved from the
degradation of PER is greater in air atmosphere than nitrogen atmosphere.

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12 F. ZHANG ET AL.

3505 3324 In nitrogen 1616

2325 1068
768°C 667

682°C

572°C

438°C

375°C

316°C

182°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)

In air 1619 1064 960

2329
762°C
640°C
558°C
455°C
394°C
386°C
379°C
366°C
338°C
326°C
311°C
305°C
200°C
180°C
4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
Figure 8. FTIR spectra of the degradation gases evolved in APP during the TG experiment
in nitrogen and air atmospheres.

The main reaction taking place during the thermal decomposition of PER
is as follows [16]:
HO OH
HO O OH
HO OH −H2O HO OH
HO OH
HO O OH
HO O OH

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Study on Thermal Decomposition of IFR-PP 13
120 0.5
Nitrogen
100 Air 0
0 100 200 300 400 500 600
Mass retention (%)

−0.5
80

DTG(%/ °C)
−1
60
−1.5
40
−2
20 Nitrogen
−2.5
Air
0 −3
0 100 200 300 400 500 600
Temperature (°C) Temperature (°C)

Figure 9. TG and DTG of PER at heating rate of 108C/min in different atmospheres.

Figure 11 shows the TG and DTG curves of the ZB. Figure 12 illustrates
the changes of the dynamic FTIR spectra obtained from the degradation
gases evolved from ZB in air and nitrogen atmospheres. The main
degradation gas evolved in ZB is water vapor, which can be verified
from the characteristic peaks 3718, 3733, 3717, 1507, and 1680 cm1
(corresponding to H2O characteristic peak) appeared in Figure 12.
It can be seen that the weight loss curves in air are similar to those in
nitrogen. The temperatures for the 5% weight loss of ZB in air and nitrogen
atmospheres are about 367 and 3668C, respectively, at which ZB starts to
release crystalline water and form boric acid. At higher temperature, boric
acid continues to decompose and forms boron oxide. The residual mass is
above 86%.
Compared with the pure PP, the thermal decomposition process of
IFR-PP composites is much more complicated. Figure 13 shows the TG and
DTG curves of the pure PP and IFR-PP composites in both nitrogen and air
atmospheres. As shown in Figure 13, for all materials tested, such as PP,
IFR-PP1, or IFR-PP2, the decomposition onset temperature is lower in air
atmosphere than that in nitrogen atmosphere. This phenomena can also be
verified using FTIR spectra of the degradation gases evolved in IFR-PP1
composite or IFR-PP2 composite (as shown in Figures 14 and 15).
For example, for IFR-PP1, its characteristic peaks i.e., the bands at about
2900 or 1716 cm1 appear at about 2658C in air, but at about 3928C in
nitrogen. This indicates that oxygen promotes the thermal decomposition of
these materials.
It can also be seen that all IFR-PP composites start to decompose
early in comparison with PP whether in nitrogen or in air atmosphere.

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14 F. ZHANG ET AL.

In nitrogen 1697
2776 1022
2333
438°C

380°C
343°C
323°C
297°C
282°C

274°C
265°C
259°C
201°C
103°C

89°C
63°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
3733 In air
2333 1673 1508
386°C

346°C
314°C
297°C
276°C
253°C
230°C
69°C

49°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)

Figure 10. FTIR spectra of the degradation gases evolved in PER during the TG experiment
in nitrogen and air atmospheres.

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Study on Thermal Decomposition of IFR-PP 15

102 0.05
100
Nitrogen 0
98 Air 0 200 400 600 800 1000
Mass retention (%)

−0.05

DTG (%/°C)
96
94
−0.1
92
90 −0.15
Nitrogen
88 Air
−0.2
86
84 −0.25
0 200 400 600 800 1000
Temperature (°C) Temperature (°C)

Figure 11. TG and DTG of ZB at heating rate of 108C/min in different atmospheres.

However, the initial volatiles decomposed from IFR-PP composites are

mainly noncombustible gases such as H2O and NH3 evolved in APP.
For example, the water vapor (H2O) around 960 cm1 has been released
from APP at about 1808C in air as shown Figure 8. The ammonium (NH3)
corresponding to characteristic peak 3324 cm1 appear in the FTIR spectra
at about 1828C. These gases can dilute the oxygen concentration around the
materials and swell the melted PP polymer. So the earlier decomposition
onset of IFR-PP composite help to improve the flame retardancy of these
materials. Meanwhile, at a temperature higher than 2908C in air and 4408C
in nitrogen, the IFR-PP composites are more thermally stable than PP. For
example, the residual mass for PP at 3508C is 7.8% in air, whereas the
residual mass at the same temperature for IFR-PP1 and IFR-PP2 are 45.7
and 49.3%, respectively. The mass of residue of the IFR-PP at 9008C is still
as high as 11% in air. The temperatures for the maximum loss of IFR-PP1
in air and nitrogen atmospheres are 340 and 4588C, respectively. Similarly,
the temperatures for the maximum loss of IFR-PP2 in air and nitrogen
atmospheres are 332 and 4658C, respectively (as shown in DTG curves of
Figure 13). This can also be interpreted by FTIR spectra of the degradation
gases evolved in IFR-PP1 composite or IFR-PP2 composite. For IFR-PP1,
for example, the maximum characteristic peak around 2900 cm1 appears
at about 4678C in nitrogen, and at about 3578C in air. In fact, it is
most likely that the mass loss of this high temperature decomposition is
controlled not only by the release of the detected small products such as
alkanes, alkenes (around 2900 cm1), and water vapor (around 1600–
1700 cm1 or 3700 cm1) but also by products, which may not be detected
because they may be not able to pass the connection between the TG and the
FTIR gas analyzing equipment due to their large molecular weight or their

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16 F. ZHANG ET AL.

3733 1508
3818 2356 1681
In nitrogen
455°C
421°C

386°C
363°C

236°C
167°C

86°C

57°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
3718
In air 2306 1507
738°C 1680

703°C
623°C
473°C
421°C
386°C
363°C
282°C
230°C
155°C
98°C
69°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
Figure 12. FTIR spectra of the degradation gases evolved in ZB during the TG experiment
in nitrogen and air atmospheres.

unfavorable condensation behavior. Quantitative analysis within the FTIR

is restricted to some extent due to these shortcomings existing in test.
Based on the thermal decomposition analysis of the intumescent additives
such as APP, PER, ZB, PA6, and pure PP, the thermal decomposition
mechanisms of IFR-PP1 or IFR-PP2 composites (for example, in air) can be
interpreted as follows [6]:
First, the temperature of the PP composites will increase steadily
when being heated. The PP begins to melt at about 1608C. When the

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Study on Thermal Decomposition of IFR-PP 17

120 0.5
PP (air)
Mass retention (%)

100 IFR-PP1 (air) 0

0 200 400 600 800 1000

DTG (%/°C)
IFR-PP2 (air)
80 −0.5 PP (air)
PP (nitrogen)
60 IFR-PP1 (nitrogen) −1 IFR-PP1 (air)

IFR-PP2 (nitrogen) IFR-PP2 (air)

40 −1.5 PP (nitrogen)

20 IFR-PP1 (nitrogen)
−2 IFR-PP2 (nitrogen)
0
0 200 400 600 800 1000 −2.5
Temperature (°C) Temperature (°C)

Figure 13. TG and DTG of PP, IFR-PP1, IFR-PP2 at heating rate of 108C/min in different
atmospheres.

composites reach the temperatures at which the 5% weight loss occurs,

it is defined as the pyrolysis temperature of the component. Thus, APP
begins to decompose first at 2018C and evolves the gases such as H2O
and NH3 (as shown in Figure 8) and form phosphoric acid and
diphosphoric acid.
Second, the formed acid begins to react with PER and generate
phosphate ester.
Third, the gases evolved during the process of the reaction starts to
swell the PP melt. When the temperature continues to increase, the PER
begins to dehydrate (as shown in Figures 9 and 10) and continues to react
with acid generated from the decomposition of APP. The formed ester
performs dehydrocyclization and crosslinking, resulting in the formation of
intumescent char in the PP composite.
In the process of formation of intumescent char, the ZB can strengthen
the dense structure of char, which will release water easily at higher temp-
erature (3678C) and form boric acid to promote the formation of charred
layers in the IFR-PP composite more effectively.
PA6nano can act as a char forming agent [4], which was prepared by
extruding the mixture of PA6 and OMMT. The temperature for 5% mass
loss of PA6 is 3728C in air atmosphere, which is higher than the thermal
decomposition temperature of ZB (3678C). The glassy boric acid formed will
retard the decomposition of PA6 and enhance the structure of char layer.
ZEO will not decompose in the range of experimental temperature, which
may act as a core to gather the residual char particle and finally form
effective char layer to protect the underlying materials.
IFR-PP2 composite shows similar thermal decomposition behavior
except that the thermal stability is better than that of IFR-PP1 because of
the increase of ratio of APP/PER. This also illustrates that the varied

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18 F. ZHANG ET AL.

2958
2915
2337 1446
1361 875
In nitrogen 1635
1141
956
588°C
501°C
478°C
467°C
432°C
392°C
351°C
311°C
265°C
236°C
167°C
98°C
80°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
In air
3710 2935 1716 1454 1357
2325
646°C
513°C
444°C
398°C
386°C
369°C
357°C
328°C
300°C
265°C
247°C
225°C
173°C
127°C
98°C
80°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
Figure 14. FTIR spectra of the degradation gases evolved in IFR-PP1 during the
TG experiment in nitrogen and air atmospheres.

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Study on Thermal Decomposition of IFR-PP 19

2958 2919

In nitrogen 960
2337
1450 1373 1130 883

692°C
518°C
490°C
478°C
467°C
450 °C
432°C
409°C
375°C
351°C
282°C
259°C
167°C
132°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
In air
3729 2329
767°C
2954 2915 1704 1450 1357 1145
588°C
525°C
496°C
479°C
455°C
438°C
415°C
392°C
380°C
357°C
317°C
288°C
253°C
242°C
161°C
103°C

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm−1)
Figure 15. FTIR spectra of the degradation gases evolved in IFR-PP2 during the
TG experiment in nitrogen and air atmospheres.

contents of intumescent additives will influence the thermal decomposition

of the IFR-PP composites.
From the previous analysis of pure PP and IFR-PP composites, it can be
concluded that the thermal stability of both IFR-PP1 and IFR-PP2
composites is higher than the pure PP.

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20 F. ZHANG ET AL.

CONCLUSIONS

The results obtained in this work show that the thermal decompositions
of pure PP, PA6, PER, IFR-PP1, and IFR-PP2 in air are different from
those in nitrogen atmosphere, indicating that some different degradation
mechanisms of these materials are subject to different environmental
atmospheres. The existence of oxygen promotes the decomposition of these
materials. However, oxygen has little influence on the thermal decomposi-
tion of polyphosphate (APP) and ZB both in air and nitrogen atmospheres.
All IFR-PP composites studied start to decompose earlier compared to PP
whether in air or in nitrogen atmosphere as evidenced by the analysis of TG
and FTIR, which results from APP and helps to improve the flame
retardancy of IFR-PP composite due to the release of noncombustible gases
such as H2O and NH3 from APP. Meanwhile, at temperature higher than
2908C in air and 4408C in nitrogen, the IFR-PP composites are more
thermally stable than PP because of the incorporation of intumescent
flame additives.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the financial support of China NSFC

Funds (No. 50176021) and China Special Doctorate Funds for Colleges and
Universities.

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