Polymer Degradation and Stability 98 (2013) 297e305

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Polymer Degradation and Stability

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Novel phosphorousenitrogen intumescent ame retardant system. Its effects on

ame retardancy and thermal properties of polypropylene
D. Enescu a, *, A. Frache a, M. Lavaselli a, O. Monticelli b, F. Marino a
a
b

Dipartimento di Scienza Applicata e Tecnologia, Politecnico di Torino, sede di Alessandria, Viale T. Michel 5, 15121 Alessandria, Italy
Dipartimento di Chimica e Chimica Industriale, Universit di Genova, Via Dodecaneso 31, 16146 Genova, Italy

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 20 June 2012
Received in revised form
31 August 2012
Accepted 18 September 2012
Available online 27 September 2012

This paper describes the effectiveness of novel phosphorousenitrogen intumescent ame retardant
system (ammonium polyphosphate 202 and PPM Triazine HF e trademark, abbrev. IS) on re retardancy
and thermal stability properties of polypropylene (abbrev. PP) at incorporation level below the standard
amount required for intumescent ame retardant system.
UL-94 vertical burning test revealed that the addition of 20 wt.% of IS into neat PP is enough to reach
V-0 rating (short burn without dripping). Further, a higher increase of the oxygen concentration for
ignition was also found with the addition of the novel intumescent ame retardant to neat PP; LOI value
of neat PP by addition of 20 wt.% IS rose from 19 to 31 vol.%.
Finally, a remarkable decrease of peak heat release rate (PHRR:
91%), total heat release (THR:
42%),
average of mass loss rate (AMLR:
92%), average of specic extinction aria (ASEA:
48%) and total smoke
release (TSR:
58%) was revealed with increasing in IS content.
Novel intumescent ame retardant system showed good ame retardancy performance pointing out
that the intumescent char formed resists oxidation; this aspect was also conrmed by the thermogravimetry analysis. Hence, it can be pointed out that the improvement of ame retardancy imparted by
the novel intumescent ame retardant system at lower concentration enables on one side a lower cost
material formulation and on the other side the impact on the mechanical properties of the polymer
might be lower.
The thermo-oxidative data have revealed an enhancement of the thermal stability of the PP matrix by
incorporation of IS (the PP/20IS composite showed a markedly increase in Tonset: 14  C and Tmax: 64  C).
2012 Elsevier Ltd. All rights reserved.

Keywords:
Polypropylene
Intumescent ame retardant system
Flame retardance
Thermal stability

1. Introduction
Although halogen ame retardants deliver an excellent balance
of performance, processability, and cost, due to the potential risk
which they pose for environment as well as to human health [1e7],
it has prompted the plastic industry to look for eco-friendly alternatives (Halogen-Free). One of the viable approach as a response to
halogen-free retardants demand, beside of using inorganic ller
(aluminum trihydrate, magnesium hydroxide, etc.) is the concept of
intumescence. Intumescence comes from the Latin word intumescere which means to swell up, thereby the mechanism of an
intumescent ame retardant refers to the formation of a foam,
when the material is heated beyond a critical temperature, which
acts as excellent insulation barrier against heat transfer from the
heat ux/ame to the unburned fuel, diffusion of the volatile

* Corresponding author. Tel.: 39 (0)131 229343; fax: 39 (0)131 229331.

E-mail address: daniela.enescu@polito.it (D. Enescu).
0141-3910/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymdegradstab.2012.09.012

degradation products in the burring zone and diffusion of external

oxygen into the degradation zone preventing, therefore, further
decomposition [8,9]. As stated by the literature [10e12], a typical
intumescent ame retardant system (IFRs) for polymers, development based on the experience required in coatings [13], should
comprises:
- an inorganic acid, either free or formed in situ on heating by
a suitable precursor, dehydration agent which promote charring (such as acids: phosphoric, sulfuric, boric; ammonium
salts: phosphates, polyphosphates, sulfates; amine, amide
phosphate: urea, guanylurea, melamine; organophosphorus
compounds: tricresyl phosphate, alkyl phosphates, etc).
- carbon rich polyhydric compounds which are capable of
supplying the char (such as starch, dextrin, sorbitol, pentaerythritol, phenol-formaldehyde resins, etc).
- organic amine or amide which release non-combustible gases for
blowing the char to a foamed structure (such as urea, ureaformaldehyde resins, melamine, polyamides, dicyandiamide, etc.).

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D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

According to the exhaustive research [[14e19] and references

cited within], it was revealed that IFRs are efcient at large amounts
(25e30 wt.%) which implicit entail a relatively high cost [20],
therefore a continuous effort is carried out to develop new highly
effective intumescent systems having impact not only on the re
properties of polymer materials but also, for instance, on the cost of
material formulation, etc.
In this context, the main goal of this work is to investigate the
effectiveness of novel phosphorousenitrogen intumescent ame
retardant system on the re retardancy of polypropylene at incorporation level below the standard amount required for intumescent ame retardant system.
Furthermore, the ame retardancy performance of this novel
intumescent ame retardant system was compared with that of
traditional IFR system, such as Exolit AP760.
2. Experimental methods
2.1. Materials
Polypropylene used was a commercial grade product (Moplen
HP 500N e trademark, abbrev. PP) supplied by Basell. Intumescent
ame retardant system comprising: ammonium polyphosphate
202 e trademark and PPM Triazine HF e trademark (see Fig. 1 for its
chemical structure) (abbrev. IS) supplied by MCA Technologies
GmbH (Germany). Pentaerythritol (Charmor PM15 e trademark;
abbrev. PER) supplied by Perstorp Winning Formulas (Sweden).
2.2. Sample preparation
All the PP/IS composites (PP/10 wt.% IS, PP/15 wt.% IS and PP/
20 wt.% IS) were prepared via direct melt compounding using
a Leistritz ZSE 18 HP (Brabender Technologies, Duisburg, Germany)
co-rotating twin screw extruder (screw diameter 18 mm, length/
diameter 40). The operating temperature of the extruder was
maintained at 200-200-195-190-190-185-180-180  C from the
hopper to the die, respectively. The screw speed was maintained at
150 rpm and the throughput was 2 kg/h. The molten material was
quenched in water and then pelletized.
2.3. Characterization techniques
2.3.1. Thermal analysis
Thermogravimetric (TG) analyses were performed with a Q 500
thermal analyzer (TA Instruments, Chicago, Illinois, USA) at a heating rate of 10  C/min from 50 to 800  C under air ow (60 mL/min).
The samples (ca. 10 mg) were placed in open alumina pans. From TG
curves, the parameters Tonset (the temperature at which the sample
lost 5 wt. % of its original mass) and Tmax (the temperature at which

Fig. 1. Chemical structure of PPM Triazine HF.

the maximum rate of mass loss occurred) were evaluated to characterize the thermal stability of the neat polymer matrix and the
composites. Furthermore, the synergistic effect between APP and
PPM Triazine HF (IS) as well as APP and PER during their pyrolysis
was investigated by comparing the experimental TG curves of the
mixtures with the calculated ones. The calculated mass loss (Mcalculated) curves were calculated by the linear combination of the
experimental TG curves of each compound taken individually: APP,
PPM Triazine HF and PER, (Equation (1)); in other words, the
calculated curves, calculated by additives rules, represent the
degradation of the mixtures when no chemical or physical interaction between the compounds takes place.

Mcalculated T xMAPP T yMPPM Triazine HF or PER T

(1)

where MAPP is the mass loss of APP, MPPM Triazine HF or PER is the mass loss
of PPM Triazine HF or PER and T is the temperature of degradation
(50e800  C), x y 1, x and y are the mass percentages of APP, PPM
Triazine HF and PER in the mixture; D(T): curve of weight difference:
D(T) Mexperimental(T)
Mcalculated(T), which allows the observation of
eventual synergy and/or antagonism during degradation between
APPeMMP Triazine HF and APPePER; synergism refers to the
combined effect of two or more additives, which is greater than the
sum of their individual effects, while antagonism effect means that
the observed effect is less than the sum of the individual effects.
2.3.2. Scanning electron microscopy (SEM)/energy-dispersive X-ray
spectroscopy (EDS)
The microstructural and elemental analyses of the crosssectional sample as well of the residues obtained at the end of
the cone calorimeter test were done with a scanning electron
microscope (LEO 1450 VP, Oberkochen, Germany) with an energydispersive X-ray probe (INCA Energy Oxford, UK) attachment. The
cross-sectional sample was prepared by cryogenic fracture in liquid
nitrogen and then sputter-coated with gold for 27 s at a working
pressure of 0.1 mbar before the SEM/EDS measurements.
2.3.3. Fire tests
The limiting oxygen index (LOI) test was carried out with a Fire
Testing Laboratories (Fire Instrumentation & Research Equipment
Ltd, Kent, UK) instrument according to the standard oxygen index
test UNI EN ISO 4589-2. This test is a procedure for measuring the
minimum oxygen concentration in a owing mixture of oxygen and
nitrogen that supports combustion in a candle like conguration of
a top-ignited vertical test specimens as follows: a Bunsen burner
propane ame is applied on the top of a vertical orientated test
specimen for up to 30 s, removing it every 5 s, just briey, to
observe whether or not the entire top surface of the specimen is
burning. The higher the LOI value, the better is the ame retardancy
(air contains approximately 21 vol.% oxygen and therefore any
material with an LOI of less than 21 will probably support burning
in an open-air situation). The dimensions of the specimens used for
this test were 75  6  3.2 mm3.
The UL-94 vertical burning (UL-94 V) test was carried out
according to ASTM D 3801-00 standard procedure. A Bunsen
burner methane ame is applied at the bottom end of a vertical
orientated test specimen for 10 s, two times, with an interval made
by the time that it takes for aming combustion to stop after the
rst application. This test classied the materials as V-0, V-1, V-2 or
not classiable according to the time period needed for extinguishment of the ame after each ignition and whether combustion occurs with dripping of aming particles which are capable of
igniting surgical cotton placed underneath the specimen. V-0 is the
most required classication. The dimensions of the specimens were
125  12.5  3.2 mm3.

D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

Cone calorimetry testing was carried out in accordance with the

ISO-5660-1 standard procedure with a Fire Testing Technology cone
calorimeter (East Greenstead, UK). The bottom and the sides of each
specimen, prepared by injection molding, were wrapped in an
aluminum foil and exposed horizontally to an external heat ux of
35 kW/m2, the recommended value for heat ux for initial studies to
mimic small-scale res [21]. The main parameters measured were:
time to ignition (TTI, s), peak heat release rate, which is proportional
to the maximum intensity reached by a re (PHRR, kW/m2), total
heat release (THR, kJ/m2), average of mass loss rate (AMLR, g/s),
average of specic extinction aria (ASEA, m2/kg), total smoke release
(TSR, m2/m2), re grow rate index (FIGRA, kW/m2/s; a parameter
dened as the ration of PHRR/time to PHRR and it is an index for
estimating re growth [22]) and re performance index (FPI, s/kW/
m2; it is dened as the ration of TTI/PHRR and has been suggested
that it relates to the time to ashover (or time available for escape) in
a full-scale re situation [23]). For each composition, a total of three
specimens were tested to ensure signicant and reproducible data.
The average values and their standard deviations (s) are reported.
The dimensions of the specimens were 100  100  6 mm3.
2.3.4. Mechanical measurements
Tensile properties (Youngs modulus, tensile strength and
elongation at break) were measured by a Zwick Roell Z/100
dynamometer at a cross-head speed of 50 mm min
1. The tensile
bars were prepared by injection molding press according to UNI
EN ISO 527-2. Six samples were tested for each material; the
average values and their standard deviations (s) are reported. The
dimensions of the samples were 170  20  3 mm3 (dog bone
shape).

299

3. Results and discussion

3.1. Fire test
3.1.1. Flammability study of the PP/IS composites by means of UL-94
vertical burning and limiting oxygen index test
The UL-94 V Flammability ratings provide an indication of
materials ability to extinguish a ame once ignited. The results,
obtained from UL-94 V test, show that neat PP pass UL-94 V rating
from not rating to V-0 rating by addition of IS at the highest
concentration, namely 20 wt.% (Table 1).
Visual observation revealed that neat PP starts burning spontaneously after the rst 10 s ame application, which continues till
the test specimen is completely burn up to the sample holding
clamp. Although the ammability behavior of the composite containing 10 wt.% IS is more or less similar to neat PP, however with
increasing in IS content (15 wt.%) even though the sample PP/15IS
drips igniting the cotton used as marker, it burns more slowly
requiring the second application of the ame. Further, the ammability behavior of PP matrix is completely changed when the
addition of IS reached 20 wt.%. Indeed, even after the second
application of the ame the composite PP/20IS does not burn,
behavior which can be attributed to the formation of intumescent
char layer at the surface of the sample which shows a good
adherence, thus hindering the ame to reach a fresh unburnt
surface sample and therefore providing an efcient barrier effect
against the propagation of the ame (Fig. 2 digital pictures taken
during the UL-94 V test).
LOI testing allows to measure the minimum oxygen concentration needed for the self-sustained combustion of polymeric

Fig. 2. Digital picture taken during the UL-94 V and LOI tests.

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D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

Table 1
UL-94 vertical burning test and limiting oxygen index of neat PP and PP/IS
composites.

1200

Sample

Neat PP
PP/10IS
PP/15IS
PP/20IS

Limiting
oxygen
Cotton
Specimen
Total aming Classication
index (vol.%)
indicator
burns up to combustion
ignited
holding
for all 5
by aming clamp
samples (s)
particles
or drops
Yes
Yes
Yes
No

Yes
Yes
Yes
No

351
446
514
20

Unclassied
Unclassied
Unclassied
V-0

2
Heat Release Rate (kW/m )

UL-94 vertical burning test

19
26
29
31

800

400

material (the LOI value is only expressed as a number). The results,

obtained from LOI testing of the PP/IS composites, are summarized
in Table 1. It was revealed that increasing in IS content is an effective
approach to enhance the ame retardancy of neat PP. LOI value of
neat PP increased from 19 vol.% to 26, 29, and 31 vol.%, respectively
when 10, 15 and 20 wt.%, respectively of IS were added. In other
words, a higher oxygen density is required to initiate and sustain
combustion of the specimen after the addition of 20 wt.% of IS into
neat PP (Fig. 2 digital image, taken during the LOI test, shows that
the increase of IS amount leads to the formation of an abundant
protective intumescent char layer at the surface of the specimen
which holds back the evolution of the combustible gases and, also,
limits the heat transfer). The LOI results are in agreement with
those of UL-94 V, showing that at higher concentration of IS, the
char strength is great enough to make it to remain during the test,
not only on top of the specimen (LOI) but also at the bottom end
(UL-94 V).

PP
PP/10IS
PP/15IS
PP/20IS

1000

2000

3000

4000

3000

4000

3000

4000

Time (s)

2
Total Heat Release (MJ/m )

300

200

100

3.1.2. Combustion behavior of the PP/IS composites by means of

cone calorimetry
The parameters measured in the re test are reported in Table 2
and Fig. 3aec.
Neat PP shows a short and intense burning by displaying only
one peak of HRR (Fig. 3a), whereas by incorporation of intumescent
ame retardant additive (IS) two peaks of HRR were seen (Fig. 3a)
which point out the typical behavior of these type of systems. The
rst peak is attributed to ignition and to the ame spread on the
surface of the material; after this, it takes place a plateau effect due
to the process of protective intumescent layer formation and followed then by a second peak, encountered toward the end of
burning, ascribed to the occurrence of cracks in the intumescent
structure caused by the scape of volatile gases given off by the
degradation of the substrate.
As Fig. 3a and Table 2 show, the incorporation of 20 wt.% of IS
into neat PP leads to a remarkable decreased of PHRR (
91%). The
primary parameter responsible for the decrease of PHRR is the fuel
mass loss rate, signicantly reduced in comparison with neat PP,
which in turn can be attributed to the formation of a solid stable
intumescent char layer on the surface of the polymer which delays
the accumulation of thermal energy within the sample and also

2 2
Total Smoke Release (m /m )

1000

2000
Time (s)

4000

3000

2000

1000

1000

2000
Time (s)

Fig. 3. Curves of (a) HRR, (b) THR and (c) TSR from the cone calorimeter test.

Table 2
Cone calorimeter data of neat PP and the PP/IS composites at 35 kW/m2.
Sample

TTI  s (s)

Neat PP
PP/10IS
PP/15IS
PP/20IS

62
44
45
43






9
1
2
4

PHRR  s
(kW m
2)
1221
313
148
115






28
12
18
8

FIGRA  s
(kW m
2 s1)
3.35
1.21
0.46
0.24






0.13
0.05
0.07
0.06

FPI  s
(s kW
1 m2)
0.05
0.16
0.31
0.38






0.01
0.02
0.03
0.05

THR  s
(MJ m
2)
265
235
191
153






16
5
9
42

AMLR  s
(g s
1)
0.132
0.027
0.014
0.011






0.001
0.003
0.001
0.003

ASEA  s
(m2 kg
1)
604
638
399
313






27
29
96
8

TSR  s
(m2 m
2)
3144
3305
1985
1309






135
139
567
346

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301

Fig. 4. (a) Digital photographs of the charred residues obtained at the end of combustion process and (b) SEM micrographs of the PP/IS charred residues.

lowers the oxygen ingress, thus preventing further decomposition

and, therefore, a decrease in the fuel mass loss rate. Furthermore,
it was found that Triazine and its derivatives are good charring
agents because of their abundant nitrogen and tertiary nitrogen
structure [24,25], therefore this aspect might explain, in one way,
the good efciency of novel intumescent ame retardant (see
Fig. 1).
With regard to time to ignition, it is revealed that it starts earlier
for all the composites (at 44, 45 and 43 s) in comparison with neat
PP (at 62 s). Nevertheless, a greater FPI value can be still achieved
owing to PHRRs. FPI may be considered to be the best individual
indicator of overall re hazard, therefore the greater the FPI value is,
the less is re hazard. From Table 2, it can be observed that in
comparison with neat PP (0.05), the composite containing 20 wt.%
of IS has the greatest value (0.38), showing a step in the right
direction in terms of re hazard. Furthermore, the above sample
showed also a markedly improvement of FIGRA value (0.24) (an

index for estimating re growth, thus a lower FIGRA value may

indicate a better ame retardancy) as compared to neat PP (3.35).
The total heat release (Table 2, Fig. 3b) is signicantly decreased
by increasing IS content (
42% for PP/20IS), thereby a part of the
PP/IS composite has not completely combusted, thus pointing out
the inuence of enhanced charring.
SEA and TSR are indicative parameters of smoke, they can play
a decisive role in human survival during a re (dense smoke in large
quantity can diminish the visibility and, therefore, it can cause
disorientation for occupants to escape by the correct routes). From
Table 2, it can be seen that with increasing the IS content, SEA and
TSR (Table 2, Fig. 3c) decrease signicantly (SEA:
48% and TSR:

58% for the PP/20IS composite). One of the explanation of a such
decrease could be attributed to a more dense and compact intumescent char layer formed on the surface of the sample during the
combustion which suppresses the release of smoke. SEM micrographs support in one way to this afrmation (see Fig. 4b).

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D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

Fig. 5. Thermogravimetry curves under air atmosphere (10  C/min) of neat PP, IS and
PP/IS composites.

3.1.2.1. Char morphology. Taking into consideration that the physical structure of the charring layer plays a signicant role concerning the performance of an intumescent ame retardant, the
morphology of the charred residue, obtained at the end of
combustion process, (Fig. 4a, digital photos taken from top as well
as from prole; from prole can be observed an increase in volume
of the residue which vary from 2 to 4 times as compared with neat
composite) was investigated. Therefore, from SEM micrographs
(Fig. 4b) it can be seen that PP/20IS charred residue shows
a compact structure with less voids. Therefore, during the process
of burning, heat and ammable volatiles penetrate less the char
layer into the ame zone, thus the samples ame retardancy and
the suppression of the smoke density are improved.

3.2. Thermal behavior

It is well known that, on heating in the presence of oxygen, neat
PP undergoes a radical peroxidation chain process and the main
volatile compounds observed in the thermo-oxidative degradation
of neat PP are hydroperoxides, alcohols, aldehydes and ketone, as
reported by Gensler and coworkers [26].
As Fig. 5 shows, the thermo-oxidative degradation of neat PP
takes place in one step with Tonset at 271  C and Tmax at 335  C and
gives a small residue at the end of the test, about 1.7 wt.%. IS is
a thermally stable additive in the processing temperature of polypropylene; it begins to lose weight at about 306  C and gives
43 wt.% of solid residue at 800  C.
Although at low IS content, the thermo-oxidative degradation of
the composite starts at the same temperature as neat PP, however

Table 3
Thermogravimetric analysis under air atmosphere of neat PP, IS1 and PP/IS1
composites.
Sample

Tonset ( C)

Tmax ( C)

Residue
at 500  C (%)

Residue
at 800  C (%)

Neat PP
IS
PP/10IS
PP/15IS
PP/20IS

271
306
272
280
285

335
404
350
381
381

1.8
62
13
14
17

1.7
43
4
5
5

with the increase in content of IS, a higher thermal stability is

produced. This increase of thermal oxidative stability could be
attributed to the higher amount of intumescent char formed on the
sample surface (insulative foamed); it can act as physical barrier
which will inhibit transmission, i.e. it will hold back the inward
diffusion of oxygen and the outward diffusion of the degradation
products. Detailed information about onset, maximum weight loss
rate temperature and residual char yield are given in Table 3.
Further, since the novel intumescent ame retardant system
showed a good ame retardancy of PP, we investigated the synergistic effectivity of APP and PPM Triazine HF (IS) with a model
intumescent system such as APP and PER; the synergistic activity
can express itself in various FR parameters: char formation, rate of
heat release, limiting oxygen index, time of afteraming, dripping,
and others. Therefore, the synergistic effect between APP and PPM
Triazine HF (IS) as well as APP and PER during the their pyrolysis
was investigated by comparing the experimental TG curves of the
mixtures with the calculated ones.
As Fig. 6a shows, the experimental curve of APPePPM Triazine
HF mixture (3:1 by weight) is very different from the calculated
one; no interaction occurs from 50  C up to 234  C between APP
and PPM Triazine HF. Interactions are observed between 234  C and
294  C and above 588  C. Indeed, a lower weight loss is found than
calculated and a large amount of charred residue is left at 800  C.
The fact that the observed charred residue is higher than the
calculated one by 30% demonstrates the effectiveness of APPePPM
Triazine HF in char formation.
Reaction mechanism of APPePER mixture has been thoroughly
investigated by our research group [27e29] who demonstrated
a strong interaction between APP and PER with the formation rst
of phosphoric ester bonds by alcoholysis of the phosphate chain.
Further intermolecular alcoholysis and/or esterication leads to
cyclic pentaerythritol phosphate structures inserted in the polyphosphate chains. As Fig. 6b shows, up to 280  C no interaction
takes place between APP and PER (3:1 by weight), but from 280  C
up to 492  C a strong interaction between the additives can be
observed. In particular, the mixture begin to lose weight at about
175  C which is earlier than expected by 65  C and above 492  C
a higher weight loss is found than calculated one. The charred
residue at 800  C is slightly higher than predicted ones by 4%.
Finally, comparing both types of the intumescent systems, it is
worthy to note that, although the char residues at 500  C (char
formation) is almost the same, however at 800  C (char degradation) for the APPePPM Triazine HF mixture, it substantially
increased (48%) in comparison with that of the APPePER mixture
(18%), pointing out the higher oxidation stability of the char.
Based on the nal char yield, it can be assumed that the
synergistic effectiveness is better for APPeMMP Triazine HF
mixture than APPePER mixture.

3.3. SEM micrographs analysis. Correlation between the state of IS

dispersion into PP and mechanicals properties
SEM micrographs of the PP/20IS composite revealed the existence of aggregates being distributed all over the matrix (some of
them having up to 19 micron in diameter) (Fig. 7). SEM micrograph
in back-scattered display a compositional contrast, the bright areas
reect the particles with high atomic number (high backscatter
electron signal) which correspond in this case to the phosphorus
atoms (IS), whereas the dark area reect the particles with low
atomic number (low backscatter signal) which correspond to
carbon atoms. Since PPM Triazine was mixed with APP, we suppose
that it is closed to phosphorous atoms. Further, the EDS mapping
conrmed the presence of phosphorous aggregates.

D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

303

Fig. 6. (a) Experimental TG curves under nitrogen atmosphere (10  C/min) of APP, MMP Triazine HF, APPeMMP Triazine HF mixture and calculated curve obtained for this mixture,
(b) Experimental TG curves under nitrogen atmosphere (10  C/min) of APP, PER, APPePER mixture and calculated curve obtained for this mixture and (c) curves of the weight
difference between APPeMMP Triazine HF experimental and calculated and APPePER experimental and calculated.

Taking into account that the strength of two-phase composite

materials depends on effective stress transfer between additive and
matrix, to get a high strength composite a strong interfacial
bonding between particles and polymer matrix is required. Fu et al.
[30] reported that mechanical properties of particulateepolymer
composites are inuenced by the particle size, particle/matrix

interface adhesion and particle loading. From SEM micrographs it

can be seen clearly that the interfacial adhesion additive/matrix is
poor and this aspect affect the strength of the PP/IS composites.
As it can be seen from Table 4, the incorporation of IS into PP
matrix leads to a decrease of Youngs modulus and tensile strength
which may be attributed to the poor interfacial adhesion caused by

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D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

Fig. 7. SEM micrographs and elemental distribution from EDS mapping of the PP/20IS composite.

Table 4
Mechanical properties of neat PP and the PP/20IS1 composite.
Sample

Young
modulus  s (MPa)

Max tensile
strength  s (MPa)

Elongation
at break  s (%)

Neat PP
PP/20IS

1201.44  27
974.36  15

28.49  1
22.15  1

307.36  33
36.59  23

the great discrepancy in polarity between the PP matrix and IS (see

SEM images Fig. 7). Furthermore, the results also revealed a limited
deformability of the composite in comparison with neat PP which
might be related to the decreased mobility of the adsorbed chains
on the additive particles surface. Therefore, to increase the
mechanical properties, addition of a compatibilizer is required in
order to optimize the dispersion of IS. Although, the incorporation
of IS into PP is at the expense of mechanical properties, however it
can be pointed out that it leads to a remarkable improvement of the
ame retardancy of it.
4. Conclusions
The present work has revealed that the incorporation of novel
intumescent ame retardant system at 20 wt.% loading into polypropylene matrix led to a remarkable decrease of PHRR:
91%,
THR:
42%, AMLR:
92%, ASEA:
48% and TSR:
58%. The obtained
results have evidenced that the novel IFRs produces a remarkable
decrease of the quantity and quality of the smoke. One of the
explanation of a such decrease could be attributed to a more dense
and compact intumescent char layer formed during the combustion
on the surface of the specimen which suppress the release of
smoke. SEM micrographs (see Fig. 4b) support in one way this

afrmation showing that PP/20IS composite displays a more

compact structure with less voids, thus during the process of
burning, it becomes less permeable to the transfer of combustibles,
therefore the samples ame retardancy and the suppression of the
smoke density are improved. Further, LOI and UL-94 V data support
the efcacy of this novel intumescent ame retardant system
increasing the oxygen concentration for ignition of polypropylene
from 19 to 31 vol.% at 20 wt.% loading of IS and passing UL-94 V
rating from not classiable to V-0 rating.
As a general conclusion, it can be said that the novel intumescent ame retardant system is clearly effective as a ame retardant
for PP. This statement is further supported by the thermogravimetric analysis which revealed a very good carbonization performance of the novel intumescent ame retardant system than the
traditional one.
SEM analysis revealed a poor interfacial adhesion of IS into the
PP matrix, caused by the great discrepancy in polarity between
them, which is at the expense of mechanical properties such as
a decrease of Youngs modulus (19%), tensile strength (22%) and
elongation at break (88%). Therefore, for an improvement of the
mechanical properties, addition of a compatibilizer is required in
order to optimize the dispersion of IS.
In the light of the aforementioned ndings, we concluded that,
the novel intumescent ame retardant system is suitable for ame
retardancy of polypropylene at just 20 wt.% loading.
Acknowledgments
The authors acknowledge the useful comments and suggestions
of Professor Giovanni Camino.

D. Enescu et al. / Polymer Degradation and Stability 98 (2013) 297e305

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