Polymer Degradation and Stability 98 (2013) 1972e1980

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Flame retardant polypropylene through the joint action of sepiolite

and polyamide 6
Fouad Laoutid, Olivier Persenaire, Leila Bonnaud, Philippe Dubois*
Center of Innovation and Research in Materials & Polymers (CIRMAP), Laboratory of Polymeric and Composite Materials, University of Mons UMONS &
Materia Nova Research Center, Place du Parc 20, 7000 Mons, Belgium

a r t i c l e i n f o

a b s t r a c t

Article history:
Received 26 November 2012
Received in revised form
9 July 2013
Accepted 30 July 2013
Available online 9 August 2013

The inuence of the incorporation of polyamide-6 (PA) and natural sepiolite nanoparticles on both the
thermal degradation and re behaviour of polypropylene (PP) matrix has been investigated by thermogravimetric analysis (TGA) and mass loss calorimetry. For that purpose, PP/PA blends and nanocomposites thereof were prepared by melt processing. TGA results evidenced that the use of maleic
anhydride grafted-polypropylene (MA-g-PP) as compatibilizer led to a signicant improvement in
thermal stability under air. Such improvement was linked to the formation of a char layer preventing the
thermo-oxidative degradation of PP. Interestingly, the thermal resistance of this char layer was further
improved by adding 5 wt% of natural sepiolite leading to important increase of time to ignition and
reduction of peak of heat release rate (pHRR) during mass loss calorimeter test.
2013 Elsevier Ltd. All rights reserved.

Keywords:
Flame retardant
Polymer blend
Nanocomposites
Sepiolite
Charring

1. Introduction
Polypropylene (PP) is commonly used in the plastic industry due
to its attractive versatility in terms of properties and processability.
For instance, PP can be found in many areas such as packaging,
automotive and ber industry. Nevertheless, poor ame retardancy
is the main drawback of PP [1,2]. To reduce its ammability, several
kinds of ame retardant additives such as halogenated compounds
[3] and metal hydroxides [4] have been used [1,5]. Due to environmental concerns, metal hydroxide microparticles are preferred.
However, their use is limited because satisfactory ame retardant
properties are only achieved at high loading level (up to more than
60 wt%). In this context, nanometric particles represent an interesting alternative to conventional ame retardants since they
proved their efciency to enhance thermal resistance and ame
retardancy of polymers even at low ller contents, when individualized and properly dispersed in polymer matrices [6,7]. They are
also known to enable synergistic effect that can improve the ame
retardant performances of conventional ame retardant additives.
For instance, the incorporation of a few percents of organomodied clay nanoplatelets (montmorillonite, MMT) in PP matrix

* Corresponding author. Tel.: 32 (0)65 373480x3482, 32 (0)65 373480x3483;

fax : 32 (0)65 373484.
E-mail address: philippe.dubois@umons.ac.be (P. Dubois).
0141-3910/$ e see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.polymdegradstab.2013.07.018

in the presence of 5 wt% of MA-g-PP proved to create a protective

char layer during combustion which leads to important decrease of
peak of heat release rate pHRR as high as 50% [8] during cone
calorimeter test (50 kW/m2). It is worth noting that the use of both
organomodied montmorillonite and organic compatibilizer such
as MA-g-PP are required to obtain a nanocomposite structure [9,10].
Organo-modied needle-like clay, such as sepiolite, has been
also considered as nanoller for polypropylene. Nevertheless, the
sepiolite-induced ame retardancy was lower than that of montmorillonite even after blend compatibilization with 5 wt% MA-g-PP.
Indeed, either native or organo-modied sepiolite allowed for
reducing pHRR values to max. 12% [11].
The superior effect of the organo-modied montmorillonite on
pHRR reduction of PP could be attributed to the plate morphology
of layered silicates that favors the formation of protecting char
layer. Several other factors including chemical action of clay surface, adsorption of volatile products on larger surface areas
(750 m2/g) of MMT particles, in comparison with the lower surface
areas of sepiolite (300 m2/g) could also explain such difference.
Interestingly enough, the superior ame retardant effect of lamellar
nanoparticles in comparison with needle-like ones was also
recently reported by some of us by lling a poly(methyl methacrylate) (PMMA) matrix with either lamellar or brous magnesium
dihydroxide (MDH) nanoparticles [12].
Although needle-like morphology of sepiolite appears less
favourable than MMT, sepiolite presents processing advantages due

F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

to its better wettability by non-polar polymers [13]. Furthermore,

the lower contact area between needles as compared to the contact
area between clay layers can favour sepiolite dispersion [14].
Therefore, the organo-modication of sepiolite is not a prerequisite
contrary to montmorillonite. Natural sepiolite can thus still be
considered as a cost-effective alternative to organomodied clays.
Polymer blends have attracted attention for a few decades as a
simple, versatile and economic method that allows for developing
new materials with controlled properties from existing polymers
[15e19]. Polymer blending is a novel approach to improve the re
properties of polymeric materials. Lizymol and Thomas [20] studied the thermal stability of three binary blends of poly(vinyl chloride) (PVC), poly(ethylene-co-vinyl acetate) (EVA) and
poly(styrene-co-acrylonitrile) (SAN). Results showed that thermal
resistance of the blends was found to be strongly dependent on the
miscibility of the homopolymers in the blend. Moreover, the
intrinsic re behaviour of individual polymer and the blend
composition strongly affect the re performances of polymer
blends. In another study, Lizymol and Thomas [21] briey investigated the re behaviour of blends of polymers having different re
behaviours, i.e., PVC (intrinsically re retardant) and EVA (weak
resistance to re). Results showed that the re properties of EVA/
PVC blends only depends on blend composition and not on blend
miscibility. Swoboda et al. [22] showed that both morphology and
the blend compatibilisation strongly affect the ame retardancy of
polycarbonate (PC)/poly(ethylene terephthalate) (PET) blends. The
ame retardancy of blends containing less than 50 wt% of PC increases linearly with PC content while blends containing more than
50 wt% of PC react to re like pure PC thanks to the formation of a
continuous PC phase. The chemical interaction between polymeric
phases in the blends could also affect the re properties of the nal
materials. As far as PET/PC blends were concerned, the transesterication reaction between the two polymers was shown to
reduce the overall re performances due to the decrease of the
viscosity of the blends resulting from PET chain breaking. Sonnier
et al. [23] investigate the relation between morphology and re
behavior of a binary polymer blend constituted of a low ammable
and charring polymer (PC) and a relatively ammable and noncharring polymer (PBT). They showed that the relative percentage
of each polymer is the main parameter which determines the re
behavior of the blend and an increase in PBT content lowers the
ame retardancy of the blend.
With a view to take advantages of the natural sepiolite properties, the preparation of nanocomposites based on PP/PA blends
has been described in this paper. In order to improve the potential
of ame retardancy of sepiolite, the incorporation of a charring
polymer such as PA-6 has been considered. It is thought that the use
of PA-6 could improve both the amount and the thermal stability of
the char. Indeed, Bourbigot et al. [24] evidenced that pristine PA
could be successfully used as charring agent in intumescent formulations for PP. In this paper, the potential synergistic ame
retardant effect of both needle-like clay and charring agent is
investigated. It is worth noting that only natural sepiolite, i.e.,
without any surface modication, has been considered in the study.
2. Experimental section
2.1. Materials and processing
The polymers used in this study are commercial products:
polypropylene homopolymer (PP) from Polychim, (B 10 FB, MFI at
240  C and 2.16 kg 15.6 g/10 min), polyamide-6 (PA) from DSM
Engineering Plastics (Akulon F136-c1, MFI at 240  C and
2.16 kg 5.75 g/10 min) and maleic anhydride grafted polypropylene (MA-g-PP) Orevac CA100 from Arkema (maleic

1973

anhydride content 1 wt%). Natural needle-like sepiolite clay

(Pangel S9) was obtained from Tolsa (Spain) and was used asreceived (thus without any surface chemical treatment).
Before processing by melt-blending, PA and natural sepiolite
were dried overnight at 100  C under vacuum. A Brabender internal
mixer was used to prepare the blends at 240  C (10min mixing at
50 rpm). Two highly lled masterbatches (MB) containing 30 wt%
of sepiolite were prepared within PP or MA-g-PP and used to
introduce sepiolite nanoparticles into PP/PA blends. In the case of
blends containing less than 5 wt% of sepiolite, additional amount of
MA-g-PP was added in order to obtain 12 wt% of MA-g-PP in all the
compositions. In order to investigate the effect of sepiolite location
within PA nodules on the ame retardancy of compatibilized PP/
40-PA composition, an additional highly lled PA masterbatch
containing 11.6 wt% of sepiolite was tested. The compositions of the
prepared blends are presented in Table 1.
For the mass loss calorimeter test, plates (100  100  4 mm3)
were compression molded at 240  C using an Agila PE20 hydraulic
press. More precisely, the material was rst pressed at low pressure
for 200 s (three degassing cycles), followed by a high-pressure cycle
at 150 bars for 180 s. The samples were then cooled down by tap
water at 50 bars and 180 s.

2.2. Characterization
2.2.1. Thermal analysis
Thermogravimetric analysis (TGA) was used to study the thermal degradation and thermo-oxidative decomposition of PP and
the different PP/PA blends. Approximately 10 mg of the sample was
submitted to a temperature ramp from 25 to 700  C at a heating
rate of 20  C/min. Thermo-oxidative degradation experiments were
performed under a ow of 60 ml/min of either air or nitrogen. All
TGA experiments were performed by using a TGA Q50 device from
TA Instruments. Alumel and chromel alloys were used for calibration (Curie temperature measurement).
2.2.2. Fire properties
The re behaviour was tested with a FTT (Fire Testing Technology)
mass loss calorimeter to measure the heat release rate (HRR) on samples
according to the ISO 13927 standard. A 100  100  4 mm3 plate was
exposed to a radiant cone (35 kW/m2) using a forced ignition. Results
correspond to mean values obtained from 3 experiments for each
formulation, for which a typical variation of 10% was observed.
2.2.3. Microscopic observations (SEM & TEM)
Scanning electronic microscopy (SEM) was performed on the
surface of samples previously fractured at liquid nitrogen
Table 1
Material designation and composition.
Designation

Composition

Parts
(weight ratio)

PP/5-S
PP/MA-g-PP/5-S
PA/5-S
PP/40-PA
PP/40-PA/MA-g-PP
PP/40-PA/5-S
PP/40-PA/MA-g-PP/5-S
PP/40-PA/MA-g-PP/3-S
PP/40-PA/MA-g-PP/1-S
PP/40-PA/MA-g-PP/5-S
(MB PA)
PP/20-PA
PP/20-PA/MA-g-PP
PP/20-PA/MA-g-PP/5-S

PP/Sepiolite
PP/MA-g-PP/Sepiolite
PA/Sepiolite
PP/PA
PP/PA/MA-g-PP
PP/PA/Sepiolite
PP/PA/MA-g-PP/Sepiolite
PP/PA/MA-g-PP/Sepiolite
PP/PA/MA-g-PP/Sepiolite
PP/PA/MA-g-PP/Sepiolite

95/5
83/12/5
95/5
60/40
48/40/12
57/38/5
45/38/12/5
46.2/38.8/12/3
47.4/39.6/12/1
45/38/12/5

PP/PA
PP/PA/MA-g-PP
PP/PA/MA-g-PP/Sepiolite

80/20
68/20/12
64/19/12/5

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F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

temperature by using a SEM Philips XL at an accelerated voltage up

to 30 kV and various magnitudes. In order to clearly determine the
morphology of the dispersed phase, nodules of PA were selectively
extracted with formic acid prior to SEM observations.
Transmission electron micrographs were obtained with a SEM
Philips CM100 apparatus using an accelerator voltage of 100 kV.
The samples (70e80 nm thick) were prepared with a Reichert Jung
Ultracut 3E FC4E ultracryomicrotome by cutting at 130  C.
3. Results and discussion
3.1. Thermal degradation properties
3.1.1. Individual polymers
As observed on thermograms (TG) curves of individual polymers
under air and N2 (Fig. 1a), PA was thermally more resistant than PP
and in addition, contrary to PP, PA exhibited a degradation behavior
in the same range of temperature under air and N2. It can be noticed
that its TG curve is only slightly affected by the presence of oxygen.
In fact, under pyrolytic conditions, PA-6 degrades in one step while
a two-step process occured under thermo-oxidative conditions
[25] consisting primarily of the decomposition of the bulk polymer
followed by the degradation of the char layer. No signicant change
was observed in the onset temperature of the main degradation
step. In contrast with that is generally reported for nanocomposites, the incorporation of 5 wt% of natural sepiolite into PA
did not lead to signicant enhancement of the thermal stability of
the nanocomposite as shown by T-20% and T-50% values (Table 2).
TG curve of PP under N2 was shifted to a higher temperature in
comparison with that obtained under air demonstrating the strong
effect of O2 on the thermal degradation of PP. Actually, the thermal
decomposition of PP led to complete volatilization in both inert and
oxidative atmosphere and the volatilization process was signicantly accelerated under oxidative atmosphere. Indeed, the thermal
decomposition of PP (Scheme 1) involves the random chain scission

Fig. 1. TG curves of: (a) pristine PP and PA under air and N2; (b) individual polymers
and blends as recorded under air ow.

Table 2
Temperature values corresponding to 20% weight loss (T-20 wt%) and 50% weight loss
(T-50 wt%) of PP, PA and the various PP/PA-6 blends as recorded under air ow.
T C
PP
PP/5-S
PP/MA-g-PP/5-S
PA
PA/5-S
PP/40-PA
PP/40-PA/MA-g-PP
PP/40-PA/5-S
PP/40-PA/MA-g-PP/5-S
PP/40-PA/MA-g-PP/3-S
PP/20-PA/MA-g-PP 5-S

300
318
338
433
434
320
406
318
403
408
362

(-20 wt%)

T C

(-50 wt%)

327
357
380
458
459
367
437
380
440
436
404

and starts by the elimination of tertiary hydrogen and the generation of radicals leading to chain scission and the formation of
lower molecular weight compounds [26]. In the presence of oxygen, the thermal oxidative degradation of PP takes place at lower
temperature via the action of a highly reactive peroxy radical intermediate that abstracts labile hydrogen radicals from polymer
chain leading to the formation of hydroperoxide species, as well as
another polymer radical, through which the process of decomposition can continue. Oxygen initiates, by hydrogen abstraction, the
PP radical degradation chain reaction at a much lower temperature
than the thermal initiation by CeC bond scission taking place in
nitrogen atmosphere [27].
In contrast with PA, the incorporation of natural sepiolite leads
to the formation to more thermally stable composites than pure PP
as shown by the higher T-20% and T-50% values (Table 2). This effect is
due to the clay barrier effect towards oxygen diffusion from the
atmosphere to the polymer and to the adsorption of the volatile
products, formed during PP degradation, on sepiolite surface and
inside the zeolitic pores that decreases the initial rate of degradation of the polymer [8].
3.1.2. Polypropylene/polyamide blends
Fig. 1b shows the thermograms (TG) of PP, PA and their blends.
The important results obtained from these curves are summarized
in Table 2. TG curves of uncompatibilized blends exhibited two
degradation steps corresponding to the degradation of PA and PP
phases and indicating the highly immiscible two-phase structure of
the blends. Interestingly, in the case of compatibilized blends with
MA-g-PP, PP phase degradation was signicantly reduced and the
so-obtained blends showed higher thermal resistance in comparison to both pristine PP and uncompatibilized PP/PA blends. The
improvement of the blends thermal resistance of seems to be more
likely due to the presence of MA-g-PP and not to sepiolite nanoparticles since the PP/40-PA/5-S composition was characterized by
a lower thermal resistance with respect to the unlled compatibilized blend. In order to further investigate the effect of blend
compatibilization, morphological analyses have been performed.
Due to the different polarity of PP and PA, their mixture led to
the formation of heterogeneous structure, containing large and
irregular PA dispersed domains (Fig. 2). The formation of such
morphology resulted from the competition between the
deformation/break-up of the dispersed phase and the coalescence
of so-formed nodules [28,29].
The addition of 5 wt% of sepiolite nanoparticles to the PP/PA
blends did not affect the blend morphology in which some large PA
domains were still observed. Only the incorporation of MA-g-PP,
alone or in the presence of sepiolite, triggered drastic renement
of the size of the dispersed phase. Such observation is consistent
with the localization of MA-g-PP at the interface preventing the

F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

1975

Scheme 1. Possible mechanism for the thermal decomposition of PP (adapted from Ref. [26]).

coalescence of PA domains and only favouring dispersed phase

break-up.
Clearly, the thermal resistance of the blends was strongly
affected by their morphology (Fig. 2) and the compositions that
showed higher thermal stability contained well dispersed PA
nodules of reduced average size as a result of the presence of MA-gPP. The drastic renement of the blend morphology when MA-g-PP
was used positively acts on the thermal resistance of PP/PA blends.
The incorporation of sepiolite alone (Fig. 2b) did not affect the
blend morphology but seemed to decrease the average size of the
PA nodules when combined with MA-g-PP (Fig. 2d).
In order to be able to determine whether any real increase of the
thermal resistance has additively or synergistically occurred as a
consequence of the presence of MA-g-PP and PA, it is necessary to
calculate additive TGA responses (theoretical curves) and compare
them with the experimental curves. Two theoretical curves have
been calculated by considering, TG curves of PP under both air and

Fig. 3. Experimental and theoretical TG curves of PP/PA blends (see text).

Fig. 2. SEM pictures of : (a) PP/40-PA; (b) PP/40-PA/5-S; (c) PP/40-PA/MA-g-PP and (d) PP/40-PA/MA-g-PP/5-S compositions (PA nodules were selectively extracted with formic acid
in the case of compositions c and d).

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F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

Fig. 4. Effect of PA content (a) and sepiolite content (b) on TG curves of PP/PA blends
under air.

nitrogen. Fig. 3 showed individual TG curves of PP, PA and experimental curves of the compatibilized and uncompatibilized blends
in comparison with the theoretical TG curves of the corresponding
blends.
As far as the uncompatibilized blend was considered, the
theoretical curve of PP/PA blend, obtained by the arithmetic addition of TGA curves of PP and PA (taking into account the blend
composition and as recorded under air) was similar to the experimental curve. This indicated the absence of interaction between PP
and PA phases all along the thermal decomposition. Each polymer
decomposed according to its own degradation process. Only a slight
increase of the thermal resistance of PP phase was observed. The TG
curve of the compatibilized blend was similar to that calculated by
using the TG curve of PP under nitrogen.
However, the second theoretical TG curve, considering PP TG
curve under nitrogen perfectly tted with the experimental TG
curve of the compatibilized blend. According to this result, it can be
assumed that, when MA-g-PP was used, PP phase was mainly
degraded by pyrolysis due to the presence of the small and well
dispersed PA nodules that limited the oxidative thermal degradation of PP. Indeed, the TGA residue obtained under air at 350  C
(20  C/min) during thermo-oxidative degradation of the compatibilized PP/PA blend exhibited a dark char structure that could limit
the oxygen diffusion and provide a heat insulator and a mass
transport barrier to the volatile products generated during the
decomposition.
In the case of the uncompatibilized blend, PA droplets are too
large in size and poorly dispersed in the major PP phase to lead to
the formation a homogeneous char layer. Therefore part of PP was
directly exposed to the action of oxygen during thermogravimetric
analysis.
The effect of relative content in polyamide and sepiolite has also
been investigated. Clearly, the decrease of PA content (from 40 to
20 wt%) induced a signicant reduction of the thermal stability of
the compatibilized blends (Fig. 4a and Table 2). This result

Fig. 5. HRR curves obtained during mass loss cone calorimeter at 35 kW/m2.

demonstrated the importance of the thermal stabilization action of

PA in compatibilized PP/PA blends. In contrast, at constant PA
content (i.e., 40 wt%), the decreasing content of sepiolite, from 5 to
3 wt%, did not affect the TG curves of the blends (Fig. 4b). In the case
of compatibilized blend, as far as TGA is concerned, the PA content
seemed to be the key parameter that governs the thermal resistance of the composition.
3.2. Fire behavior
3.2.1. Individual polymers
It is generally accepted that the formation of a nanocomposite
(whether intercalated or exfoliated) enables good ame retardant
properties to be achieved. Before testing PP/PA blends, the ame
retardant effect of sepiolite nanoparticles on PP and PA were
separately evaluated. As observed on Fig. 5a and Table 3, the

Table 3
Time to ignition, peak of heat release and pHRR reduction for PP, PA and their blends.

PP
PP/5-S
PP/MA-g-PP/5-S
PA
PA/5-S
PP/40-PA
PP/40-PA/MA-g-PP
PP/40-PA/5-S
PP/40-PA/MA-g-PP/5-S
PP/40-PA/MA-g-PP/3-S
PP/40-PA MA-g-PP/1-S
PP/20-PA/MA-g-PP/5-S

TTI (s)

pHRR
(Kw/m2)

pHRR
reduction (%)

54
55
55
140
140
56
70
65
90
82
75
56

860
660
600
780
550
770
790
706
425
575
845
406

e
24
30
e
e
10
8
18
51
33
2
53

F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

incorporation of 5 wt% of sepiolite nanoparticles into individual

polymers led to a slight decrease of pHRR by ca. 24% when PPsepiolite nanocomposite is tested and by ca. 30% in the case of
PA-sepiolite nanocomposite. Even the increase of the dispersion
state of sepiolite nanoparticle into PP by using highly lled MA-gPP masterbatch, did not lead to a signicant reduction of pHRR
value (ca. -30%). These results are in accordance with what was
observed by Marosfoi et al. [11]. The low ame retardant effect of
needle-like clay nanoparticles into PP could be explained by the
strong catalytic effect of sepiolite on PP pyrolysis attributed to the
reactivity of the tertiary carbon atoms of PP, which can easily form
carbon radicals and initiate thermal volatilization of PP. The
mechanism of the catalytic action of sepiolite seems to be similar to
that of zeolites during catalytic thermal cracking of alkanes, via
Brnsted acid sites of Al in the zeolitic framework [27].
3.2.2. Polypropylene/polyamide blends
The effect of the incorporation of 40 wt% of PA and/or 5 wt% of
sepiolite nanoparticles on the ame retardancy of compatibilized
and uncompatibilized PP/PA blends has been investigated by mass
loss cone calorimeter test. Results are summarized in Table 3 and
presented on Fig. 5b.
As previously evidenced by TGA, the blend compatibilization
allowed improved the thermal stability of PP/PA blend. Such
improvement was also associated to a resistance to ignition during
mass loss calorimeter. Indeed, the use of 5 wt% of MA-g-PP to PP
containing 40 wt% of PA led to an important increase of the time to
ignition (TTI) from 56 to 70 s. The resistance to ignition was further
improved when 5 wt% of sepiolite nanoparticles are incorporated
into the compatibilized blend. TTI increased up to 90 s while the
incorporation sepiolite-based uncompatibilized blend only led to
limited improvement of TTI that reaches 65 s. These results are in
contrast to the observations achieved by TGA that highlighted
similar thermal resistance of both lled and unlled compatibilized
blends.
However, only the combination of compatibilizing agent and
5 wt% of nanoparticles allowed signicant reduction of pHRR of
about 50% as a result of the formation of a cohesive char layer at the
surface of the material during the combustion. This char is an
important factor that considerably improves the ame retardant
behaviour of the blend. In the case of unlled PP/PA blend, no
signicant pHRR reduction was observed in both compatibilized
and uncompatibilized blends. Despite the enhancement of thermal
resistance evidenced by TGA, the char formed during the combustion of unlled PP/PA compositing was not able to produce
efcient layer that ensure good barrier protection during re
testing. It is worth nothing that the incorporation of natural sepiolite into uncompatibilized blend did not lead to signicant
reduction of pHRR. This could be related to the blend morphology

1977

of uncompatibilized blend that contains large and poorly dispersed

PA nodules. This kind of morphology promoted the formation of
isolated domains of carbonaceous char that could not allow the
formation of coherent char network. When incorporated into
compatibilized blend, sepiolite nanoparticles improved the thermal
stability of the char formed via the presence of well dispersed small
PA nodules. These nodules allowed obtaining consolidated char
consisting in interlinked islands-in-the-sea carbonaceous domains. Similar model was also suggested by Horrocks et al. [1] and
Bourbigot et al. [30] in intumescent systems. This char protected
the underlying material from igniting and acted as an insulating
barrier that reduces heat transfer between the heat source and the
polymer surface and thus limited fuel transfer from the polymer
towards the ame as well as the diffusion of oxygen into the materials. The efciency of the char layer formed during the combustion of several systems was studied by sonnier et al. [31] by
using an innovative method based on the comparison of results
obtained in both cone calorimeter and pyrolysis combustion ow
calorimeter (PCFC).
PP is also partly involved in the char formation taking advantage
of the charring of PA/sepiolite domains. In addition, SEM analyses
(Fig. 6) performed on the combustion residues of PP/40-PA/MA-gPP/5-S showed that sepiolite nanobers are involved in the structuration and consolidation of the carbonized residues. Such observations evidenced the key-role of sepiolite nanoparticles in the
strengthening of the char against cracking.
3.2.2.1. Inuence of sepiolite content. The combination of MA-g-PP
and sepiolite appeared necessary for the formation of thermally
stable char layer that signicantly improved the ame retardancy
of PP/PA blends. Indeed, when used separately, neither MA-g-PP
nor sepiolite nanoparticles led to signicant reduction of pHRR
values. Moreover, the decrease of nanoparticles content strongly
affected the ame retardancy of the blends and pHRR was found to
increase from 425 kW/m2 with 5 wt% of sepiolite to 575 kW/m2 and
845 kW/m2 with 3 wt% and 1 wt% of sepiolite, respectively (Fig. 7
and Table 3). As evidenced in Fig. 8, the sepiolite content strongly
affected the amount of char and its thermal stability. This behavior
is similar to what is usually reported in re retardancy of polymer
nanocomposites and is due to the formation of a barrier that limits
volatiles mass transport, heat and oxygen diffusion owing to the
formation of char layer at the material surface. As far as MA-g-PP is
concerned, Shartet el al [32] showed that the peak of heat release
rate decreased considerably with increasing montmorillonite content. However, authors observed an absence of signicant char
formation since the increase in residues observed corresponded to
the amount of clay incorporated.
Phosphorus ame retardant additives act mainly in condensed
phase and could promote the char formation in polar polymers

Fig. 6. SEM images of the char formed during the combustion of PP/40-PA/MA-g-PP/5-S composition.

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F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

Fig. 7. HRR curves of compatibilized blend containing different amounts of sepiolite

nanoparticles (35 kW/m2).

[33,34]. The promotion of the char layer action is possible also by

combining different nanoparticles. For example, the incorporation
of sepiolite nanoparticles has been shown to affect positively the
char structuration of PLA lled with carbon nanotubes (MWNT).
The best performance with a 58% drop in PHRR was obtained with a
ternary blend containing 10 wt% of MWNT and 2 wt% of sepiolite
nanoparticles. This enhancement was attributed to the creation of a
tighter char network when sepiolite was used in contrast with
MWNT lled specimen that showed some porosity during heating
at 325  C in oven [35].
3.2.2.2. Inuence of polyamide content. In order to investigate the
effect of PA content on the re behavior of compatibilized PP/PA
nanocomposite, an additional blend containing 20 wt% of PA has
been prepared and tested. Fig. 9a shows HRR curves obtained
during mass loss calorimeter test. At constant sepiolite content
(5 wt%), the decrease of PA content from 40 to 20 wt% triggered
some modications on HRR curve showing a detrimental effect,
especially on the resistance to ignition while the pHRR level remains similar (Fig. 9a). The decrease of PA content, from 40 to 20 wt
%, did not seem to generate a discontinuous PA/sepiolite -rich
carbonaceous surface layer upon combustion since pHRR level

Fig. 9. HRR curves obtained during mass loss cone calorimeter test at (35 kW/m2).

remains similar to that obtained with 40 wt% of PA. Thus, this PA

content is still greater than the critical concentration that allows
generation of coherent char network. However, this reduction
affected the time to ignition (from 90 s to 56 s). The decrease of PA
content also induced a reduction of the number of isolated domains
of carbonaceous char that needs longer time to connect and form
continuous char.

Fig. 8. Effect of sepiolite content on residues at the ignition and at the end of mass loss calorimeter test.

F. Laoutid et al. / Polymer Degradation and Stability 98 (2013) 1972e1980

1979

Fig. 10. TEM images of PP/40-PA/MA-g-PP/5-S (MB PA) composition.

3.2.2.3. Inuence of sepiolite localization. In order to better understand the effect of the localization of sepiolite nanoparticles on the
ame retardant properties of the compatibilized blends, an additional composition has been prepared by using a PA/sepiolite
masterbatch. Such composition allowed the connement of sepiolite nanoparticles into PA nodules (Fig. 10). The HRR curve (Fig. 9b)
obtained during the mass loss calorimeter test of this composition
was similar to the one obtained by using MA-g-PP-based masterbatch suggesting that the protective char layer results mainly from
the charring of PA nodules. The presence of sepiolite nanoparticles
in the continuous polyolenic phase did not seem necessary to
obtain good re properties. This result highlighted that the
connement of sepiolite into PA nodules is an efcient way for
promoting re resistance of the blend and reducing the catalytic
action of sepiolite nanoparticles. It is concluded that the connement at PA nodules of a minimum content in sepiolite nanoparticles, i.e., ca.5 wt%, was able to improve both thermal resistance
and re properties of compatibilized blend.
4. Conclusions
In the present study, we have reported the effect of the combination of both sepiolite and polyamide on both thermal and re
behaviour of PP. The compatibilization of the compositions was also
studied. The thermal and re properties of the different studied
compositions showed that the joint action of MA-g-PP and natural
sepiolite improved the thermo-gravimetric resistance and the re
properties of PP/PA blends. Interestingly, no signicant pHRR
reduction was obtained and only a slight improvement of the time
to ignition is recorded due to the improvement of the thermogravimetric resistance when MA-g-PP and sepiolite were used
separately.
It came out that the size, dispersion state and amount of PA
nodules are the key-parameters that allow obtaining higher thermal resistance owing to the generation of a cohesive char layer. The
efciency of the char layer formed during the combustion was
found to depend on the amount of both sepiolite and PA. In compatibilized blends, the presence of well dispersed small PA nodules,
allowed for obtaining of cohesive charring due to the presence of
interlinked islands-in-the-sea carbonaceous domains. The incorporation of sepiolite nanoparticles improved the thermal resistance
of the char formed during the combustion is required for obtaining
good ame retardant properties since they.
As demonstrated, polymer blending allowed enhancing the re
properties of PP through a judicious choice of the nanoparticles/

compatibilizer pair. This concept can be more generally applied to

other polymers as a new efcient route for the production of ame
retarded thermoplastics.
Acknowledgements
Authors thank Wallonia Region, Nord-Pas de Calais Region and
European Community for the nancial support in the frame of the
IINTERREG IV e NAVARE project. This work was also supported by
the European Commission and Rgion Wallonne FEDER program
(Materia Nova) and OPTI2MAT program of excellence, by the
Interuniversity Attraction Pole program of the Belgian Federal
Science Policy Ofce (PAI 6/27) and by FNRS-FRFC.
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