Fire Retardancy of polypropylene/kaolinite composites

Marcos Batistellaa,b, BelkacemOtazaghinea, Rodolphe Sonniera, Carlos Petterb, Jose-Marie Lopez-Cuestaa

a
Ecole des Mines dAls, Centre des Matriaux (C2MA) - Ple Matriaux Polymres Avancs, 6 Avenue de
Clavires, 30319 Ales cedex, France
b
Universidade Federal do Rio Grande do Sul, Av. Bento Gonalves, 8500 Porto Alegre RS Brazil
(marcos.batistella@mines-ales.fr)

Abstract

Introduction
Polymers are more and more used in many applications due to their versatile properties. Nevertheless,
one of their main drawbacks is their high flammability. Research about the flame retardancy of
polymers is then a great concern. Flammability of polypropylene (PP) composites was extensively
studied [14]. Fina et al. reported the use of polyhedral oligomeric silsesquioxane (POSS) compounds
with different structures as flame retardants for PP. They showed a decrease in the peak heat release
rate (PHRR) with relatively low concentration (10-20%wt.) of POSS. Zhao et al. [5] showed that
montmorillonite (MMT) modified with amipropylisooctyl POSS improved the mechanical behavior of
polyamide 12 (PA12). Yei et al. [6] also studied the influence of a surface treated MMT with the same
POSS on the thermal behavior of polystyrene (PS). The authors showed that composites with
functionalized MMT were more thermally stable than pure polymer or composites with untreated
MMT. Even if the use of POSS structures seems to give good results in terms of fire retardancy, few
studies concerns its use in polymers (parler du prix???).

The use of mineral fillers as fire retardants in polymer matrix are well known and widely studied [7
10]. Aluminum and magnesium hydroxides (respectively ATH and MDH) are the most widely used
inorganic fire retardants. To achieve fire retardancy with these mineral fillers, about 50-60% loading is
required which decrease the physical properties of the composites. Beyond ATH and MDH, other
mineral fillers have been studied in the literature [8], [9], [1113]. Clerc et al. reported that the
incorporation of talc particles in an EVA copolymer could lead to a swelling of the sample.
Furthermore, the authors suggested a relationship between viscosity and the final thickness of the
sample: If the viscosity is too high, trapped bubbles cannot grow and swelling effect is reduced.
Recently Kashiwagi et al. have compared the storage modulus (G) of PS filled with MMT and multi
walled nanotubes (MWNT) [10]. The authors showed a decrease in the normalized peak of mass loss
with the increase in the storage modulus (G). It is well known that the addition of mineral fillers into
polymers increases the viscosity and decreases the melt elasticity. An extensive study on particle
orientation and rheological properties of talc-filled PP systems has been done by Chang and White
[14]. They showed that at relative high filler loadings (~20 wt %), the talc particles are oriented in the
direction of flow. Also, rheological tests showed the increase in viscosity with the increase in filler
loading and the decrease in particle size. Beyond particle size and aspect ratio of fillers, polymer/filer
interaction can modify rheological properties of the composites. The surface modification of mineral
fillers has generally been directed towards improving the mechanical properties of composites by
improving the filler-matrix interface. The surface modifications of mineral fillers may significantly
affect rheological properties of the polymer composites. The modification of the particle/particle
and/or particle/polymer interactions can affect the viscosity of the composites by changing the filler
dispersion or wetting effects. It was showed that surface treatment can lead to an increase in the
viscosity if chemical bonds occur between fillers and polymer chains [15], [16]. Nishitani et al. have
studied the effect of silane coupling agents on the rheological properties of short and long glass fiber
reinforced polypropylene composites in molten state [16]. Surface treatment by silane coupling agents
increased the storage modulus and reduced the peak in the loss tangent. Furthermore, decrease in the
dynamic viscosity was affected by the concentration of coupling agents.

In this study the influence of the surface treatment of kaolinite and the changes in the rheology and fire
performance of composites were studied.

Materials and methods

Trisilanol Isooctyl POSS were used as purchased from Hybrid Plastics (Figure a faire). PP was a 505P
from Sabic (MFR 2.0 g/10 min at 230C/2.16 kg).

Two clay minerals were used in this study: a kaolinite kindly supplied by Vale and talc supplied by
Imerys. Commercial designation and characteristics of both fillers are showed in Table 1.

Table 1.Characteristics of fillers.

Commercial Mean diameter Specific surface

designation (m) area (m2/g)
Kaolinite Paralux 0.9 12
(a verifier o a
Talc Jetfine 0.7C 0.7
faire)

Preparation of PP composites

Compositions were extruded using a Clextral BC21 twin-screw extruder (CLEXTRAL SAS &
AFREM, Firminy, France) and injection molded using 50 ton Krauss-Maffei equipment (Munich,
Germany). Square specimens were prepared with dimensions of 100 100 4 mm.
Characterization

Thermogravimetric analysis was carried out on 102 mg samples at 10C*min-1 to 800 C under
nitrogen flow using a Perkin-Elmer Pyris-1 TGA. A Scanning Transmission Electron Microscopy (FEI
Quanta 200 SEM) was used to study the morphology of the samples. All images were obtained under
high vacuum at a voltage of 15.0 kV. The cone calorimeter experiments were carried out using a Fire
Testing Technology apparatus with an irradiance of 50 kW*m -2 according to ISO 5660 standard.
Viscosity measurements were carried out in dynamic mode at 160 C using 0.5 % strain and a
frequency ranging from 10-1s-1 to 102s-1 (ARES, Rheometric Scientific).

Surface modification of kaolinite

Surface treatment of kaolinite particles were carried out in ethanol/water mixture (96/4). 10 g of
kaolinite, 0.3 g of trisilanol isooctyl POSS and 90 mL of an ethanol/water (90/10) solution were
introduced in a 250 ml flask fitted with a condenser. The mixture was then stirred and heated at solvent
reflux for 4h. The mixture was next centrifuged to eliminate the liquid phase and washed three times
with ethanol. The POSS modified kaolinite was dried at 50 C overnight. Surface treated kaolinite is
referred as Kaol-POSS.

Discussion
Cone calorimeter tests

HRR plots of PP/Kaol and PP/Talc composites are shown in . The behavior of PP is typical of a non-
charring polymer with a high PHRR (c.a. 1500 kW.m -2) and without formation of residue. The
incorporation into the polymer of kaolinite or talc showed a reduction in PHRR even for 10% wt.
loading, with a larger reduction for talc composites. At higher filler loading, both fillers showed the
same PHRR reduction (c.a. 70 -80 %) with a longer time burning. The total heat release (THR) did not
show a significant difference for all these compositions. This is an expected behavior because the
kaolinite like the talc is supposed to act in the condensed phase and to have a barrier effect (Table 2).

Table 2. Cone calorimeter results for PP/Kaolinite and Pp/talc composites.

PHRR THR THE Mass Residue Mass Residue

TTI (s)
(kW/m2) (MJ/m2) (MJ/m2) (%) (Theoretical)*

PP 505P 0 0
PP/Kaol-10 634 35 144 9.8 8.6

PP/Kaol-20 396 38 136 20.9 17.2

PP/Kaol-30 348 41 126 29.4 25

PP/Talc-10 377 49 137 19 9.6

PP/Talc-20 341 56 135 28 19.2

 PP/Talc-30 395 50 107 39 28.6
* Theoretical mass calculated as the mass loss of the filler and the neat polymer.

Time to ignition .

Fig.1. HRR plots of different PP composites at 50 kW*m-2.

At the end of combustion, there is no residue for PP while the residue of PP/Kaoland PP/Talc was
voluminous with a little swelling behavior (Fig.2). It is interesting to note that the incorporation of talc
in PP leads to the formation of 10% of char for all formulations. This effect

For samples filled with kaolinite, the char formation was also observed and increased with kaolinite
content. The formation of this char could be due the formation of a protective layer at the surface of
the sample.

A B

Fig.2. Cone calorimeter residues for the PP/Kaol-30 (A) and PP/Talc-30(B) samples.
Surface modification of kaolinite

Frost et al. [17] have reported that kaolinite has five infrared active modes in the 3800 3400 cm -1
region, centered at 3693 (1), 3681 (4), 3667 (2), 3651 (3), ascribed to the inner surface
hydroxyls and 3619 (5) cm -1 (inner hydroxyl groups). The kaolinite used in the present work
displays bands at 3692, 3665, 3650, and 3617 cm -1, in agreement with the literature. The Kaol-POSS
sample shows a band centered at 2900 cm -1 characteristic of C-H bonds and indicates that the POSS
part was successfully grafted on the kaolinite surface (Fig. 3).

Fig. 3. FTIR of Kaol and Kaol-POSS.

Thermal stability of Kaol and Kaol/POSS are shown in Fig .6. Kaol shows a single mass loss between
450 and 500 C corresponding to mass loss of structural water (about 14 %). Kaol-POSS shows a
decrease in the thermal stability in comparison to Kaol. The mass loss starts at about 320 C which
corresponds to the degradation of the POSS group. The mass loss for Kaol-POSS is about 16.7%. (a
faire ATG du POSS).
 Fig.4. TGA of untreated (K) and surface treated (KP) kaolinite under N2 at 10C.min-1.

Effect of surface treatment of Kaolinite

Fig.5. HRR plots of PP/K and PP/KP at 50kW*m-2.

Values of HRR for the composites filled with Kaol-POSS are shown in Fig.5 and compared to the
PP/Kaol-30 sample. The grafted kaolinite shows a decrease in fire performance compared to PP/Kaol
composites. Contrary to the PP/Kaol samples, no char was formed for the PP/Kaol-POSS composites
and the final residue was due to the mineral filler. As it was previously discussed, char formation in the
case of talc and Kaol composites could be due to the formation of a protective barrier during the cone
test at the sample surface. Viscoelastic changes due the presence of the mineral fillers could also
explain this behavior by a reduction of the mass transfer from the sample to the flame. In the case of
Kaol-POSS, the formation of a rigid protective layer was observed as for Kaol. Thus, the difference of
behavior for Kaol and Kaol-POSS could be explained by differences of viscosity. In order to
understand the role of viscosity, rheology analyses were performed.
 Table 3.Cone calorimeter results for the PP/Kaol-POSS composites.

Mass Mass Residue

PHRR THR THE
TTI (s) Residue (Theoretical)*
(kW/m2) (MJ/m2) (MJ/m2)
(%)
PP 0 0
PP/Kaol-POSS-10 850 140 7 8

PP/Kaol-POSS-20 650 141 15.8 16

PP/Kaol-POSS-30 430 137 23 24

* Theoretical mass calculated as the mass loss of the filler and the neat polymer.

Thermal Stability of PP composites

Thermal degradation of talc occurs in one step between 550 and 600C and corresponds to a mass loss
of about 4%. Thermal degradation of PP was well studied and consists in a mass loss in a single step
which starts at about 310C [1821]. PP thermally degrades to volatile products through a radical
chain process originated by carbon-carbon bond scission. The addition of talc particles into a PP
matrix lead to a slightly improvement in PP thermal stability: mass loss starts at a higher temperature.
Moreover, adding Kaol or Kaol-POSS leads to a better improvement of the thermal stability of PP
composites (pour quoi?). It should be noted that for all the composites, no char was formed and the
final mass corresponds to fillers after degradation.
 Fig .6. Representative curves of TGA results of PP/ kaolinite at 30% wt. under N2 at 10 C/min.

Rheological behavior
Fig.7 compares the G and * of pure polypropylene and the composites with talc, Kaol and Kaol-
POSS at 30%wt. The incorporation of Kaol dramatically changes the linear viscoelastic response to
shear deformation. PP/talc and PP/Kaol composites showed the same behavior, with an increase in the
storage modulus at lower frequencies. Storage modulus of PP/Kaol-POSS has not changed in
comparison with pure polymer. Generally, it is suggested in the literature that the modification of the
particles surface increase the viscosity and modulus values if chemical bonding occurs between
mineral particles and matrix [22], [23]. Some coupling agents could also act as wetting or dispersant
agents. In our case, the reduction in viscosity and modulus could be due to a lubricating effect at the
particle-polymer interface or plasticizingeffect of the polymer matrix [23]. Moreover, the surface
treatment of mineral fillers could improve their dispersion in the polymer matrix, and reduce the
viscosity and modulus. To verify this hypothesis, an image analysis (a voir avec Anne-Sophie) of
PP/Kaol-30 and Kaol-POSS-30 samples was conducted. As can be seen in Table 4, mean agglomerate
area and mean interparticle distance for PP/Kaol-POSS composite

Table 4.

Mean agglomerate Mean Interparticle

Composite
area (m2) distance (L) (m)
PP/Kaol-30 27 108.9
PP/Kaol-POSS-30
It is known in the literature that the presence of agglomerates creates an apparent situation of higher
filler loading. This is due to the agglomerates which traps part of the surrounding polymer in their
interparticle voids [24].

Fig.7. Rheological behavior of PP composite for 30% wt. of mineral filler.

Viscosity vs. fire behavior

In a previous work (REF), we have shown a relation between the viscosity at the melt state and the
PHRR value for different composites. This study showed a decrease of the PHRR values with the
increase of viscosities for EVA/kaolinite composites. Fig.8 plots the relative PHRR versus the relative
elastic modulus (G) for PP/Kaol, PP/Kaol-POSS and PP/Talc samples. Relative values were
calculated as the PHRR or elastic modulus of the composite divided by the PHRR or elastic modulus
of neat polymer. It should be noticed that rheological analyses were performed at 200 C, while the
temperature of the condensed phase during the cone calorimeter tests increases from ambient to
polymer pyrolysis temperature (i.e. approximately 450-500 C for PP). Nevertheless we assume that
the differences in viscosity between composites are qualitatively similar at processing temperature
(200 C) and during cone calorimeter test.
 Fig.8. Comparison of normalized G vs. normalized PHRR.

As in our previous study, two distinct tendencies could be observed: in the Regime 1, relative
PHRR decreases quickly from 1 to 0.2 when G increases from 1 to 2.5. Below this value a second
Regime is observed (Regime 2): relative PHRR remains almost constant close to 0.2 whatever the
further increase in relative G. This behavior supports the hypothesis that a more elastic composite (i.e.
a higher G) could lead to an improved fire behavior by limiting the bubbling, convection into the
condensed phase and pyrolysis gases transfer to the flame. When these phenomena are limited enough
(i.e. when elastic modulus becomes higher than a threshold value) the PHRR is stabilized and does not
decrease anymore.

It is interesting to note that the PP/Kaol-POSS composites showed a decrease in PHRR with no change
of the normalized G values, but it was in the Regime 1 zone. This could indicate that, in the case of
PP/Kaol-POSS composites, the reduction in the pHRR could be due to a barrier effect and/or a dilution
effect.

Based on the fire behavior and rheological analyses of the different composites, one can conclude that
the increase of G, and thus, the elastic character, can limit the release of pyrolysis gases and,
consequently, improve the flame retardancy.

Conclusions
Incorporation of kaolinite and talc improve the fire behavior of PP. and leads to the formation of a char
depending on the

Incorporation of kaolinite leads to a better thermal stability in TGA.

Surface treatment of kaolinite leads to a lower G in comparison to untreated kaolinite and talc.
Surface treatment of kaolinite leads to a less sharp decline of PHRR values in comparison to untreated
kaolinite.

Comparison between viscosity and PHRR showed a decrease in PHRR with the increase of relative
G. We assume that a high viscosity could limit the pyrolysis gases transfer to the gas phase.

References

[1] A. Fina, J. Feng, and F. Cuttica, In-depth radiative heat transmittance through
polypropylene/nanoclay composites, Polymer Degradation and Stability, Feb. 2013.

[2] L. Morice, S. Bourbigot, and J.-M. Leroy, Heat Transfer Study of Polypropylene-Based
Intumescent Systems during Combustion, Journal of Fire Sciences, vol. 15, no. 5, pp. 358
374, Jan. 1997.

[3] X. Wang, X. Cheng, L. Li, S. Lo, and H. Zhang, Effect of ignition condition on typical
polymers melt flow flammability., Journal of hazardous materials, vol. 190, no. 13, pp.
76671, Jun. 2011.

[4] A. Szczygielska and J. Kijeski, Studies of properties of polypropylene/halloysite

composites, Polish Journal of Chemical Technology, vol. 13, no. 3, pp. 6165, Jan. 2011.

[5] F. Zhao, X. Bao, A. R. McLauchlin, J. Gu, C. Wan, and B. Kandasubramanian, Effect of POSS
on morphology and mechanical properties of polyamide 12/montmorillonite nanocomposites,
Applied Clay Science, vol. 47, no. 34, pp. 249256.

[6] D.-R. Yei, S.-W. Kuo, Y.-C. Su, and F.-C. Chang, Enhanced thermal properties of PS
nanocomposites formed from inorganic POSS-treated montmorillonite, Polymer, vol. 45, no.
8, pp. 26332640, 2004.

[7] K. McGarry, J. Zilberman, T. R. Hull, and W. D. Woolley, Decomposition and combustion of

EVA and LDPE alone and when fire retarded with ATH, Polymer International, vol. 49, no.
10, pp. 11931198, 2000.

[8] T. R. Hull, A. Witkowski, and L. Hollingbery, Fire retardant action of mineral fillers,
Polymer Degradation and Stability, vol. 96, no. 8, pp. 14621469, Aug. 2011.

[9] L. Clerc, L. Ferry, E. Leroy, and J.-M. Lopez-Cuesta, Influence of talc physical properties on
the fire retarding behaviour of (ethylene-vinyl acetate copolymer/magnesium hydroxide/talc)
composites, Polymer Degradation and Stability, vol. 88, no. 3, pp. 504511, Jun. 2005.

[10] T. Kashiwagi, M. Mu, K. Winey, B. Cipriano, S. R. R. Raghavan, S. Pack, M. Rafailovich, Y.

Yang, E. Grulke, J. Shields, R. Harris, and J. Douglas, Relation between the viscoelastic and
flammability properties of polymer nanocomposites, Polymer, vol. 49, no. 20, pp. 43584368,
Sep. 2008.
[11] S. Duquesne, F. Samyn, S. Bourbigot, P. Amigouet, F. Jouffret, and K. Shen, Influence of talc
on the fire retardant properties of highly filled intumescent polypropylene composites,
Polymers for Advanced Technologies, vol. 19, no. 6, pp. 620627, Jun. 2008.

[12] A. Durin-France, L. Ferry, J.-M. M. Lopez Cuesta, and A. Crespy, Magnesium hydroxide/zinc
borate/talc compositions as flame-retardants in EVA copolymer, Polymer International, vol.
49, no. 10, pp. 11011105, Oct. 2000.

[13] X. Almeras, M. Le Bras, P. Hornsby, S. Bourbigot, G. Marosi, S. Keszei, and F. Poutch, Effect
of fillers on the fire retardancy of intumescent polypropylene compounds, Polymer
Degradation and Stability, vol. 82, no. 2, pp. 325331, Jan. 2003.

[14] C. H. Suh and J. L. White, Talc-thermoplastic compounds: particle orientation in flow and
rheological properties, Journal of Non-Newtonian Fluid Mechanics, vol. 62, no. 23, pp. 175
206, Feb. 1996.

[15] H.-L. Luo, C. D. Han, and J. Mijovi, Effects of coupling agents on the rheological behavior
and physical/mechanical properties of filled nylon 6, Journal of Applied Polymer Science, vol.
28, no. 11, pp. 33873398, Nov. 1983.

[16] Y. Nishitani, I. Sekiguchi, B. Hausnerova, N. Zdrazilova, and T. Kitano, Rheological

properties of aminosilane surface treated short glass fibre reinforced polypropylenes. Part 1:
Steady shear and properties in molten state, Polymers & Polymer Composites, vol. 15, no. 2,
pp. 111119, 2007.

[17] R. L. Frost, Hydroxyl Deformation in Kaolins, Clays and Clay Minerals, vol. 46, no. 3, pp.
280289, 1998.

[18] M. Zanetti, G. Camino, P. Reichert, R. Mlhaupt, Z. Marco, C. Giovanni, R. Peter, and M.

Rolf, Thermal Behaviour of Poly(propylene) Layered Silicate Nanocomposites,
Macromolecular Rapid Communications, vol. 22, no. 3, pp. 176180, Feb. 2001.

[19] J. D. Peterson, S. Vyazovkin, and C. a. Wight, Kinetics of the Thermal and Thermo-Oxidative
Degradation of Polystyrene, Polyethylene and Poly(propylene), Macromolecular Chemistry
and Physics, vol. 202, no. 6, pp. 775784, Mar. 2001.

[20] J. H. Chan and S. T. Balke, The thermal degradation kinetics of polypropylene: Part III.
Thermogravimetric analyses, Polymer Degradation and Stability, vol. 57, no. 2, pp. 135149,
Aug. 1997.

[21] T. E. Davis, R. L. Tobias, and E. B. Peterli, Thermal degradation of polypropylene, Journal

of Polymer Science, vol. 56, no. 164, pp. 485499, Feb. 1962.

[22] D. M. Bigg, Rheological analysis of highly loaded polymeric composites filled with non-
agglomerating spherical filler particles, Polymer Engineering and Science, vol. 22, no. 8, pp.
512518, Jun. 1982.

[23] C. D. Han, T. Van Den Weghe, P. Shete, and J. R. Haw, Effects of coupling agents on the
rheological properties, processability, and mechanical properties of filled polypropylene,
Polymer Engineering and Science, vol. 21, no. 4, pp. 196204, Mar. 1981.

[24] A. V. Shenoy, Rhology of Filled Polymer Systems. AA Dordrecht: Kluwer Academin Publisers,
1999, p. 475.