FIRE AND MATERIALS Fire Mater. 2011; 35:183192 Published online 5 November 2010 in Wiley Online Library (wileyonlinelibrary.com).

DOI: 10.1002/fam.1048

Natural mineral re retardant llers for polyethylene

Sverine Patricia Bellayer1, , , E. Tavard2 , S. Duquesne1 , A. Piechaczyk2 and S. Bourbigot1
1 Unit

Matriaux et Transformations (UMET) - UMR CNRS 8207 Equipe Ingnierie des Systmes Polymres (ISP) Ecole Nationale Suprieure de Chimie de Lille (ENSCL), BP90108, 59652, Villeneuve dAscq Cedex, France 2 Nexans Research Center, 170 Av. Jean Jaures, 69353 Lyon Cedex 07, France

SUMMARY In this article, we study the behaviour of common and low cost mineral llers into a polyethylene matrix when exposed to mass loss calorimeter conditions. The different systems are made of linear low-density polyethylene (LLDPE), with 50 wt% of calcium carbonate (CaCO3 ), magnesium carbonate or talc treated with stearic acid or nontreated. These systems were exposed to an external heat ux of 50 kW/m2 and their burning behaviours were compared. Signicant decrease of heat release rate peaks (PkHRR) was obtained with all these mineral llers; however, even better results were obtained when particles were treated with stearic acid. Indeed, the system with CaCO3 -treated stearic acid leads to a surprising intumescent behaviour. A rheological study showed no impact of stearic acid on the viscosity of the system and did not explain the appearance of the intumescent phenomenon. However, scanning electron microscopy (SEM) shows that stearic acid enhances the dispersion of particles into the polymer and acts as a dispersive agent. The results also show that the aspect ratio of the particles, the cation nature of the carbonates and the polarity of the polymer matrix have an effect on the appearance or not on the intumescent phenomenon. Copyright 2010 John Wiley & Sons, Ltd.
Received 6 January 2009; Revised 8 April 2009; Accepted 22 March 2010 KEY WORDS:

flame retardance; intumescence; polyethylene; carbonates

INTRODUCTION Polyethylene (PE) is commonly used in the plastic industry and especially for cable covering due to its abrasion resistance, exibility, excellent electric insulation properties, low toxicity and easy processing. However, PE is highly ammable and drips when burning, hence ame retardant (FR) systems have to be incorporated into the polymer to reduce re hazards and to meet the required standard performance. The most common re retardants are halogen-based FRs, heat sink FRs or intumescent systems [1, 2]. Nowadays, due to environmental problems and concerns about smoke production, FRs have to meet multiple requirements and many industries avoid using halogens. In addition to the intrinsic re retardant properties conferred to host polymers, they have to be ecologically friendly; they must be nontoxic and not produce corrosive and opaque smoke during combustion. The progressive shift away from halogenated FR, due to the potential risks related to their decomposition products, has led to an interest in mineral llers [3, 4]. The most effective halogen-free re retardant formulations for this kind of application are based on metal hydroxides,
Correspondence

to: Sverine Patricia Bellayer, Unit Matriaux et Transformations (UMET) - UMR CNRS 8207 Equipe Ingnierie des Systmes Polymres (ISP) Ecole Nationale Suprieure de Chimie de Lille (ENSCL), BP90108, 59652, Villeneuve dAscq Cedex, France. E-mail: severine.bellayer@ensc-lille.fr Copyright 2010 John Wiley & Sons, Ltd.

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such as alumina trihydroxide or magnesium dihydroxide [5, 6]. Such mineral llers act as re retardants mainly through their endothermic dehydration, evolving water and the formation of a protective ceramic-like layer at the surfaces of the material [7, 8]. Even if the surface of carbonates and talc does not contain hydroxyl groups or active ions, the addition of mineral llers into a polymer can contribute to its re retardant properties. Many articles in the literature report on the additional effect of talc into a re retardant system through synergistic mechanisms [911]. For instance, Lopez-Cuesta et al. [12, 13] have studied the inuence of talc physical properties on the re retarding behaviour of ethylene-vinyl acetate copolymer/magnesium hydroxide/talc composites. They have shown that the increase of talc lamellarity and the specic surface area induces a signicant improvement of its re behaviour. They also showed that a too high specic surface area of the particle decreases the cohesion of the combustion residue resulting in a decrease of the re properties. CaCO3 in association with silicon has also been investigated into ethyleneacrylate copolymer [914]. For instance, Hermansson et al. [9] studied the intumescent behaviour of this system and correlated the chemical reactions occurring during the cone calorimeter test, with temperature and visual observations of the foaming process and showed how the dispersion of the additives correlates with the ame properties of this system. However, as far as we know, there is a lack of understanding the FR impact of common and low cost mineral llers such as talc or carbonates by themselves into a polymer matrix. Thus, the aim of the present article is to investigate the potential of the ame retardancy of systems made of linear low-density polyethylene (LLDPE) melt mixed with different kinds of mineral llers, such as talc or carbonates using mass loss calorimeter. The inuence of aspect ratios, carbonate cations, compatibilization, dispersion or polymer matrix on the re properties of the resulting systems will be discussed.

EXPERIMENTAL Materials Linear low density polyethylene (LLDPE) LL1004 (melt ow index 2.8 g/10 min (190 C, 2.16 kg) and density 0.918 g/cm3 ) was supplied by ExxonMobil. EVA is an ethylene-vinyl acetate copolymer with a 2628% vinyl acetate content (Evatane 28-03, melt index (190 C, 2.16 kg = 3 4.5 g/10 min), density = 0.95 g/cm3 ) supplied by Arkema. All polymer pellets were dried at 80 C overnight before use. Calcium carbonate (CaCO3 ) used was Micronic O provided by Imeris, Omya BL and Durcal 40 provided by Omya SAS. They have, respectively, a d50 = 3.3 m (CaCO3 3), 6.6 m (CaCO3 6) and 30 m (CaCO3 30). Magnesium carbonate (MgCO3 , Magfy, d50 = 3 m) was supplied by Nuova Sima and talc 10M2 (d50 = 3 m) (Talc 3), A3 (d50 = 1.2 m) (Talc 1) and A60H (d50 = 9 m) (Talc 9) were supplied by RioTinto Minerals. Stearic acid (StAc) was provided by Brenntag (stearic acid 12). Sample preparation Polymeric matrices were melt mixed with the different additives in a Brabender mixer at 50 rpm, for 15 min at 140 C for PE- and EVA-based systems. The ratio between the polymeric matrix and the additives was maintained at 100:100 (wt/wt) for all the different systems except when stearic acid is added (ratio 100:99:1 wt/wt/wt). Plates measuring 3 mm 100 mm 100 mm were prepared using a molding press by applying a pressure of 10 N at 140 C for 3 min and then a pressure of 40 N for 5 min at the same temperature. All the different formulations studied are listed in Table I. Characterization A FTT (re testing technology) mass loss calorimeter was used to measure the heat release rate (HRR) and total heat released (THR) on samples following the procedure dened in ISO 13927 standard. Our procedure involves exposing specimens measuring 100 mm 100 mm 3 mm in
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Table I. Systems processed and their formulation (material contents indicated in phr).
System 1 2 3 4 5 6 7 8 9 10 11 12 LLDPE 100 100 100 100 100 100 100 100 100 100 EVA 100 100 CaCO3 3 100 99 100 99 CaCO3 6 99 CaCO3 30 99 Talc 3 100 99 Talc 1 99 Talc 9 99 MgCO3 100 99 StAc 1 1 1 1 1 1 1 1

horizontal orientation to an external heat ux of 50 kW/m2 using a forced ignition. For more accurate results, the PkHRR recovered is the mean of three experiments. The maximum uncertainty obtained was 10%. In order to make temperature measurements during the mass loss calorimeter experiment, a thermocouple was positioned at the surface of the specimen. UL-94 tests were carried out on 10 10 3 mm3 sheets according to the UL-94 testing (tests for ammability of plastics materials for part devices and appliances, Underwriters Laboratories Northbook IL: ANSI/ASTM D-635/77.1977). Each specimen is xed on a testing holder. A 20-mm high blue Bunsen burner ame is applied to the free end of the specimen for 10 s and then removed. SEM (scanning electron microscope) images were taken at various levels of magnication using an Hitachi S4700 SEM at 6 kV and 15 A. All samples were ultra microtomed with a diamond knife on a Leica UltraCut microtome at cryo temperature (120 C) to obtain smooth surfaces for scanning electron microscopy analysis. Rheological measurements were carried out using a Rheometric Scientic ARES 20A thermal scanning rheometer in a parallel plate conguration. Samples were positioned between the two plates. A constant normal force was systematically applied in order to obtain good adhesion between samples and plates. The conditions were strain value : 1 % and frequency: 1 rad/s. The viscosity values were recovered over the complete temperature range (100 500 C) with a heating rate of 10 C/min. The char expansion measurements were carried out using the same Rheometric Scientic ARES 20A. A low constant force (10 g) was applied to the sample in order to avoid the destruction of the char and to guarantee the validity of the results. The heating rate was also 10 C/min in the range 100 500 C.

RESULTS AND DISCUSSION 1- Inuence of aspect ratio and carbonate cation Talc particles are sheet-like particles compared to carbonates which are sphere-like particles. Because of its geometry, talc should form a better percolative network and should decrease the heat release rate peak (PkHRR) by forming a more cohesive and protective structure at the surface of the sample during burning [15]. However, HRR curves of the two LLDPE-based systems containing untreated CaCO3 3 and talc 3 show that CaCO3 3 decreases more the PkHRR than talc 3 (Figure 1). Virgin LLDPE exhibits a PkHRR of 600 kW/m2 , and the incorporation of mineral llers decreases the PkHRR by 50% for LLDPE/Talc 3 and by 75% for LLDPE/CaCO3 3. An increase of the time to ignition is also observed in the case of the two llers. Thus, those two llers are effective to reduce the PkHRR but calcium carbonate (PkHRR around 160 kW/m2 ) is more effective compared with talc (PkHRR at around 275 kW/m2 ).
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Figure 1. Heat release rate curves of the three systems LLDPE/MgCO3 , LLDPE/CaCO3 3 and LLDPE/talc 3 and pure LLDPE.

Figure 2. HRR curves of the three systems LLDPE/MgCO3 /StAc, LLDPE/CaCO3 3/StAc and LLDPE/talc 3/StAc (a) and comparison of HRR curves of LLDPE/CaCO3 3 and LLDPE/CaCO3 3/StAc (b).

Comparing talc and CaCO3 , we observed that the shape of the particle is an important factor in obtaining a signicant PkHRR reduction. Here, we have also substituted CaCO3 3 particles by MgCO3 particles into the LLDPE polymer matrix. The results show that no difference is noticeable between the HRR curves of LLDPE/CaCO3 3 and of LLDPE/MgCO3 systems under the mass loss calorimeter conditions (Figure 1). 2- Inuence of stearic acid Stearic acid (StAc) is known to compatibilize carbonates, especially calcium carbonate, in polymeric matrices [16]. It is then selected to study the effect of the compatibilization of the mineral llers on the re properties in LLDPE composites. Figure 2(a) shows the same LLDPE/CaCO3 3, LLDPE/Talc 3 and LLDPE/MgCO3 systems but with the incorporation of a small amount of stearic acid (1 phr). The use of stearic acid contributes to decrease even more the HRR peaks of all the systems. The larger decrease is observed in the case of the LLDPE/CaCO3 3/StAc system (Figure 2(b)), PkHRR is decreased by 50% compared with the same system without StAc. An other effect of stearic acid on the LLDPE/CaCO3 3/StAc system is the signicant and surprising swelling of the sample when burning. Figure 3 shows the two different residues obtained after the mass loss calorimeter measurements of the LLDPE/CaCO3 3 systems with (Figure 3(a)) and without (Figure 3(b)) stearic acid. This homogeneous expansion occurs during burning at the same rate whatever the point considered at the surface of the material (rectangular-like shape). This kind of expansion is usually called intumescence and is often obtained with organic FR additives. However, the traditional intumescent
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Figure 3. Images of the residues of LLDPE/CaCO3 3 (a) and LLDPE/CaCO3 3/StAc (b) after the mass loss experiment.

Figure 4. The relative THR of LLDPE, LLDPE/CaCO3 3 and LLDPE/CaCO3 3/StAc systems under the mass loss experiment conditions.

systems exhibit the formation of hemisphere-like coating after burning. In our case and as far as we know, it is the rst time that this phenomenon is reported in the literature with pure calcium carbonates in a polymeric matrix. The formation of this barrier provides the additional lowering PkHRR compared with the system without StAc. Figure 4 shows the relative THR (total heat release) of LLDPE, LLDPE/CaCO3 3 and LLDPE/CaCO3 3/StAc systems. When the steady state is achieved, the THR for the LLDPE/CaCO3 3 and LLDPE/CaCO3 3/StAc systems are 20% lower than the THR for the LLDPE system. This behaviour is explained by the high amount of CaCO3 introduced in the LLDPE. Fifty per cent of the sample is mineral and does not burn. The relative THR of the two systems LLDPE/CaCO3 3 and LLDPE/CaCO3 3/StAc is similar (80%); however, it is noteworthy that the time to reach the steady state is longer in the case of the LLDPE/CaCO3 3/StAc system than for the LLDPE/CaCO3 3 system. The intumescent phenomenon slows down the release of degradation products into the gas phase. CaCO3 decomposes to calcium oxide (CaO) and carbon dioxide (CO2 ) at 900 C. Thus,CO2 release could also affect the combustion efciency and the HRR when burning. However, the temperature at the surface of the sample was measured at a maximum of 750 C during the mass loss experiment. As a consequence, decarbonation does not occur during burning and decarboxylation does not play a role into the appearance of the intumescent behaviour [17]. As stearic acid induces the intumescence of the LLDPE/CaCO3 3/StAc char during the mass loss calorimeter experiment, UL 94 test has been carried out to see whether this char would be efcient enough to pass the test. However, the LLDPE/CaCO3 3/StAc system does not pass this
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test, the ame spreads to the entire sample and the char is not strong enough to prevent the polymer from dripping. 3- Rheological study Viscoelastic measurements were carried out to evaluate the rheological behaviour of the system when the temperature increases. Figure 5(a, b) presents the relative expansion and the complex viscosity versus temperature of the LLDPE/CaCO3 3 system (not intumescent) and of the LLDPE/CaCO3 3/StAc system (intumescent). It is noteworthy that the two systems behave in the same way. In organic-based intumescent systems, studied by Bourbigot et al. [18, 19], the formation of an effective char occurs via a semi-liquid phase, which coincides with the gas formation and the expansion of the surface. Gases released from the degradation of the intumescent material are trapped and diffuse slowly in the highly viscous melt degraded material to create a layer with appropriate morphological properties. If the degraded matrix has too low viscosity, easy diffusion of gases takes place and the gases will not be trapped but will rather escape to feed the ame. If the viscosity is too high, there can be a formation of some cracks which allow the oxygen to diffuse into the char and thus decrease the efciency of the protective layer. However, in the present case, no viscosity difference is observed between the two systems. Consequently, the visco-elasticity properties of the system do not explain the appearance of the intumescent phenomenon observed for the system LLDPE/CaCO3 3/StAc during burning. Moreover, the char expansion of the LLDPE/CaCO3 3/StAc system is not observed (Figure 5(b)). The relative char expansion for the LLDPE/CaCO3 3/StAc is only 120% and should be around 500%. As the char is very brittle, the force applied to the sample can break the sample and prevent it from swelling. 4- Dispersion study of the CaCO3 into the polymer matrix As stearic acid is a compatibilizing agent for calcium carbonates, it should increase the dispersion of particles into the polymer matrix. Thus SEM analyses were performed. SEM images of LLDPE/CaCO3 3/StAc and LLDPE/CaCO3 3 samples are shown in Figure 6(a, b). These images

Figure 5. The complex viscosity versus temperature (a) and the relative expansion (b) of the LLDPE/CaCO3 3 system (not intumescent) and of the LLDPE/CaCO3 3/StAc system (intumescent).

Figure 6. SEM images of LLDPE/CaCO3 3/StAc (a) and of LLDPE/CaCO3 3 (b) systems.
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Figure 7. Low magnication SEM image of LLDPE/Talc 3/StAc system.

provide a general representation of the dispersion of CaCO3 3 particles. The average theoretical particle size incorporated in LLDPE is around 3 m for LLDPE/CaCO3 3/StAc system, which corresponds to the size of the particles as seen in Figure 6(a) (system with stearic acid). This is not the case in Figure 6(b) where many agglomerates of 10 m and more can be detected. It conrms that stearic acid acts as a dispersion agent for CaCO3 3. It increases the afnity of CaCO3 for the polymer matrix and lowers its tendency to agglomerate. Therefore, this result suggests that the extent to which the CaCO3 particles are dispersed is a factor to obtain an intumescent mechanism as observed for the LLDPE/CaCO3 3/StAc system. Indeed, if the particle size is homogeneous, we can assume that the structure created during burning will also be more homogeneous and more efcient to produce a re protective barrier. If we follow this idea, talc particles should not be well dispersed in the LLDPE matrix in the presence of stearic acid since no intumescent behaviour was observed during the mass loss experiment. However, when LLDPE/talc/StAc was analysed by SEM, the talc dispersion is homogeneous and no agglomeration is observed (Figure 7). Talc 3 is a sheet-like particle and CaCO3 3 a sphere-like particle, as both particles disperse well with stearic acid we can conrm that the aspect ratio of the particle is an important factor in obtaining an intumescent phenomenon and improved re retardant properties. The shape of the particles inuences the way in which the particles pack during burning and have an impact on the cohesion of the obtained residue structure. In the case of MgCO3 particles, no difference is noticeable between the HRR curves of LLDPE/CaCO3 3 and of LLDPE/MgCO3 systems. However, when stearic acid is added to the two systems, PkHRR is higher in the case of the LLDPE/MgCO3 /StAc system than that of the LLDPE/CaCO3 3/StAc system (Figure 8). Moreover, no intumescent phenomenon was observed even if the aspect ratio of the particle was the same as CaCO3 3. The dispersion checked by SEM was good (not shown). Consequently, the type of carbonate also has an effect on the intumescent behaviour of the systems under the mass loss conditions. 5- Inuence of polymer polarity The same experiment was carried out within a polar polymeric matrix, EVA, and the dispersion of the CaCO3 particle was studied. The two different systems, EVA/CaCO3 3/StAc and EVA/CaCO3 3, have been characterized by SEM before performing the mass loss calorimeter experiment. The results are shown in Figure 9(a, b). SEM images provide a general representation of particle dispersion in EVA/CaCO3 3 with and without stearic acid. Both images show agglomerates of about 10 m and even more when stearic acid is added. In EVA, stearic acid does not drastically improve the dispersion of CaCO3 3. The mass loss calorimetry tests showed no intumescent behaviour for the EVA/CaCO3 3 with or without stearic acid systems and no cohesion of the residue after burning (Figure 10). Moreover, the
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Figure 8. Heat release rate curves of the three systems LLDPE/MgCO3 , LLDPE/MgCO3 /StAc and LLDPE/CaCO3 3/StAc under mass loss condition.

Figure 9. Low magnication SEM of EVA/CaCO3 3/StAc (a) and of EVA/CaCO3 3 (b) systems.

Figure 10. Image of the EVA/CaCO3 3 with or without stearic acid systems after burning in the mass loss condition.

PkHRRs obtained during the mass loss experiment (not shown) are higher than those obtained with both CaCO3 systems (with or without StAc). Hence, these results reinforce the role of dispersion in obtaining the intumescent behaviour. 4- Inuence of particle sizes In order to investigate the effect of the particle size of the llers on the intumescent behaviour, different systems were processed and tested. Table II sums up the tested systems and the obtained results. Three particle sizes of CaCO3 were used: 3.3, 6.6 and 30 m. The results with 3.3 or 6.6 m particles are quite similar. The PkHRR decreases and the system swells during burning. When the particle size is too large (30 m), the system is no longer sufciently efcient to lower the PkHRR even with a good dispersion of the particles. The particle size has an effect on the resulting swelling and PkHRR of the LLDPE/CaCO3 /StAc system. Thus, the effect of the talc particle size on the re properties of the resulting system was studied to improve its re retardant property or obtain an intumescent behaviour. However, mass
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Table II. Mass loss calorimeter data for LLDPE/CaCO3 /StAc systems processed with different CaCO3 particle sizes.
LLDPE 100 100 100 CaCO3 30 30 m 99 CaCO3 6 6 m 99 CaCO3 3 3 m 99 StAc 1 1 1 PkHRR (kW/m2 ) 92 95 170 Swelling Yes Yes No

Figure 11. HRR curves of LLDPE/talc/StAc systems with 9, 3 and 1 m talc particles during a mass loss test at 50 kW/m2 .

loss calorimeter results presented in Figure 11 showed no signicant differences. The lower PkHRR value is obtained with the 9 m talc particles and corresponds to the value of a LLDPE/CaCO3 3 system without stearic acid. It is noteworthy that no swelling was observed and a noncohesive residue was obtained.

CONCLUSION In the present study, we have reported the behaviour of common and low cost mineral llers such as calcium and magnesium carbonates or talc into an LLDPE polymeric matrix when exposed to mass loss calorimeter conditions. After melt mixing the different components into a mixer, and pressing them into sheets, mass loss calorimeter experiments showed that the LLDPE/CaCO3 /StAc (1 wt%) system exhibits an unexpected intumescent behaviour and a signicant decreased of the PkHHR compared with the LLDPE/CaCO3 system. A rheological study showed no impact of stearic acid on the viscosity of not only the system and do not explain the appearance of the intumescent phenomenon. However, SEM analyses of the composites showed that the stearic acid has a strong impact on the dispersion of CaCO3 into the LLDPE matrix. Stearic acid acts as an organo-modier of CaCO3 . Furthermore, we have demonstrated that the choice not only of the appropriate polymer (apolar) but also carbonate type, particle shape and size are important to obtain the intumescent effect during burning.
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Fire Mater. 2011; 35:183192 DOI: 10.1002/fam