Current Applied Physics 6 (2006) 259261 www.elsevier.com/locate/cap www.kps.or.

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Fire retarded polymer nanocomposites

B. Marosfo i, Sz. Matko, P. Anna Gy. Marosi
Received 28 January 2005 Available online 20 October 2005

Department of Organic Chemical Technology, Budapest University of Technology and Economics, Budapest H-1521, Hungary

Abstract Nanocomposite structure of polymer intercalated montmorillonites was formed in ethylene vinyl acetate copolymer/magnesium hydroxide ame retarded polymer system. Generally the presence of magnesium hydroxide ame retardant particles disturbs the structural analysis of such systems. Raman microscopic method was successfully applied for evaluating the distribution of components in presence of high concentration of ame retardant additives. The interphase formed around the nanoparticles inuences the structure and the temperature dependency of the rheological characteristics, which was evaluated by thermal Scanning Rheometer. Surprisingly the combination of unmodied and modied montmorillonites provided the most advantageous rheology prole for improving the re retardancy (reducing dripping and increasing the char-stability). 2005 Elsevier B.V. All rights reserved.
PACS: 81.07.Pr; 81.70.Pg; 82.35.Np; 83.50.Xa; 82.30.Lp; 82.65.+r; 78.67.n Keywords: Ethylene vinyl acetate; Magnesium hydroxide; Montmorillonite; Intercalation; High char stability; Raman microscopy; Rheology

1. Introduction The re retardancy is one of the elds where the nanomaterials could be used successfully. Nanoparticles embedded in various polymer matrices are reported to reduce considerably the heat released from these materials [1]. The investigation of the size, shape, interfaces and concentration of nanoscale (fumed) silica, nanoakes, nanotubes and other nanoparticles on the ame retardant performance increased the role of re protected polymers within the material science [2]. Various methods have been elaborated for combining synergistically the nanollers with other ame retardants including metal hydroxides [3]. Research for establishing relationship between the structure and ame retardant performance of such complex systems is challenging. Well designed interphases (IP) are required in such mul-

ticomponent re retarded systems in order to achieve optimal properties. The IP inuences the rheological characteristics and thus the processability and the dripping in case of re. Rheological behaviour at higher temperature describes the mechanical stability of char residue, which is in connection with the re resistance. In this paper the eect of metal hydroxide/montmorillonite additive system was studied by means of Thermal Scanning Rheometer.

2. Experimental Ethylene-vinyl acetate copolymer (EVA) IBUCELL K 100 with VA content of 28% (H.B. Fuller); Namontmorillonite (MMT), Microtec (Eurotrade Ltd. Hungary); Polybutene/polysiloxane intercalated MMT (IMM), laboratory product, prepared by solvent method; magnesium hydroxide (Mg(OH)2) (Dead Sea Bromine Group) were investigated. The compounds were prepared in a Plasti Corder PL2000 internal-mixer

Corresponding author. Tel.: +36 1 463 3654; fax: +36 1 463 1150. E-mail address: gmarosi@mail.bme.hu (P. Anna Gy. Marosi).

1567-1739/$ - see front matter 2005 Elsevier B.V. All rights reserved. doi:10.1016/j.cap.2005.07.052

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B. Marosfo i et al. / Current Applied Physics 6 (2006) 259261

(Brabender) at a rotor speed of 180 rpm, at 180 C, in 10 min. Sheets (120 120 2 mm) were obtained by compression moulding using Collin P 200 E type laboratory press at 180 C and a pressure of 5 MPa. Raman imaging was performed by a LabRam type confocal Raman microscope (Jobin Yvon, France). The excitation source was frequency doubled Nd-YAG laser emitting at 532 nm. Rheological data were collected by AR 2000 Thermal Scanning Rheometer (TA Instruments) in a parallel plate conguration. The samples of 25 25 2 mm size were heated from 130 to 550 C at a heating rate of 15 C/min at 8 Hz frequency. 3. Results and discussion The studied MH/MMT additive system has signicant ame retardant eect in EVA matrix if the metal hydroxide is applied in high concentration ($50%). The MMT nanoparticles were expected to contribute to the ame retardant action of MH by controlling the rheology at lower and high temperature. In order to promote this action polymeric (polybutene/polysiloxane) interlayer was formed around the nanolayers of MMT resulting in intercalated montmorillonite (IMM). A great challenge was to examine the distribution of MMT nanoparticles in such a highly lled system. Raman microscopic chemical mapping method was applied for evaluating the distribution of components in presence of high concentration of ame retardant additives. In Fig. 1 the bright areas represent the distribution and size of the non-modied and modied MMT particles in the polymer matrix (no disturbing eect of the Mg(OH)2 occurs). In the EVA- Mg(OH)2-MMT system (Fig. 1a), large size ($20 lm) of the non-modied MMT agglomerates could be observed. The image of the EVA-Mg(OH)2-IMM compound, in which polymer was intercalated between the layers of montmorillonit, is shown in Fig. 1b. Due to the polymeric interphase (IP) the dispersion is much ner but not perfectly homogeneous. The formation of polymeric interphase (IP) around the nanoparticles was expected to aect the rheological
Fig. 2. Viscositytemperature plots of EVAMg(OH)2 systems containing unmodied and modied MMT-s.

behavior by increasing the contact between the additives and thus reducing the dripping in case of re. The thermal dependency of viscosity of MH/MMT containing EVA system was compared to the systems in which polymer IP surrounded the montmorillonit layers (IMM) and mixed IMM + MMT was also studied (Fig. 2). The MH increases the viscosity comparing to pure EVA but in the temperature range between 400 C and 475 C the viscosity is too low to avoid dripping of burning melt. Only slight improvement could be achieved by adding MMT, while IMM reduces the width of the low viscosity range. The eect of the mixed additive is especially interesting. This additive system not only keeps the viscosity at a relatively high value, but even increases it gradually in the temperature range between 390470 C where other compositions loose their consistency. This character contributes to good ame resistance. It is important to note that, according to the rheological measurements, the char remains resistant and stabile even above 500 C in case of systems containing IMM, while the char of the other studied materials collapses at this temperature.

4. Conclusion Ethylene vinylacetate copolymers ame retarded with metal hydroxides are widely used in the cable industry. The ame retardancy of these cable coating systems can be improved by introduction of nanoparticles. The re resistance is in connection with the dripping of burning melt due to very low viscosity at a certain temperature range. Polymer interlayer formed around the nanoparticles improves the rheology prole by preserving consistency of the burning material even above 500 C. Based on these results the concentration of additives needed for certain levels of ame retardancy can be

Fig. 1. Raman imaging of (a) EVAMg(OH)2MMT and (b) EVA Mg(OH)2IMM.

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