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Effect of Inorganic Fillers on the Flammability Behavior of Polypropylene Composites

J. Abd. Razak, H. Md. Akil and Huilin Ong Journal of Thermoplastic Composite Materials 2007 20: 195 DOI: 10.1177/0892705707073181 The online version of this article can be found at: http://jtc.sagepub.com/content/20/2/195

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Effect of Inorganic Fillers on the Flammability Behavior of Polypropylene Composites

J. ABD. RAZAK, H. MD. AKIL* AND HUILIN ONG School of Materials and Mineral Resources Engineering Engineering Campus, University Science of Malaysia 14300 Nibong Tebal, Penang, Malaysia
ABSTRACT: This report summarizes the effect of various inorganic fillers such as alumina (-Al2O3), calcium carbonate (CaCO3), silica (SiO2), and feldspar (KAlSi3O8) on the flammability behavior of polypropylene (PP) composites. The effect of various filler loadings (by weight percent), typically at 40 and 60% has also been investigated for each of the fillers used. Initially, the compounding of composites (filler and polypropylene) was carried out using a two-roll mill; later, the test specimens were prepared using the compression molding technique. For each composite system, the linear rate of burning at two filler loadings was calculated, analyzed, and compared. Consequently, the characteristics of the flame, typically smoke suppression and char formation, were also analyzed as recommended by ASTM and UL 94 methods. From the results, it is clear that adding alumina fillers to polypropylene, at both percentages, results in decreasing the linear rate of burning, and hence improves flammability resistance. It is also interesting to note that alumina-filled PP shows greater flame-retardant behavior at both the 40 and 60% filler loadings. KEY WORDS: flammability, composites, polypropylene.

INTRODUCTION

many outstanding material properties and are economical. Their usage is steadily rising in various applications, replacing other materials like wood and metal [1].
HERMOPLASTIC COMPOSITES HAVE

*Author to whom correspondence should be addressed. E-mail: hazizan@eng.usm.my Figures 1, 2 and 4 appear in color online: http://jtc.sagepub.com

Journal of THERMOPLASTIC COMPOSITE MATERIALS, Vol. 20March 2007

0892-7057/07/02 019511 $10.00/0 DOI: 10.1177/0892705707073181 2007 SAGE Publications

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Popular applications include the building sector, public transport, and electrical equipment. For all applications, increasing emphasis is being placed on stricter safety guidelines, including fire precaution for materials used in high-risk fire applications [2]. Flame-retardant thermoplastic composites that do not generate a considerable amount of smoke and toxic gases in the event of fire are needed. One way to improve the flameretardant behavior of composites or polymers is by incorporating flame-retardant agents. The main issue associated with using these additives is that they are highly toxic and harmful to the environment. The inherent flammability of many thermoplastic composites, especially those with high carbon content, requires that measures be taken to allow their safe use where the potential for fire exists [3]. Efforts to develop flame-retarding composite materials have increased with the increasing use of thermoplastics, especially polypropylene, as a matrix for composites. Polypropylene (PP) represents a large fraction of world polymer usage, falling right below polyethylene (PE) and polyvinyl chloride (PVC) [4]. Due to its low cost and easy processing, PP is widely used in many industrial applications. These applications require a degree of flame retardancy that can be obtained using additives [5]. PP is often modified with fillers such as talc and calcium carbonate to reduce costs. However, improvement of performance becomes the main driving force behind their widespread usage. Recently, several authors have worked on flame-retardant polymer-based composites. Marosi et al. [6] found a significant improvement in flame retardancy of PP modified with organophilized montmorillonite nanoparticle-coated silicone in the presence of an intumescent flameretardant additive system. Zhao and co-workers [7] studied the flammability of PE/clay nanocomposites, which were prepared by melt compounding with different intercalating agents. The peak heat release rate of the nanocomposite was reduced by 54% when only 2 parts per hundred (phr) organoclay were added. They also reported improvement of the thermal stability and flammability in the clay-enriched protective char during combustion. Meanwhile, epoxy-based composites have been studied by Toldy and co-workers [8]. They have incorporated monophosphorylated hydroxyl phenols in varying percentages into epoxy resin as flame retardants and found that a higher phosphorous content in the epoxy resin results in better fire resistance. For safety reasons, flame-retarding formulations are available today for all thermoplastics and thermosets as well, which will significantly reduce the probability that they will burn in the initiating phase of a fire. The choice of flame retardant to be used in specific plastics materials is not arbitrary [1]. In the case of fire, the effectiveness of the flame retardant

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is highly dependent on the duration of the fire exposure and the intensity of the flame. It should also offer such properties as high thermal stability, high decomposition temperature, and inertness so that it will not undergo a reaction with the base materials [9,10]. In this study, various inorganic fillers are used as flame-retardants in place of commercially available flame-retardants. These inorganic fillers have been used due to the outstanding combination of chemical and physical properties such as high resistance to heat, good oxidation resistance, and potential flame-retardant for polymers [11]. The expected benefits of adding inorganic filler include slower burning rate, lower smoke emission, and less char formation. EXPERIMENTAL Raw Materials The polypropylene (PP) used was a homopolymer grade (TITANPROPM-255) purchased from Titan PP Polymers (M) Sdn. Bhd., with density and melt flow rate at 230 C of 0.9 g/cm3 and 1.6 g/10 min, respectively. Alumina powder is supplied by Sulzer Metco Company, USA. Silica, calcium carbonate, and feldspar were obtained from Mineral Laboratories, University Science of Malaysia. Preparation of Composites All fillers were dried in an air oven at 100 C for 3 h to expel moisture prior to blending with polypropylene. Prior to mixing, fillers (all in powder form) and polypropylene granules were weighed to obtain 40 and 60% of filler loading by weight. The PP and filler were mixed using a two-roll mill at the speed of 50 rpm, temperature of 230 C, and common nip setting distance of 1 mm. The mixing time was fixed at 20 min to ensure a high homogeneity level of the final compound. Upon completion of mixing, the composites were removed from the two-roll mill and sheeted through a laboratory mill at 2 mm nip setting. The composite sheets were then stored at ambient temperature for 24 h before compression molding. Samples of the composites were compression molded in an electrically heated hydraulic press model GT-7014-A30C. The lower and upper mold temperatures were set at 185 C, with hydraulic pressure of 100 kg/cm2. For the flammability sample, the material was preheated for 10 min before being compression-molded for 2 min. The subsequent cooling process was carried out under hydraulic pressure of 100 kg/cm2 for 3 min.

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Figure 1. The orientation of flammability test specimen and the test set-up.

Flammability Testing Flammability tests were carried out in accordance with ASTM D 635. The composite sheet was cut into bar-shaped test specimens with dimensions of 125 13 3 mm using a band saw (see Figure 2). At least 10 specimens were prepared for each composition and composite system. The flammability characteristics were based on the test methods, which cover a small-scale laboratory screening procedure for comparing the relative linear rate of burning, the extent of time of burning, or both. Composites specimens were placed in the flammability chamber in the horizontal position as shown in Figure 1. To evaluate self-extinguishing behavior, a less rigorous test, the 94-HB, was adopted. The sample was scribed with marks 100 mm on one end for calculating the rate of burning and then mounted horizontally, with the flame applied at 45 to the sample. The sample was exposed to the gas flame for 30 s. The time and extent of burning are measured and rated on the basis of the mean values from the three measurements, which are as follows: HB 1 Burning rate between marks 38 mm/min HB 2 Burning rate between marks 76 mm/min HB 3 Extinguishment occurring before the 102 mm marks

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Figure 2. Specimen for flammability tests.

Calculation for Linear Rate of Burning Calculation of the linear rate of burning (V ) in millimeters per minute (mm/min) for each specimen where the flame front reaches the 100 mm reference mark is given as follows: V 60L t 1

where, L the burned length in millimeters (mm) t the time in seconds (s) The other method for flammability evaluation includes the measurement of the length and width of the flame during burning. This can be done using the ACD photo enhancer approach. In this technique, the flame was digitally photographed, and observations were made on the flame characteristics such as the smoke suppression, the dimensions and color of the flame, and char and droplet formation. RESULTS AND DISCUSSION Self-extinguishing Characteristic and Linear Burning Rate (V ) The flame-retardant behavior, typically the self-extinguishing characteristic of various PP composites was evaluated based on observation of the

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J. A. RAZAK ET AL. Table 1. Summary of burning rate for various inorganic-filled polypropylene composites.
Sample A (40% SiO2) B (40% CaCO3) C (40% Al2O3) D (40% Feldspar) E (60% SiO2) F (60% CaCO3) G (60% Al2O3) H (60% Feldspar) Ignition time to reach 100 mm (s) 269 234 333 311 200 245 302 176 Burning rate (mm/s) 22.2 25.8 18.0 19.2 30.0 24.6 19.8 34.2

flame propagation before reaching the 100 mm mark. In order for the test to be valid, the specimens must not swell after 30 s of exposure to fire. In this study, all specimens were subjected to this test; it was found that all specimens were burnt without swelling after a period of 30 s and thus can be evaluated under the flammability test category. The summary of the results for the initial time of burning for a distance of 100 mm along the specimen is given in Table 1. From Table 1, it is clear that at 40% filler loading, alumina recorded the lowest value of linear burning rate, V, whereas PP with calcium carbonate filler shows the highest value. Since V represents the rate of fire propagation, it can be concluded that the composite with a higher V value is more flammable than that with the lower one. All composite systems at 40% filler loading can be conveniently rated as HB 1, in reference to the extent time of burning. At 60% filler loading, Al2O3 and CaCO3 fillers show the lowest V value at 19.8 mm/s and 24.6 mm/s, respectively. From the results, it can be said that the fire retardancy behavior of PP composite has been improved over that of unfilled PP. This is strongly supported by the reduction of burning rate and flame propagation rate for both composites (Al2O3 and CaCO3). In this case, the KAlSi3O8 composite shows the highest value of V, which can be classified as the poorest fire-retardant additive among all fillers. To explain these differences among Al2O3, SiO2, CaCO3, and KAlSi3O8, it is useful to look at the chemistry of the fire retardant of polymer with added filler. It is widely accepted that any oxides, carbonates, or hydroxides of the metals could restart the fire by the mechanisms shown in Figure 3 [12]. Assuming Al2O3, SiO2, CaCO3, and KAlSi3O8 will behave in the same manner during exposure to fire, it is clear that the formation of hydroxyl radicals, which will oxidize the solid carbon

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Effect of Inorganic Fillers on Polypropylene Composites

MO MOH M(OH)2 H OH + + + + + H2 H2O (X) H2O C(s) MOH M(OH)2 MO OH CO + + + + + H H H 2O H2 H + X

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M = Si, Al, Ca, KAlSi

Figure 3. Proposed mechanisms for destruction of solid carbon in the dispersed phase.

via decomposition into hydrogen/or water vapor. However, the presence of oxides, carbonates, or hydroxides of the metals will significantly reduce the carbon content in the specimen and thus reduce the decomposition. Other mechanisms have been postulated, including a reaction with metal oxides in which carbon is oxidized directly or in which intermediates or precursors of soot are neutralized by contact with metal species [12]. Flame Characteristic Another useful indication of flammability is the physical characteristic of the flame generated. Attempts were made to measure the flame using a suitable technique. In this study, the width and weight of the flame were measured (Figure 4). The image of the flame for each composite is digitally analyzed using the ACD See V3.1 photo enhancer systems approach. It proved difficult to quantitatively measure the size of the flame even with the help of the photo enhancer. From Table 2, the data for the height and width of the flame are reliable only at 40% filler content. Al2O3 and CaCO3 composites provided the flame-retardancy action by controlling the size of the flame. The flammability of the composites decreases and is not so obvious compared with KAlSi3O8 and SiO2-filled polypropylene composites. Length Dimensional Change Based on the result of the length dimensional change, it can be concluded that the addition of 40% of filler is sufficient to reach a level of fire

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40% SiO2 composite

40% CaCO3 composite

40% Al2O3 composite

40% Feldspar composite

60% SiO2 composite

60% CaCO3 composite

60% Al2O3 composite

60% Feldspar composite

Figure 4. Flame characteristics for each composite system.

protection that would enable the material to potentially serve as a flame retardant (Table 3). The dimensional change can be attributed to the fire propagation level of the composite bodies. If the length dimension changes dramatically, even after 30 s of burning, it means that the fire propagation was very rapid and that the composite is not suitable as a flame-retardant. Composites with 40% of Al2O3 filler have the smallest changes in length

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Effect of Inorganic Fillers on Polypropylene Composites Table 2. Measurement of flame dimensions during sample burning.
Flame dimensions during sample burning Sample A (40% SiO2) B (40% CaCO3) C (40% Al2O3) D (40% KAlSi3O8) E (60% SiO2) F (60% CaCO3) G (60% Al2O3) H (60% KAlSi3O8) Height (mm) 7.1 12.5 4.1 7.0 9.7 6.1 9.9 6.7 Width (mm) 4.1 1.5 1.5 1.5 2.1 2.1 1.5 2.5

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Table 3. Change in length of the specimens after 30 s of flame exposure.

Sample A (40% SiO2) B (40% CaCO3) C (40% Al2O3) D (40% Feldspar) E (60% SiO2) F (60% CaCO3) G (60% Al2O3) H (60% Feldspar) Length dimensions (mm) 109 114 105 101 100 118 117 106

among all the composite systems, after burning for 30 s. This means that the 40% of filler loading is enough to extend the time of burning. Flammability versus Mechanical Properties An increase in flammability behavior always occurs at the expense of other properties such as mechanical performance. Therefore, it is useful to benchmark the flammability behavior with the mechanical performance of the composite. For this reason, a comparative study between the flammability behavior and the tensile properties was conducted. The results are summarized in Table 4. While higher filler loading improves the flammability behavior of the composites, at 60% filler loading, agglomeration will start to occur and wetting of the filler will become a problem, since the quantity of resin is less than that of filler. Therefore, a reduction in mechanical properties is expected to occur.

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J. A. RAZAK ET AL. Table 4. Flammability vs mechanical properties of various PP composites.

Sample A (40% SiO2) B (40% CaCO3) C (40% Al2O3) D (40% Feldspar) E (60% SiO2) F (60% CaCO3) G (60% Al2O3) H (60% Feldspar) Burning rate (mm/s) 109 114 105 101 100 118 117 106 Ignition time (s) 22.2 25.8 18.0 19.2 30 24.6 19.8 34.2 Tensile modulus (GPa) 2 3.5 1.6 1.8 1.8 3 1 1.2

CONCLUSIONS The effect of various fillers on the flammability properties of PP composites has been studied. Self-extinguishing capability, linear rate of burning, flame characteristics, and length dimensional change were measured. From this study, it was found that none of the fillers was capable of promoting self-extinguishment in PP composites. The addition of 40% filler does enhance the flammability behavior by reducing the linear burning rate of PP composites, especially Al2O3-PP composites. ACKNOWLEDGMENT The authors acknowledge the research grant provided by Universiti Sains Malaysia that has resulted in this article. REFERENCES
1. Bosshard, A.W. and Schlumpf, H.P. (1987). Filler and Reinforcement: Plastics Additives, 2nd edn, In: Gachther and Muller (eds), Hanser Publisher, Munich. 2. Paul, K. (ed.). Testing for Fire: Handbook of Polymer Testing. Marcel Dekker, Inc., New York. 3. Ranken, P.F. (ed.). (2001). Flame Retardants: Plastics Additives Handbook, 5th edn, Hanser Publication, Munich. 4. Almeras, X., Le Bras, M., Hornsby, P., Bourbigot, S., Maroji, G., Keszei, S. and Poutch, F. (2003). Effect of Fillers on the Fire Retardancy of Intumescent Polypropylene Compounds, Polymer Degradation Stability, 82: 325. 5. Almeras, X., Dabrowski, F., Le Bras, M., Hornsby, P., Delobel, R., Bourbigot, S., Marosi, G. and Anna, P. (2002). Using Polyamide 6 as Charring Agent in Intumescent Polypropylene Formulations II. Thermal Degradation, Polymer Degradation Stability, 77: 315. 6. Marosi, G., Marton, A., Szep, A., Csontos, I., Keszei, S., Zimonyi, E., Toth, A., Almeras, X. and Le Bras, M. (2003). Fire Retardancy Effect of Migration in Polypropylene Nanocomposites Induced by Modified Interlayer, Polymer Degradation Stability, 82: 379.

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7. Zhao, C., Qin, H., Gong, F., Feng, M., Zhang, S. and Yang, M. (2005). Mechanical, Thermal and Flammability Properties of Polyethylene/Clay Nanocomposites, Polymer Degradation Stability, 87: 183. 8. Toldy, A., Anna, P., Marosi, G., Keglevich, G., Almeras, X. and Le Bras, M. (2003). Selective Phosphorylation of Hydroxyphenols for Forming Reactive Flame Retardants, Polymer Degradation Stability, 82: 317. 9. Bertelli, G., Camino, G., Marchetti, E., Costa, L., Casoroti, E. and Locatelli, R. (1989). Polymer Degradation Stability, 25: 277. 10. Dabrocoski, F., Le Bras, M., Delobel, R., Le Maguer, D., Bardollet, P. and Aymami, J. (2002). Flame Retardant, Interscience Publishers, London, UK. 11. Md. Akil, H., Johar, B., Ahmad, Z.A., Abu Bakar, A. and Alias A. (2003). In: Proceedings of 3rd International Conference on Recent Advances on Materials, Minerals and Environment, pp. 279284. 12. Lewin, M., Atlas, S.M., and Pearce Eli, M. (1982). Methods for Reduction of Smoke from Burning Polymers: Flame-retardant Polymeric Materials, Vol. 3, Plenum Press, New York, pp. 5455.

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