FIRE AND MATERIALS Fire Mater. 2012; 36:661670 Published online 23 February 2012 in Wiley Online Library (wileyonlinelibrary.com).

DOI: 10.1002/fam.1128

Featured structures of re residue of high-impact polystyrene/ organically modied montmorillonite nanocomposites during burning
Jun Zhang1,2,*,, Maojuan Bai1,2, Yong Wang2 and Fengyan Xiao1
Key Laboratory of Rubber-Plastics, Ministry of Education/Shandong Provincial Key Laboratory of Rubber-plastics, Qingdao University of Science & Technology, Qingdao 266042, China 2 College of Environment and Safety Engineering, Qingdao University of Science & Technology, Qingdao 266042, China
1

SUMMARY The structures and constituents of re residue of high-impact polystyrene/organically modied montmorillonite (HIPS/OMMT) nanocomposite during burning was investigated using scanning electron microscopy, thermogravimetric analysis, X-ray diffraction analysis, and elementary analysis techniques and based on quenched samples obtained during the cone calorimeter test. It was found that during burning the HIPS/ OMMT nanocomposite tends to form a two-layer structure of re residue on the surface of material. This two-layer structure contains a thin and condensed skin layer at the top and a loose and expanded cellular layer under the skin layer. The skin structure contains many small sizes of voids, while the cellular structure includes a large number of large-size voids. Both the skin and cellular layers are composed of mainly montmorillonite platelets, which are aggregated to form a nanoscale network structure, in which certain amounts of carbonaceous char components are trapped during burning but decompose above approximately 550 C in the presence of oxygen. Finally, an idealized model was put forward to explain the featured structures of re residues for the nanocomposite studied. Copyright 2012 John Wiley & Sons, Ltd.
Received 16 August 2011; Revised 13 September 2011; Accepted 4 October 2011 KEY WORDS:

HIPS; OMMT; nanocomposite; residue; structure

1. INTRODUCTION Flame retardancy of polymer-layered silicate (PLS) nanocomposites has attracted much attention over the last decades. Compared with their neat polymers, the PLS nanocomposites added with a low concentration of silicate, usually clays, can reduce the heat release rate (HRR) dramatically during burning. Accompanied with the signicant reduction of HRR, a large volume of re residues tends to be generated on the exposed surface of the materials, acting as a protection barrier, which is a favorable expectancy from the point of view of environment-friendly ame retardancy. All these boost greatly research interest in this new type of ame retardant material as well as the fundamental aspects associated with its desirable performances [14]. To date, many efforts have been made to understand the ame retardant mechanisms of the nanocomposites [511]. A number of researches proposed ablation as the main mechanism of protection layer formation for PLS nanocomposites during burning [5,6]. A detailed study based on cone calorimeter combustion and gasication investigation of poly(ethylene-co-vinyl acetate)-layered silicate nanocomposites showed that a substantial decrease of the rate of combustion of the nanocomposite is due to surface
*Correspondence to: Prof Jun Zhang, College of Environment and Safety Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao 266042, China. E-mail: safetyqust@163.com

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charringceramization, which creates a more effective protective shield for the polymer than in the case of microcomposites [7]. A mechanism study on polystyrene-layered silicate nanocomposite investigated the silicate-reinforced char layer formed during various states of decomposition using the National Institute of Standards and Technology gasication apparatus and put forward a charring mechanism that after the polymer decomposed and volatilized, the silicate layers collapsed and possibly catalyzed carbonaceous char formation, yielding a stable silicate-carbon char layer [8]. A migration hypothesis assumed that during burning, montmorillonite (MMT) accumulated on the burning surface because of its lower surface free energy relative to polymer, forming a high MMT concentration char layer and leading to the ammability reduction [9]. A detailed mechanism study on polyamide-6clay nanocomposites by means of collecting and analyzing the residues at various decomposition stages of gasication process concluded two possible charring mechanisms, one is recession of the polymer resin from the surface by pyrolysis with dewetted clay particles left behind, and the other is the transportation of clay particles toward the surface, driven by rising bubbles and associated convection in melt [10]. Some reports also show that polymer melting behavior and bubbling strongly inuence residue formation [11,12]. In spite of the different assumptions on the mechanisms, it is generally accepted that a protective silicate-rich re residue layer is formed on the surface of the PLS nanocomposites during burning, which acts as a physical barrier to heat transfer and mass transportation processes and plays a major role in ammability reduction [512]. However, with respect to the residue structure, previous studies were mainly based on the experimental results from the gasication process in nitrogen, and few attempts have been made to examine the virtual internal structures of re residue formed in real burning conditions. During the preparation of this report, we noticed two very recent publications partially involved with the investigation of the internal structure of re residue subjected to real burning conditions [13,14]. However, more efforts are needed to understand the detailed structures and constituents of re residues and their relationships with ame retardant mechanisms. The present article focuses on the featured structures of re residue from a high-impact polystyrene (HIPS) and organically modied montmorillonite (OMMT) system during burning with the cone calorimeter and discusses preliminarily their possible inuences on re retardancy.

2. EXPERIMENTAL The main materials used in this study include HIPS, manufactured by Zhenjiang Chimei Chemical Co. Ltd, China, and clay (Na+MMT), made by Zhejiang Fenghong Clay Chemical Co. Ltd, China. The OMMT was prepared by modifying the clay with an alkyl ammonium salt [15]. The HIPS/OMMT (5 wt%) nanocomposite was made by mixing the polymer with organoclay at designed proportion using two-roll mill at 160 C and then molded into the sample sheets with dimensions of 100 100 4 mm for the cone calorimeter tests, employing a high temperature press at 180 C. The burning behaviors of the sample sheets were tested using an FTT standard device (FTT, West Sussex, UK) according to ISO 5660-1 at an incident heat ux level of 50 kW/m2. Exceptional cone calorimeter experiments were also conducted in order to obtain samples for observations of residue structures. In the exceptional experiments, the burning was stopped manually at a preset time. The stopping process included quickly stopping the burning by simultaneously covering over the ame with an aluminum foil cover to quenching aming and pulling out the sample holder and shifting the extinguished sample to a cooling cabinet immediately without any touch on the surface of the half-burnt sample. The surface temperature of the half-burnt sample was measured by an infrared gun immediately after the ame was being put out, and the result showed that the surface temperature was approximately 308 C, which is unable to support continuous decompositions. With the aids of a knife and a razor blade, the samples were manually and carefully broken into small pieces with at least one fractured surface being untouched for scanning electron microscopy (SEM) examinations as seen in Figure 1(a) and scraped at the three different layers, dened as a skin layer, a cellular layer, and a melting layer, respectively, for thermogravimetric analysis (TGA) and X-ray diffraction analysis (XRD) as shown in Figure 1(b).
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Figure 1. Fractured surface of the cross section of the half-burnt sample for scanning electron microscopy examinations (a) and the half-burnt sheet scraped to collect powder samples for the X-ray diffraction and thermogravimetric analyses (b).

A JEM-1200EX SEM (JEOL, Tokyo, Japan) was used for the morphology examinations, and in most cases, the samples were observed not only on the fractured samples but also on a few powder samples. The TGA experiment was conducted with TGA-7 (Perkin-Elmer, Waltham, Massachusetts, USA) thermogravimetry at heating rate of 10 C/min. An elementary analyzer (Vario EL, Elementar Corporation, Hanau, Germany) was used to determine the compositions of the re residues. The XRD data were collected on a D/MAX-YA X-ray diffraction (Rigaku, Tokyo, Japan) using CuKa radiation (a = 0.1542 nm). XRD samples were ground to particle form prior to analysis.

3. RESULTS AND DISCUSSIONS 3.1. Burning behavior in the cone calorimeter The full historical HRR curves of neat HIPS, HIPS/OMMT (5 wt%) nanocomposite, and HIPS/MMT (5 wt%) composite are shown in Figure 2. As shown in the HRR curve for the nanocomposite, the HRR rises up to a peak, and after that, the HRR goes down dramatically, while the HRR curves for the neat polymer and the composite continuously rise up. In addition, the HRR curves of the exceptional cone calorimeter experiments are also illustrated in Figure 2. The experiments were stopped at 180 and 120 s, respectively, for HIPS/OMMT and HIPS/MMT. The HRR of HIPS/OMMT at 180 s is lower, demonstrating the ame retardant effect of the formed protective surface residue layer, which is shown in Figure 3(a). The formed protective layer at 180 s further developed to be the residue at the end of burning, which is shown in Figure 3(b). It is seen that the residue for HIPS/OMMT is a continuous shielding with some surface cracks. For the comparison purpose, Figure 3(c) shows the half-burnt sample for the HIPS/MMT (5 wt%) composite. As seen from Figure 3(c), the untreated MMT particles are burnt to be black and precipitate on the surface to form some separated islands surrounded by yellow molten matrix, which clearly cannot provide an effective protective layer and thereby do not reduce HRR signicantly. Clearly, the formed residue and its particular structure

Figure 2. Sampling points for high-impact polystyrene/organically modied montmorillonite (HIPS/ OMMT) (5 wt%) nanocomposite at 180 s and for HIPS/MMT (5 wt%) composite at 120 s at 50 kW/m2.
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Figure 3. Digital photographs for residual sheets of the half-burnt (a) (180 s) and full-burnt (b) (500 s) highimpact polystyrene/organically modied montmorillonite (HIPS/OMMT) (5 wt%) nanocomposite and the half-burnt (120 s) HIPS/MMT (5 wt%) composite (c) at 50 kW/m2.

should be crucial to the ame retardancy, and therefore it is important to know what special structures are created with the nanocomposite after the peak HRR. 3.2. Structure and morphology observed by scanning electron microscopy The SEM micrographs for the fractured surfaces of cross-sectional area of the half-burnt nanocomposite are shown in Figure 4(a) for the upper portion and Figure 4(b) for the lower portion. It can be seen from Figure 4(a and b) that the half-burnt sheet of the nanocomposite is basically composed of four layers from the surface top to the bottom successively, namely a black top layer on surface, a black cellular layer in the upper middle, a brown and thin layer pyrolyzed partially beneath the cellular layer, and a yellow-white melting layer at the bottom layer. However, it should be noted that the partially pyrolyzed brown layer is actually very thin and hence hard to make a precise distinction from either the cellular layer above it or the yellow layer beneath it. Thus, for a half-burnt sample, its texture structures can be simply considered as two main layers, that is, a burnt layer and an unburnt layer. What we are most interested here is the structure of the burnt layer. By carefully examining the detailed structures in the burnt layer as shown in Figure 4, it can be found that the surface layer and the cellular layer are quite different in their structure and morphology. It can be observed from Figure 4(a and a-1) that the total thickness of surface layer is quite small and approximately 100 mm. This surface layer looks like a skin. Its texture structure is constructed compactly and contains many relatively small sizes of voids. Most voids seem to be suppressed. In the cellular layer as shown in Figure 4(a and a-2), however, a large number of cell walls are stacked loosely and irregularly, leaving a great number of large sizes of voids in the structure and forming a texture structure somewhat like a cellular structure. The sizes of voids are relatively large, and the estimated diameters of the voids ranged from a few hundreds of micrometers to approximately 2 mm. It is the cellular structure layer that enlarges signicantly the volume of re residue of the nanocomposite, which is an astonishing character of the residues generated by most PLS nanocomposites when being incorporated with only a small amount of organoclay. It is considered that both the skin layer and the cellular layer contribute to the heat and mass barrier effects of the residue and the reduction of HRR. Particularly, the compact skin layer might effectively hinder the permeability of gases, while the expanded cellular layer might act as a good thermal insulation layer. From the preceding discussions, it is known that both the skin layer and the cellular layer are porous and their main differences are in the size of voids. Actually the structures of cell walls in the two different layers are quite similar, which could be concluded through examining the SEM micrographs shown in Figure 4. From Figure 4(a-1 and a-2), it is seen that the cell walls of both the skin layer and the cellular layer are in the thickness of a few tens of micrometers. However, it should be noted that although a similar structure is formed in both the skin layer and the cellular layer, large voids result in more disordered cell walls. In fact, there are only small amount of vertically orientated cell walls in the skin layer, while there are a large number of vertically orientated cell walls in the cellular layer. In terms of the barrier effect of residue layer, the latter obviously has less effectiveness than the former. To further magnify the structure of skin and
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a-1

b
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a-2
burnt layer

un-burnt layer

a-1

a-2

a-4 a-3

a-3 x10000

a-4 x10000

a-3 x50000

a-4 x50000

Figure 4. Structure and morphology of half-burnt high-impact polystyrene/organically modied montmorillonite (5 wt%) nanocomposite at 50 kW/m2: (a) upper portion and (b) lower portion.

cellular layers by SEM as shown in Figure 4(a-3 and a-4), it seems that for both the skin layer and the cellular layer, the cell walls are composed of aggregated MMT platelets in a similar network structure. It is also interesting to examine the detailed texture structure and morphology of the unburnt layer. As demonstrated in Figure 4(b), the unburnt layer contains a great number of large sizes of gas bubbles, which are possibly created by early decomposed products of organoclay and certain low-molecularweight substances [16,17]. These bubbles may play an important role in two aspects: as a driving force to push the melting portion moving upward and as an extender to enlarge the bulk nanocomposite. More importantly, the voids in the cellular layer should be converted from these bubbles when they were arising with the melting layer. As compared with the full-burnt residue structures of the nanocomposite shown in Figure 5, it can be seen from Figure 5(a and b) that at the end of burning, only the skin layer and the cellular layer remain in the residue structure. Interestingly, comparing Figure 4(a-1) at 180 s of burning with Figure 5(c) at the end of burning, the total thicknesses of their skin layers are almost the same for
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Figure 5. Structure and morphology of the high-impact polystyrene/organically modied montmorillonite (5 wt%) nanocomposite at the end of burning at 50 kW/m2: (a) upper portion, (b) lower portion, (c) the skin layer, and (d) high-magnication skin layer.

the two residues, showing that during burning, the skin layer will not increase much, but the cellular layer is growing signicantly. From the magnied SEM micrograph of the skin layer as shown in Figure 5(d), it is also found that the cell wall of the skin layer at the end of burning is composed of aggregated MMT platelets, which is similar to the cell walls of the skin layer in the half-burnt sample as shown in Figure 4(a-3). By contrast, the cross-sectional structures of the half-burnt sample containing the untreated MMT are shown in Figure 6. As seen from Figure 6(a), the total thickness of the whole sample is reduced to approximately 2 mm, and the surface leaves many bumps and caves, while Figure 6(b and c) show neither skin and cellular structures nor a network-like structure, demonstrating a completely different residual structure compared with the organoclay case. Clearly, only the PLS nanocomposites can form this particular skin cellular structure residue and also a network-like structure within the cell walls.

3.3. Constituents of residue and dispersion of montmorillonite platelets The aforementioned SEM observations illustrate that in the burnt residue, the MMT platelets tend to aggregate to form the cell walls, which construct the skin layer and the cellular layer. Thus, it is necessary to further examine the microstructure and constituents of cell walls in the skin and cellular layers.

Figure 6. Scanning electron micrographs for the half-burnt (120 s) sample of the high-impact polystyrene/ montmorillonite (5 wt%) composite at 50 kW/m2: (a) whole cross-sectional area and (b) top portion.
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In this study, TGA was used to identify the fractions of any possible components in the skin and cellular layers. Figure 7 shows the TGA results for the original material, the skin layer, the cellular layer, and the melting layer, respectively. As shown in Figure 7(a), the results for half-burnt samples show that until 800 C, the total mass losses for the original sample, the skin layer, the cellular layer, and the melting layer are 95%, 51%, 49%, and 96%, respectively. Because only the two materials, that is, HIPS and OMMT, are contained in the original nanocomposite, the total mass losses indicate the relative proportions of inorganic MMT and organic polymer with its decomposed derivatives in the residues. Clearly, both the skin layer and the cellular layer leave a higher amount of residue containing a high proportion of MMT component, while the melting layer and the original nanocomposite show a very small proportion of residue, which is approximately equivalent to their corresponding MMT loading levels. These results indicate that in the skin and cellular layers that underwent severe burning for 180 s, in this case approximately a half of the residue is MMT component and another half is organic components. Further examining these with mass loss rate curves as shown in Figure 7(b), it was found that the skin and cellular layers have two different decomposition peaks, the rst one at around 380 C and the second one at approximately 565 C. The position of their rst peak is close to that of the original nanocomposite but slightly shifts to lower temperature range, which should be related to the partial degradation undergone for the residue. Compared with the original nanocomposite, the rst peak should be due to a normal decomposition process for the HIPS, while the second peak clearly is resulted from a new fraction. According to a 565 C of high decomposition temperature, this new fraction is likely a carbonaceous residue. An elementary analysis was conducted to verify the possible composition of organic components in the skin and cellular layers, respectively. The results show that the skin layer contains 28.17% carbon while the cellular layer contains 47.26% carbon. It shows that both the rst peak and second peak are due to the decomposition of carboncontaining substances, and thereby the second peak is highly possibly due to a carbonaceous residue. However, it should be noted that from different atmosphere TGA tests for the cellular layer, the second mass loss rate peak did not occur in the nitrogen atmosphere, showing that the residue is easy to be oxidized. The results show that MMT is able to promote charring but only produce a carbonaceous precursor, which is unable to bare a high temperature up to 550 C approximately in the presence of oxygen. This result may implicate a possible way to further improve the ame retardancy of PLS nanocomposite by increasing the thermal oxidation stability of carbonaceous precursor produced in burning condition. Indeed, for the half-burnt nanocomposite studied in this work, relatively large quantity of carbonaceous residue (approximately over 30% based on estimation by mass loss rate peak area) is produced. However, for the skin and cellular layers collected at the end of burning, the carbonaceous components in the residue actually are reduced to a much less level. As shown in Figure 8(a), the total volatiles from the skin layer are about 9.8%, and those from the cellular layer are approximately 22.5%. Also as shown in Figure 8(b), the second mass loss rate peaks for both the skin and cellular layers are lower, indicating lower contents of carbonaceous residue.
2

Mass loss rate (%/min)

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Residual mass (wt%)

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original HIPS/OMMT(5wt%) skin layer(half-burnt,air) cellular layer(half-burnt,air) melting layer(half-burnt,air) cellular layer(half-burnt,nitrogen)

Temperature (oC)

Temperature (oC)

(a)

(b)

Figure 7. Thermogravimetric analysis residual mass in percentage (a) and mass loss rate (b) for the half-burnt sample and the original nanocomposite, 10 C/min.
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2 100 0

Mass loss rate (%/min)

Residual mass (wt%)

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original HIPS/OMMT(5wt%) skin layer(full-burnt,air) cellular layer(full-burnt,air)

100 200 300 400 500 600 700 800 900

100 200 300 400 500 600 700 800 900

Temperature (oC)

Temperature (oC)

(a)

(b)

Figure 8. Thermogravimetric analysis residual mass in percentage (a) and mass loss rate (b) for the full-burnt sample and the original nanocomposite, 10 C/min.

In this study, the XRD technique was used to investigate the dispersion of the MMT platelets in each layer of the residue. As shown in Figure 9, the XRD data for the skin layer, the cellular layer, and the melting layer show neither a characteristic peak for the intercalated structure nor that for the organoclay structure. Compared with the original nanocomposite sample, it can be seen that the peak at 2 = 2.29 for the polymer intercalated structures and the peak at 2 = 4.49 for the organoclay structure disappear in all the three layers for the half-burnt samples. From the XRD data, it is shown that only the exfoliated MMT platelets are present in both the skin layer and the cellular layer. However, it is surprisingly found that in the melting layer, the intercalated structure vanished as well, indicating that the polymer melting process during burning will further delaminate the intercalated clay stacks to become exfoliated platelets for the nanocomposite studied. Figure 10 shows the results for the skin and cellular layer collected at the end of burning. Similarly, both layers show neither a characteristic peak for the intercalated structure or organoclay. Clearly, from the XRD data, there is no fundamental difference in the dispersion of MMT platelets in cell walls between the skin and cellular layers. On the basis of the network-like structure observed by SEM and the exfoliated form of MMT platelets in the structure detected by XRD, it is assumed that the MMT platelets are aggregated together possibly by interaction between platelets themselves and form the cell walls in the structure, while carbonaceous components would be trapped in the aggregated network structure. To summarize the aforementioned results, we put forward an idealized structure model for the re residue of the nanocomposites, which is illustrated in Figure 11. This model is featured in a coarse structure constructed by a skin layer and a cellular layer and a ne structure consisting of nanoscale
300 250 original HIPS/OMMT (5wt%) skin layer (half-burnt) cellular layer (half-burnt) melting layer (half-burnt)

Relative intensity (cps)

200 150 100 50 0

10

2 ( )

Figure 9. X-ray diffraction analysis results for the half-burnt sample and the original nanocomposite.
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Relative intensity (cps)

200

original HIPS/OMMT (5wt%) skin layer (full-burnt) cellular layer (full-burnt)

150

100

50

10

2 ()

Figure 10. X-ray diffraction analysis results for the full-burnt sample and the original nanocomposite.

Skin layer

Cellular layer Void

Aggregated platelet network structure

Figure 11. Schematic skin cellular structure model for the re residue of the nanocomposite.

MMT platelet network structure. The skin and cellular structure signicantly enlarged the volume of residue and hence acted as an effective thermal insulation layer while the condensed ne structure acted as a good physical barrier. Both of them can contribute to ammability reduction.

4. CONCLUSIONS It can be concluded from this study that during burning, the HIPS/OMMT nanocomposite tends to form a two-layer structure of re residue on the surface of a material. This distinct two-layer structure contains a thin and condensed skin layer at the top and a loose and expanded cellular layer under the skin layer. The skin structure is composed of mainly horizontally orientated cell walls and many small sizes of voids, while the cellular structure is constructed with both horizontally and vertically orientated cell walls accompanied with a large number of large-size voids. The voids possibly act as a good thermal insulation layer because of the considerable enlargement of residue volume, like a foam material. Thus, a skin cellular layer structure would contribute to HRR reduction effectively. Further investigation shows that the cell walls in both the skin and cellular layers are composed of mainly MMT platelets, which are aggregated to form a nanoscale network structure. TGA and elementary analysis results show that certain amounts of carbonaceous char components are formed in the network during burning but decompose above approximately 550 C in the presence of oxygen. Although the network structure occupies only a relatively small volume in the re residue, its compact structure will be a better barrier for heat transfer and mass transportation. Thus, both the dense network structure and the expanded cellular structure would benet the ammability reduction of the nanocomposites greatly.
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The authors are grateful for the nancial support from the National Natural Science Foundation of China (NSFC No. 50876048).
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Fire Mater. 2012; 36:661670

DOI: 10.1002/fam