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FIRE AND MATERIALS Fire Mater. 2012; 36:241253 Published online 22 June 2011 in Wiley Online Library (wileyonlinelibrary.com).

DOI: 10.1002/fam.1104

Flame resistant performance of nanocomposites coated with exfoliated graphite nanoplatelets/carbon nanober hybrid nanopapers
Jinfeng Zhuge1, Jihua Gou1,*, and Christopher Ibeh2
1

Composite Materials and Structures Laboratory, Department of Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, FL 32816 USA 2 Center for Nanocomposites and Multifunctional Materials, Pittsburg State University, Pittsburg, KS 66762 USA

SUMMARY Exfoliated graphite nanoplatelets (xGnPs) were used to improve the ame resistant performance of glass berreinforced polyester composites. Along with xGnP, traditional intumescent re retardant ammonium polyphosphate (APP) was introduced into the polymer matrix as the dominant additive to reduce the heat release rate (HRR) and total heat released (THR) of the composites. The cone calorimeter test results Indicate that the optimal weight ratios of xGnP and APP were 3% and 17% by weight, respectively. At such weight ratio, a synergistic effect between xGnP and APP was demonstrated. The ame resistant performance of the nanocomposites was further improved by applying xGnPdominant carbon nanober (CNF)/xGnP hybrid nanopaper onto the surface of the samples. Compared with the control sample, the integration of the HRR (THR) from 0 to 100 s of the sample coated with the nanopaper of CNF/xGnP = 1/3 shows more than 30% decrease in THR. Based on the results of mass loss, the nanopaper coating is also shown to enhance the structural stability of the samples under re conditions, which affects the mechanical properties of the composites. The results show that the thermal properties, permeability of composites, and char formation play important roles in determining the re behavior of the composites. Copyright 2011 John Wiley & Sons, Ltd.
Received 25 October 2010; Revised 21 March 2011; Accepted 26 April 2011 KEY WORDS:

exfoliated graphite nanoplatelets; nanopaper; nanocomposites; permeability; synergistic effect

1. INTRODUCTION Fiber reinforced polymers (FRP) have excellent physical and mechanical properties, such as high specic strength, light weight, good fatigue, and corrosion resistance. They have become viable alternatives to conventional metallic materials in many industries such as aircraft, marine structures, ships, buildings, transportation, electrical and electronics components, and offshore structures. However, since FRP contains polymer matrix, the composites and their structures are combustible. FRP will degrade, decompose, and sometimes yield toxic gases at high temperature or subject to re conditions. Due to their combustible nature, re safety and re protection of FRP are of great concern. Consequently, improving the ame resistance of polymers is crucial to increase the utilization of FRP. Understanding the combustion process of composite laminates has led to the knowledge that re resistant performance can be improved chemically and physically in both vapor phase and condensed phase of the combustion process by controlling the heat and/or fuel to keep it below a critical level. In

*Correspondence to: Jihua Gou, Department of Mechanical, Materials and Aerospace Engineering, University of Central Florida, Orlando, FL 32816, USA. Email: jihua.gou@ucf.edu Copyright 2011 John Wiley & Sons, Ltd.

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short, re can be prevented if the concentration of gaseous mixture and autoignition temperature are maintained below a critical value [1, 2]. For the analysis of the re resistance performance of polymer composites, open literature primarily focuses on parameters such as heat release rate (HRR), peak heat release rate (PHRR), and time to ignition. If the evaluation on materials re performance is based solely on these data, however, it runs the risk of oversimplication and, possibly, misleading [3]. For example, when analyzing the ame resistant performance of structural materials, their capability to sustain loading under combustion conditions is also extremely important [46]. Whereas the glass transition temperature Tg is an intrinsic material property that cannot be modied without changing the molecular structure of the polymer, it is possible to control the mass loss and mass loss rate during combustion. In this case, it is important to determine the parameters such as mass loss and mass loss rate of the material, which would otherwise have been ignored. In this study, exfoliated graphite nanoplatelets (xGnPs) were introduced into the polymer matrix to enhance the ame resistance of the composites. The selection of xGnP was to take advantage of their anisotropic thermal conductivity (K = 3000 W/m; K = 6 W/m), so the heat could be easily dissipated during heat transfer process. Additionally, their planar structure is such that the permeability [7] of the composites would be lowered down and the path of decomposed polymer (fuel) would become more torturous, which will be discussed in the later section [810]. However, it must be noted that the addition of nanollers alone into the polymer will often not satisfy the requirements of re regulations. The traditional additives still need to be used to satisfy them [11, 12]. Therefore, when preparing samples, APP particles were used as major additives to satisfy this need with a weight ratio of 1:4. Under this ratio, 25, 15, 10, and 5 wt% of APP particles were incrementally replaced by xGnPs, and the samples were then characterized by Xray diffraction (XRD) and cone calorimeter tests. In previous research, a papermaking technique that combined carbon nanober, nanoclay, and polyhedral oligomeric silsesquioxanes into a selfstanding nanopaper was developed. Those nanopapers successfully improved the ame resistant performance of FRP [1315]. To attempt a further improvement of the ame resistant efciency of the nanocomposites, xGnp/CNF hybrid nanopapers were developed and coated onto the surfaces of the laminates. xGnP and APP were also mixed into the polymer matrix at a given ratio of xGnP/APP/resin = 2/18/80. The samples coated with hybrid nanopapers were characterized by cone calorimeter tests, and their chars collected after testing were examined by scanning electron microscopy (SEM).

2. EXPERIMENTAL 2.1. Materials Vapor grown carbon nanobers (Polygraf III PR25HHT) were supplied by Applied Sciences, Inc. (Cedarville, OH, USA), with an average diameter of 80 nm and average surface area of about 50 m2/g. xGnP Graphene Nanoplatelets were supplied from XG Sciences (Lansing, MI, USA), and APP (AP423) was supplied from Clariant International Ltd (Charlotte, NC, USA). The glass ber was supplied by Composites One, Inc. (Lakeland, FL, USA) with a surface density of 800 g/m2. The unsaturated polyester resin (product code: 7126117, Composites One) was used as matrix material for laminated composites with the methyl ethyl ketone peroxide as a hardener at a weight ratio of 100:1. 2.2. Processing of nanocomposites containing exfoliated graphite nanoplatelets and ammonium polyphosphate Prior to mixing with the unsaturated polyester, xGnP was rinsed with acetone to improve its wettability with respect to the resin. Specically, xGnP powders were suspended in acetone, and then the mixture was sonicated using a Misonix S3000 sonicator with a power of 90 W for 20 min. The acetone was then drained using a vacuum system; nally, the treated xGnP and asreceived APP were mixed into the unsaturated polyester by a mechanical shear mixer (Model 5000230; manufactured by ColeParmer Instrument Company, Vernon Hills, IL, USA) with a speed of 1400 rounds per minute
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for 2.5 h. After preparing the matrix, a resin transfer molding process was used to manufacture glass berreinforced nanocomposites. The polymer was injected into an aluminum mold containing eight layers of glass ber mats at a pressure of 80 psi. After the resin was allowed to cure in the mold at room temperature overnight, the composites were postcured at 120 C in an oven for 2 h. Table I shows the compositions of the xGnP nanocomposite samples. 2.3. Processing of hybrid nanopapers and nanocomposites The asreceived CNF and xGnP were dispersed in distilled water with the aid of surfactant Triton X100. Then, the mixture was sonicated with the S3000 for 30 min at a power of 3050 W. After the suspension was well dispersed, the nanopaper was fabricated by ltering the suspension with a high pressure compressed air system (see Figure 1) at a pressure of 80 psi. The nanopaper was then applied to the surface of the nanocomposite during the resin transfer molding process. The compositions of the hybrid nanopapers and nanocomposites are shown in Table II. 2.4. Characterization and evaluation 2.4.1. Cone calorimeter tests. The re retardant performance of the nanocomposites with and without nanopaper coatings was evaluated by cone calorimeter (manufactured by Fire Testing Technology Ltd, UK) with an incident heat ux of 50 kW/m2 in accordance with ISO 56601 standard. The under and side edges of the composite samples were wrapped in an aluminum foil prior to the cone calorimeter test. All the samples were evaluated in a horizontal position with the surfaces coated with nanopapers, when applicable, directly exposed to the heat ux during cone calorimeter tests. The thickness of the samples is about 8 mm, with a resin volume and weight fraction of 70% and 50%, respectively. The experiments were repeated three times for each sample, and the results were reproducible to within 10%. The cone calorimeter data reported in this study represent an average of three replicated tests.
Table I. Composition of exfoliated graphite nanoplatelet nanocomposites.
Sample ID* GF xGnP APP0 laminates xGnP APP15 laminates xGnP APP17 laminates xGnP APP18 laminates xGnP APP19 laminates xGnP APP20 laminates 51.75 48.23 49.18 47.30 49.78 50.71 Contents (wt%) Resin 48.25 41.41 40.66 42.16 40.18 39.43 Additives 0.00 10.35 10.16 10.54 10.04 9.86 Weight ratios of GnP/APP/resin (%) 0/0/100 5/15/80 3/17/80 2/18/80 1/19/80 0/20/80

GnP, graphite nanoplatelets; APP, ammonium polyphosphate; GF, glass ber. *For the purpose of simplication, the above sample IDs are called control, APP15, APP17, APP18, APP19, and APP 20 later, respectively.

Figure 1. High pressure system for papermaking.


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Table II. Composition of hybrid nanopapers and nanocomposites.


Nanocomposites sample ID* GAL C0G1 GAL C1G3 GAL C1G5 GAL C1G1 GAL C3G1 GAL C5G1 GAL C1G0 GAL Composition (wt%) GF 49.83 50.17 49.16 49.10 48.12 48.85 48.88 48.27 Resin 40.14 38.91 39.73 39.81 40.59 39.99 40.01 40.46 xGnP 1.00 1.10 1.11 1.10 1.13 1.12 1.11 1.13 APP 9.04 9.84 9.99 10.00 10.17 10.04 10.00 10.14 Nanopaper 0.00 1.20 1.17 1.16 1.15 1.17 1.17 1.15 Weight ratios in the nanopaper No paper CNF/xGnP = 0/1 CNF/xGnP = 1/3 CNF/xGnP = 1/5 CNF/xGnP = 1/1 CNF/xGnP = 3/1 CNF/xGnP = 5/1 CNF/xGnP = 1/0

GF, glass ber; xGnP, exfoliated graphite nanoplatelets; APP, ammonium polyphosphate; CNF, carbon nanober. *For the purpose of simplication, the above sample IDs are called GA, C0G1, C1G5, C1G3, C1G1, C3G1, C5G1, and C1G0 later, respectively; GA is the control sample.

2.4.2. Xray diffraction. Xray diffraction analysis was carried out for the mixing samples (without nanopaper coating) using a Rigaku D/MAX Xray diffractometer (45 kV, 30 mA) equipped with copper Xray tube (wavelength of 1.54 ) at a scanning rate of 0.06 and 7 s per step. 2.4.3. Scanning electron microscopy. The hybrid nanopapers and char materials of the samples coated with nanopapers after cone calorimeter test were sputter coated with a conductive gold layer. They were analyzed by a Zeiss Ultra 55 SEM machine at an EHT of 5 kV.

3. RESULTS AND DISCUSSION 3.1. Cone calorimeter test of nanocomposites containing exfoliated graphite nanoplatelets and ammonium polyphosphate Figure 2 shows the HRRs of the samples containing different weight ratios of polyester, APP, and xGnP. Compared with the control sample, the HRRs of the samples containing APP and/or xGnP were

Figure 2. Heat release rate of the samples with different weight ratios of ammonium polyphosphate and exfoliated graphite nanoplatelets.
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visibly lower. The sample APP17 labeled as composed of 80% of resin, 17% of APP, and 3% of xGnP shows the lowest HRR curve. However, the other samples with the content of APP greater than 17% (xGnP is lower than 3%) or lower than 17% (xGnP is higher than 3%) show a higher HRR. With this information, it is inferred that there is an optimized weight ratio between APP and xGnP. A model for these results is one where the APP particles serve to reduce the HRR of the samples by acting as blow agents to generate air bubbles, which are expected to lower the thermal conductivity in the thickness direction (Figure 3). Simultaneously, the presence of xGnP would impair the thermal isolation ability of the protective char layer because of its platelet structure, high thermal conductivity, and heat absorption ability [16]. Therefore, there is a competing mechanism associated with introducing xGnPstheir high heat absorption and thermal conductivity will stimulate the pyrolysis of the polymer; conversely, the high thermal conductivity and the stimulation of polymer pyrolysis will accelerate the heat dissipation and rate of char creation, respectively. In addition, the platelet structure of xGnP might serve as barrier to prevent the decomposed fuel to feed the ame as shown in Figure 4 where it is proposed that the underlying mechanism that the platelet structure of xGnP will decrease the permeability of the samples, inhibiting the diffusion of the decomposed resin (fuel). This mechanism is supported by the mass loss rate of the samples. Figure 5 shows the mass loss rates of the control sample and sample containing 3% of xGnP and 17% of APP within its matrix. (Other samples were observed to have similar results but are excluded in this gure for ease of reading.) It can been seen that the curves closely line up with the HRR curves, which suggests that the reduced HRR is the consequence of reduced mass loss rate. In other words, the xGnPs effectively slow down the migration of the decomposed fuel, and it can be presumably concluded that under an optimized ratio, the synergistic effect between APP and xGnP is revealed.

Figure 3. Air bubbles trapped in the char structure of the exfoliated graphite nanoplateletsAPP17 laminates after cone.

Figure 4. The presence of exfoliated graphite nanoplatelets (xGnP) particles inhibits the diffusion of the decomposed resin.
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Figure 5. Mass loss rate (MLR) of the samples.

From the cone calorimeter tests results shown in Table III, it can be seen that the variations in weight ratios of xGnP and APP among these samples yield only differences in total HRR and char yielding. This indicates that the relatively large amount of traditional intumescent ame retardant, APP, has a dominant effect. With the exception of APP15, the PHRR of APP17, APP18, APP19, and APP20 are very close, as shown in Table III, suggesting that the addition of small amounts of these nanoparticles into the polymer would not signicantly affect the thermal properties of the samples that already have a high concentration of APP additives, unless the concentration of xGnP is very high (5% in this case). The HRRs of those samples coated with xGnP/CNF hybrid nanopapers are shown in Figure 6. As shown in Figure 6(b), the PHRR of C0G1 is 11% less than that of the control sample GA, and PHRRs of the sample C1G5, C1G3, C1G0, C3G1, C1G1, and C5G1 are 7%, 11%, 28%, 33%, 39%, and 100% higher than that of the control sample, respectively. Such a high PHRR is undesirable for the purpose of re retardancy, and a more sophisticated material design is needed. However, it can be seen in Figure 6(a) that immediately following the peaks of the papercoated samples, there is the dramatic decrease of the HRR. It is unlikely that the drop is due to the complete consumption of the composite material but rather is likely due to the formation of a protective char layer, considering long high HRR after the peak. In fact, it is intended that the introduction of the hybrid nanopaper should serve as a pre existed char layer and to prompt the formation of the protective char. In terms of analyzing the long term heat release behavior, the total HRR during different periods can be calculated by THR tt0 HRR dt (1)

Table III. A summary of the cone calorimeter test data of the mixing group.
Sample ID Total mass (g) Char yielding (wt%) Total heat released (MJ/m2) Peak heat release rate (kW/m2) Total smoke release (m/m2) Control 55 0 135 410 6063 APP15 58.0 17.8 111.0 389.0 6455.0 APP17 58.0 14.6 115.0 281.0 5270.0 APP18 57.0 10.9 115.0 310.0 5677.0 APP19 57.0 15.9 118.0 295.0 6104.0 APP20 56.0 14.1 116.0 270.0 4948.0

The thickness of all the samples is about 8 mm.


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Figure 6. Heat release rate of the samples coated with exfoliated graphite nanoplatelets CNF hybrid nanopapers. (a) 0 800 s; (b) 0 100 s.

By integrating the HRRs from 0 to 100 s, the total heat released (THR) before 100 s is shown in Table IV. The THR before 100 s of the samples coated with C0G1, C1G5, and C1G3 papers are, respectively, 33%, 16%, and 31% less than that of the GA sample. The differences between the GA sample and the rest of the samples are within 10%. During the major burning stage (100350 s) where most of the mass has been consumed, Figure 7 shows that the samples coated with xGnPdominated
Table IV. A summary of cone calorimeter test data of the papercoated group.
Sample ID GA C0G1 C1G5 57.0 18.9 331.0 115.0 14.4 62.0 5582.0 C1G3 57.0 11.1 344.0 112.0 11.8 57.2 5765.0 C1G1 59.0 19.9 430.0 117.0 17.3 60.7 5760.0 C3G1 58.0 19.1 411.0 113.0 16.7 60.6 5578.0 C5G1 59.0 19.3 621.0 122.0 18.9 59.0 5670.0 C1G0 57.0 18.9 396.0 114.0 18.1 67.5 6011.0

Total mass (g) 57.0 57.0 Char yielding (wt%) 10.9 18.3 310.0 276.0 Peak heat release rate (kW/m2) 114.0 110.0 Total heat released (MJ/m2) 17.1 11.5 Heat released (MJ/m2) (0 100 s) 69.3 60.3 Heat released (MJ/m2) (100 350 s) 5677.0 4811.0 Total smoke release (m/m2) The thickness of all the samples is about 8 mm.

Figure 7. Heat release rate between 100 s and 350 s.


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hybrid nanopapers exhibit lower heat release. By integrating the curve, it can be seen that the sample coated with C1G3 has the lowest THR (as listed in Table IV). The difference of THR between this sample and the GA sample is more than 17%. Only the sample coated with a pure CNF nanopaper has similar THR value with that of the GA sample. This is attributed to the fact that the pure CNF nanopaper has much higher permeability, thermal conductivity, and heat absorption ability than the nanopapers containing xGnP. The above results demonstrate the improvement in the THR of the composites achieved by coating with the hybrid nanopapers. The contents of the hybrid nanopapers that are dominated by xGnP have better ame retardancy than those of the CNFdominant hybrid papers. Similar to the re retardant mechanism previously discussed (Figure 4), it is reasonable to conclude that the xGnPdominant nanopapers have much lower permeability, thereby slowing the evaporation of the decomposed polymer that feeds the ame above the surface of the nanopaper. In addition, despite resulting in a higher PHRR, the CNF/xGnP hybrid nanopaper accelerates the char formation process. This re retardancy mechanism is further conrmed by the analysis of the smoke production rate data, as shown in Figure 8; these curves are highly similar to the HRR curves. Most of the smoke generated before 350 s, with the peaks of the GA samples (a in Figure 8) and the sample coated with CNFdominated nanopapers (c, d, g, and h in Figure 8) occurring before 150 s, whereas those of the samples coated with xGnPdominated nanopapers (b, e, and f in Figure 8) occurring near 350 s with rates before 150 s being much less than those of the GA sample. Although HRR is an important parameter to evaluate the re performance of polymer [3], other parameters such as mass loss are useful in regards to the materials post re mechanical properties. Figure 9 shows the change of mass percentage of matrices during re tests, mathematically, dened as the change in the mass percentage of matrices obtained by normalizing the total mass of matrix during cone calorimeter test. Because the mass of glass ber remains stable during the whole testing procedure, the matrix weight of a sample can be obtained as the difference of the mass of glass ber and the total mass. Mass percentage of matrix Mt M G Mi M G (2)

where Mt is the mass of the sample recorded during test, MG is the mass of the glass ber that equals 800 g/m2 Asample 8, and Mi is the initial mass of the sample. As shown in Figure 9(a), the polymer matrix of the control sample has been almost completely consumed, whereas the samples containing APP and xGnP within their polymer show an improved ability to retain their matrices during re testing. The sample containing 17% of APP and 3% of xGnP exhibits similar effectiveness as the sample where 20% of pure APP has been incorporated into the matrix. For the nanopapercoated samples, as shown in Figure 9(b), all the samples show an improved

Figure 8. Smoke production rate of the samples coated with the nanopapers. (a) 0 700 s; (b) 0 350 s.
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Figure 9. Mass percentage of matrices during cone calorimeter tests. (a) Direct mixing samples; (b) paper coated samples.

capability in preventing the mass loss compared with the control sample. In addition to the lower permeability of CNF/xGnP hybrid nanopaper that will effectively slow down the diffusion of the decomposed resin, another possible explanation is that carbonbased material might accelerate the process of forming the protective char layer on the surface of the samples. Thermally, a carbonbased coating layer would stimulate the decomposition of APP to form a foaming char layer, with the nanopaper itself structurally serving as a preexisted char layer. 3.2. Xray diffraction results of the samples containing different concentrations of ammonium polyphosphate and exfoliated graphite nanoplatelets As shown in Figure 10(a), there is no peak for the sample only composed of glass ber and polyester resin, whereas the peaks for APP powder (curve b in Figure 10) and the sample only containing APP
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Figure 10. Xray diffraction results of the samples with different concentrations of ammonium polyphosphate and exfoliated graphite nanoplatelets.

are similar, only differencing in their intensity, which is due to the fact the concentration of APP in the composite sample is lower than that of pure APP powder. Figure 10(b) shows the XRD pattern of xGnP powder, the sample containing APP only, and the samples containing both APP and xGnP on the same axes. It can be seen that the peak for xGnP is around 26.5. When the particles are mixed into the polymer with APP, the XRD patterns of the mixed samples are simply the combination of the patterns of APP and xGnP. For example, there are two peaks around 26 for the samples containing 2% and 3% (curves d and e, respectively, in Figure 10) of xGnP. The lower angle peak is attributed to APP, and the higher angle peak comes from xGnP. When the concentration of xGnP is increased to 5%, the contribution from xGnP around 26 becomes more obvious. These curves indicate that the mixing of xGnP into the polymer using mechanical mixer at room temperature will not result in a signicant change of intercalated distance between xGnP. As shown in Figure 10(c), it is interesting to note that there is no peak for the sample matrix composed of 1% of xGnP, 19% of APP, and 80% of polyester. If the xGnP particles had been exfoliated, there should be peaks for APP. The possibility of signicant experiment errors for the APP19 samples XRD data is highly unlikely, because the test for this sample was repeated four times with different locations, yielding the same results. This might have resulted from the APP and xGnP particles becoming amorphous at such a ratio. However, the phenomenon needs further investigation to determine its exact reason.
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Figure 11. Scanning electron microscopy images of nanopapers. (a) C1G3, (b) C3G1, (c) C0G1, and (d) C1G0.

3.3. Morphology of the nanopapers and char materials of the paper coating samples after cone calorimeter tests 3.3.1. Morphology of the nanopapers. The morphology of the nanopaper before coating onto the surface of FRP is shown in Figure 11. SEM images Figures 11(a) and 11(b) indicate that xGnP

Figure 12. Scanning electron microscopy images of char materials of the sample C0G1GAL.
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particles are well dispersed and entangled within the CNF networks. When the loading of xGnP is increased within the hybrid nanopapers, the permeability of the nanopapers decreases because of more xGnP particles lling into the pores of CNF networks. As shown in Figures 11(c) and (d), the pure xGnP and CNF nanopapers should have the lowest and highest permeability, respectively. 3.3.2. Morphology of chars after cone calorimeter tests. Figures 12 and 13 show the char characteristics of the composite samples coated with the nanopapers after cone calorimeter tests. There are three types of char formed during combustion reaction, labeled as A type, B type and C type. It is clear that A type char is the most compact, while the C type char has the lowest density. Generally, a sample that generates more compact char demonstrates improved ame retardancy [17]. The sample C0G1 shows a largest amount of A type chars in the surface and also shows good ame resistance (Figure 12). However, most of the chars from the sample C1G0 are composed of types B and C (Figure 13), and the sample shows a higher ammability than even the control sample.

4. CONCLUSIONS Through the analysis of cone calorimeter test data and char characteristics, it was found that the thermal properties and permeability of composites and char materials play important roles in determining the ammability of the materials. xGnP particles, used as an alternative to clay, show an excellent barrier effect when they are mixed in polymers and incorporated into CNFbased nanopapers. Specically, with an addition of 3% xGnP and 17% by weight APP into the polymer matrix, the re performance of the sample is the best of those tested, suggesting that there is an optimized weight ratio between xGnP and

Figure 13. Scanning electron microscopy images of char materials of the sample C1G0GAL.
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APP that uses their synergistic effect. By coating hybrid nanopapers onto the surfaces of those samples, the re resistance performance of the composite is further enhanced, both thermally and structurally, with the traditional ame retardant APP proving to be important to control the overall heat release of the composite materials during combustion reaction process.
ACKNOWLEDGEMENTS

The materials presented here are based upon the work supported by the Ofce of Naval Research under grant no. N000140910429 managed by Program Manager Dr Ignacio Perez. In addition, this work is partially funded by the National Science Foundation Nanomanufacturing Program under grant no. CCMI 0757302. Any opinions, ndings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reect the views of the Ofce of Naval Research and the National Science Foundation.
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Fire Mater. 2012; 36:241253


DOI: 10.1002/fam