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Electrical properties and microstructure of vinyl ester resin/compressed expanded graphite-based composites
Jie Fu, Hongfeng Xu, Yanbo Wu, Yu Shen and Chao Du Journal of Reinforced Plastics and Composites 2012 31: 3 originally published online 5 December 2011 DOI: 10.1177/0731684411431355 The online version of this article can be found at: http://jrp.sagepub.com/content/31/1/3

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Article

Electrical properties and microstructure of vinyl ester resin/compressed expanded graphite-based composites
Jie Fu1, Hongfeng Xu1,2, Yanbo Wu1, Yu Shen1 and Chao Du2

Journal of Reinforced Plastics and Composites 31(1) 311 ! The Author(s) 2011 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav DOI: 10.1177/0731684411431355 jrp.sagepub.com

Abstract In the present article, highly conductive vinyl ester resin/compressed expanded graphite sheet-based composites were investigated. The composites were prepared by vacuum impregnation with resin solution in compressed expanded graphite sheets of various densities. The microstructures of the composites were systemically characterized by X-ray diffraction, scanning electron microscopy, and mercury intrusion porosimetry. The composites were found to be still the basic constituent unit (i.e., carbon-crystal layer) of the compressed expanded graphite sheets after resin impregnation, although the pore diameter distribution of the composites changed. The effects of resin content on the electrical conductivity of the composites were also investigated. The effective media theory and a simple generalized effective media equation were employed to predict the electrical conductivity of the composites. The experimental results of electrical conductivities (in- and through-plane directions) and the microstructure of the composites were highly consistent with simulated data in the model.

Keywords compressed expanded graphite sheets, vinyl ester resin, electrical properties, effective media theory, generalized effective media equation

Introduction
Expanded graphite (EG) is a porous, layered modied graphite. Depending on the methods and conditions for preparation, the multipore structure of EG is diversiform. The diameters of the pores range from nanometer to hundreds of micrometer.13 The thickness of EG layers is approximately 10 nm, and the interlayer spacing is approximately 30 nm.4 Compared with natural graphite akes, there are abundant functional acids and OH groups at the edges of graphite layers. The EGs have a better anity to polymers because of their modied properties and structure.47 Thus, EG is a promising candidate for carbon/polymer composites. Many researchers have paid attention to the properties and structures of polymer/EG composites. Two methods are generally used to prepare the composites, namely, hot press molding and vacuum resin impregnation.

In hot press molding, the polymers and the EG particles are chosen as matrix and llers, respectively. Zheng1 studied the conductive polymethyl methacrylate (PMMA)/EG composites prepared using direct solution-blending method. These composites exhibited the lowest percolation threshold (s 1 weight percent [wt.%]) compared with conventional PMMA/carbon black (CB) conductive composites (s 8 wt.%) and PMMA/graphite composites (s 3.5 wt.%). The electrical conductivity of the composites can

1 College of Environmental and Chemical Engineering, Dalian Jiaotong University, 794 Huanghe Road, Dalian, P.R. China. 2 Sunrise Power Co., Ltd, No.907 Huangpu Road, Hi-Tech Zone, Dalian, P.R.China.

Corresponding author: Jie Fu, College of Environmental and Chemical Engineering, Dalian Jiaotong University, 794 Huanghe Road, Dalian 116028, P.R. China Email: fj@djtu.edu.cn

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4 reach 105 S cm1. Zheng4 and Wang5 reported the properties of EG/poly(styrene-co-acrylonitrile) composites. The in- and through-plane electrical resistivities of the composites were 8.5 103
cm and 1.2 102
cm, respectively. Song6,7 prepared a kind of aromatic polydisuled/EG nanocomposites reinforced by the short carbon ber. Electrical conductivity increased sharply when the EG content was more than 40% and became constant when it increased to 60%. The highest electrical conductivity was approximately 140 S cm1 when the EG content was approximately 70%. The introduction of short carbon ber reinforced the nanocomposites, but the electrical conductivity deteriorated slightly. Furthermore, other kinds of polymers have been used to prepare polymer/EG composites, for example, polyamide-6, polystyrene, polyfurfuryl alcohol, poly (vinyl acetate), epoxy resin, phenol resin, and so on.717 According to previous literatures, molecular chains of polymers can be easily intercalated into the pores by adsorption mechanisms because of the abundant pores and high EG aspect ratio. The other method for the preparation of composites is through vacuum resin impregnation in compressed expanded graphite (CEG) sheets, achieved by compression of EG particles. By this method, the polymer is considered as a dispersed phase, and the electrical conductivity of the composites is improved by the conductive EG networks. Only a few studies, however, have studied the preparation of polymer/EG composites from CEG sheets. Celzard reported a method by which CEG sheets were immerged with polyfurfuryl alcohol through three successive vacuumpressure cycles, and then the CEG-based composites were obtained after pyrolyzation and activation.18 A similar method was used in Krzesinska and Celzards research to prepare mica/EG nanocomposites.19 Ballard Power Systems,20 Dalian Institute of Chemical Physics, and Sunrise Power Co., Ltd.2123 separately reported several kinds of epoxy/CEG composite bipolar plates produced by this method. The good electrical property of the composite could be ensured by the continuous conductive phase obtained from the CEG sheets in the resinimpregnation method. In the present article, a kind of vinyl ester (VE) resin/ CEG-based composite was obtained by vacuum

Journal of Reinforced Plastics and Composites 31(1) impregnation with dierent CEG sheets. The eect of resin content on the morphological and electrical (both in- and through-planes) properties of the composites were studied. Many characterization methods were used to determine the relationship between the microstructure and the electrical properties of the composite. The eective-medium theories (EMT) were chosen to interpret the electrical conductivity from another point of view.

Experimental Preparation of composites

The VE resin was supplied by Shanghai Showa Highpolymer Co., Ltd. (Figure 1). Benzoyl peroxide (BPO) was chosen as curing agent. The resin and its curing agent were used as received. The properties of the CEG sheets are listed in Table 1. The raw CEG sheets were rst compressed into different densities. With the compressive pressure altered from 0 to 0.3 MPa, the densities ranged from 0.20 to 0.61 g cm3, correspondingly. Three densities of the CEG sheets were chosen, namely, 0.20, 0.27, and 0.61 g cm3, with corresponding sheet thicknesses of 7, 5, and 2.3 mm. The CEG sheets were put in a sealed vessel in vacuum (0.08 MPa, gage pressure), followed by VE resin solution impregnation. The samples were removed after the lapse of dierent impregnating times to form a series of composites with diverse resin content. After cleaning the residual resin on the surface of the samples, the composites were cured at 80 C for 12 h, followed by a postcure at 140 C for 2 h. Thus, the VE/ CEG-based composites were obtained. The composites were classied according to the densities of the CEG sheets and were named as CEG-0.20, CEG-0.27, and CEG-0.61 composite, respectively. The weight of added VE resin was dened by the ratio, y: y mVE mCEG 1

where mVE and mCEG are the weights of VE resin and CEG sheet used in the preparation of composites, respectively.

Figure 1. The structure of vinyl ester resin.

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Fu et al.
Table 1. Main characteristics of the raw CEG sheet Materials characteristics Density of raw CEG (g cm ) Thickness of raw CEG (mm) Packing density of pure raw EG particles (g cm3) Ash (%)
3

5 The pore diameter distribution of samples was characterized by mercury intrusion porosimetry (MIP) with Pore MasterGT 60. The in- and through-plane electrical conductivities (sin-plane and sthrough-plane) were measured through the four-point probe method with the in-house-built xture, whereby samples were kept under low pressure in the measurement setup (Figure 2). Samples were cut to rectangles (50 10 mm2). Current was applied using a programmable power supply (GW INSTEK PSP-2010) through two gold-coated copper plates, and the resulting voltage was measured by ESCORT EDM-3150 PRO multidisplay multimeter. The electrical conductivity was calculated according to the following equation:  IL VA 2

Raw CEG sheet 0.20 7 0.005 1.5

CEG: compressed expanded graphite, EG: expanded graphite.

where I is the applied current, V is the resultant voltage, A is the contact area of the specimen, and L is the thickness of the specimen.
Figure 2. Schematic diagram of experimental setup used in the electrical conductivity measurement.

Results and discussion

The presence of resin changed the properties of the CEG sheets. The plot of the density of the composites vs. the VE resin content is shown in Figure 3. The density of the composites increases with the ratio y. A denser CEG sheet results in faster increase in the density with the ratio y. The resin content in the composites can only vary within a certain range because of the high viscosity of the VE resin. Hence, the range of the ratio y in the series of composites based on heavier EG backbones (CEG-0.61) is smaller.

Microstructure of the VE/CEG composites

Graphite is a layered material that has strong intralayer covalent bonds within the carbon layers and weak Van der Waals interaction between successive carbon layers. During resin impregnation, the resin is infused into the pores of the CEG sheets. To identify whether the resin destroys the original microstructure of the CEG sheets, the XRD patterns of the CEG sheets (0.20 g cm3 and 0.61 g cm3), as well those of the CEG-0.20 and CEG0.61 composites, are shown in Figure 4. In all the curves, there is a narrow and sharp diraction peak (002) at 2y 26.42 and the d-spacing is . This condition suggests that compression and 3.37 A impregnation cannot change the basic constituent unit of CEG sheets, that is, the carbon-crystal layer. Compared with the 0.20 g cm3 CEG sheet, the (002) diffraction peak of CEG-0.20 composites becomes narrow and the intensity declines. Meanwhile, a broad weak

Figure 3. Apparent density of composites vs. Vinyl ester (VE) resin content, that is, ratio y.

Characterization
X-ray diraction (XRD) was performed on a RINT D/ MAX-2500/PC XRD, using CuKa radiation ( 0.154178). Generator tension was 40 kV, and generator current was 200 mA. Scans were taken from 5 to 50 , and scan rate was chosen as 5 min1. A scanning electron microscope (SEM, JEOL JSM-6360 LV) was used to study the microstructure of the composites.

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Journal of Reinforced Plastics and Composites 31(1)

Figure 4. X-ray diffraction (XRD) patterns of compressed expanded graphite (CEG) sheets and vinyl ester (VE)/CEG-based composites.

peak from 12.5 to 25 appears, attributable to the amorphous portion. The diameter of the particles can be calculated using the Scherrer equation. After resin impregnation, the diameter changes from 19 to 23 nm. The presence of resin does not alter the carbon-crystal layer, but the particles in the composites have magnied slightly because of the incursion of the resin. Meanwhile, the remarkable decline in the intensity of the diraction peak indicates the reduction in the crystallinity of the composites. The behavior of the CEG0.61 composites is dierent from that of the CEG-0.20 composites. In contrast to the 0.61 g cm3 CEG sheets, the XRD patterns of the CEG-0.61 composites have no obvious dierences, except for the broad weak peak from 12.5 to 22.5 . This phenomenon implies that the composites can maintain better crystallinity when the CEG sheets are compact. The cross-sectional morphology of CEG sheets and VE/CEG-based composites through SEM micrographs are shown in Figure 5. Comparing Figures 5(a) and (c), the apertures of the pores become smaller as the density of the CEG sheets increases. The composites of the CEG-0.20 series gain more resin because of the looser original porous structures. After impregnation, the resin occupies a part of the pores, reducing the size of the pore aperture. In the series of CEG-0.61 composites, however, the size range of the apertures is almost similar to the CEG sheets. This phenomenon indicates that the compact structure of the high-density CEG

sheets blocks the resin from penetrating into the composites. Hence, the composites retained their pore structure as the original materials. The anisotropy and layered structure of the CEG sheets and composites can be observed in the SEM micrographs. The anisotropy becomes more obvious with increasing density. Although resin impregnation does not alter the carbon-crystal layer, this process can change the pore structure of the CEG sheets. The detailed information of the pore structure is shown in Figure 6 and Table 2. For the CEG sheet, the pore diameter, porosity, and specic pore volume decrease with increasing density, but the specic surface area increases. This phenomenon suggests that compression reduces the pore size distribution range of the CEG sheets, and the pore diameter has an obvious downtrend. When the resin enters into the pores of the CEG sheets, the resin prefers interparticle to intraparticle pores (Table 2) because viscous resin is inclined to occupy the macropores. For the series of composites on the lighter EG backbones, for example CEG-0.20, their diameter, porosity, and specic pore volume decrease sharply after resin impregnation, but the specic pore area increases slightly. Otherwise, for the series of composites on the heavier EG backbones, such as CEG-0.61, resin impregnation has no obvious eect on diameter, porosity, and specic pore volume, but the specic pore area increases remarkably. Thus, resin impregnation

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Fu et al.

Figure 5. Scanning electron microscope (SEM) micrographs of (a) 0.20 g cm3 compressed expanded graphite (CEG) sheet, (b) 0.69 g cm3 CEG-0.20 composites, (c) 0.61 g cm3 CEG sheet, and (d) 0.71 g cm3 CEG-0.61 composites.

has a distinct eect on the pore structure of low density CEG sheets. The diversications of pore diameters are consistent with the information from SEM micrographs (Figure 5).

Electrical properties of the VE/CEG composites

The resin can occupy a part of the pores in the CEG sheets during impregnation, resulting in a change in porosity. The electrical conductivities measured both on in- and through-plane directions vs. ratio y of the composites are plotted in Figure 7. The VE/CEG-based composites evidently inherit an obvious anisotropy derived from the CEG sheets in electrical conductivity. The existence of VE resin reduces the electrical conductivity of the composites. When the resin content increases, both the in- and through-plane electrical conductivities decrease, and the decline in the in-plane direction is more evident. When the CEG sheet is denser, the anisotropy of the composites is more evident because of the progressive orientation of the graphite sheets having higher conductivity along the

Figure 6. Pore size distribution curve of raw compressed expanded graphite (CEG) sheets and vinyl ester (VE)/CEG-based composites.

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Journal of Reinforced Plastics and Composites 31(1)

Table 2. Pore structure parameters of CEG sheets and VE/CEG-based composites CEG sheet (0.20 g cm3) Mean pore diameter (mm) Specific pore volume (cc g1) Specific surface area (m2 g1) Porosity (%) Interparticle porosity (%) Intraparticle porosity (%) 0.98 5.69 23.22 93.25 19.67 73.57 CEG-0.20 composite (0.65 g cm3) 0.12 0.73 24.33 64.25 13.47 50.78 CEG sheet (0.61 g cm3) 0.13 1.28 38.25 74.11 5.33 68.78 CEG-0.61 composite (0.67 g cm3) 0.09 1.21 53.21 73.95 3.79 70.16

CEG: compressed expanded graphite, EG: expanded graphite, VE: vinyl ester.

Figure 7. Electrical conductivity vs. vinyl ester (VE) resin content ratio y. Notation: () in-plane direction, (#) through-plane direction. Solid lines represent the fitting of experimental data and dashed lines represent conductivity values of compressed expanded graphite (CEG) sheets.

plane direction. This condition indicates that, in principle, the composites maintain the intrinsic structure of the CEG sheets. Resin impregnation does not destroy the continuous EG networks. This phenomenon explains why the composites exhibit outstanding electrical properties.

Many investigators2,19,24 have studied the electrical conductivity of binary systems, consisting of insulating and conducting particles distributed disorderly. The electrical conductivity is interpreted by two main theories, namely, the percolation theories (PT) and EMT. In the present article, EMT is chosen to interpret electrical

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Fu et al. conductivity. The VE/CEG-based composites could be considered as intermediate morphologies between completely Bruggeman symmetric and asymmetric medium. The composites are governed by the following assumptions: (I) Each ellipsoidal particle is surrounded by a medium that has the eective conductivity of the composite. (II) The particles of each phase are homogeneously distributed, and the average electric eld inside the composite is equal to that applied to the material. The general eective media (GEM) equation2,19,25,26 is used for describing the electrical conductivity of binary mixtures. However, the VE/CEG-based composites in the present article consist of the following three phases: graphite, resin, and voids. To predigest this model, graphite and voids are considered as a conducting phaseEG phase. Hence, the composites can be regarded as binary conductorinsulator systems (sl 0), and they follow the simple GEM equation:  0 c t m h 1 c 3

9 ratio of the apparent density of the powder to the density of the particles) and conforms to the following empirical formula2,27: c p 5 % 4

The three series of composites studied in the present article were all derived from the same pure raw particles with the same packing density of 0.005 g cm3. The worms have a density of 0.015 g cm3 and a high porosity of 99.32%, assuming a bulk density of 2.2 g cm3 for graphite.2 Therefore, the critical volume fraction cworms (0.005/0.015)% 0.05% 28.33 volume percent (vol%) of the worms for CEG sheets, and the critical density; dc (0.2833 0.015) g cm 3 0.00425 g cm3, accordingly. Finally, the critical volume fraction of graphite is equal to: c dc/density of graphite 0.00425/2.2 vol% 0.1932 vol%. By such method of calculating EMT, all the particles are regarded as randomly oriented spheroids, with semiaxes dened: a b 6 c, and: 2 3La 1 3Lc h h a c 3La 3Lc h 1 2Lh h 1 Lh a c 3L 1 5 3Ll mh a l a 6Ll 1 Ll 3 1 2Lc l

mh

where sm and sh are the conductivities of the composites and the high-conductivity phase, respectively. The is the volume fraction of the high-conductivity phase. The c is the critical volume fraction of the high-conductivity phase. t is an exponent related to both c and the shape of the particles. The c of randomly oriented composites is close to the volume fraction p at the packing density (i.e., the

where mh (l) is the coecient describing randomly oriented particles, with that values can be calculated c within the limits sh ! 1 and sl ! 0.2,29 La nl expresses the eective depolarization factors of the high-/lowconductivity phases on the axis a(c) of the spheroids.

Figure 8. Electrical conductivity s vs. volume fraction of conducting phase in the composites. The lines are the fits of the simple general effective media (GEM) equation (Equation (3)) to the experimental data (c 0.1932 volume percent [vol.%]). Notation: () in-plane direction; (#) through-plane direction.

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Journal of Reinforced Plastics and Composites 31(1)

Table 3. Parameters describing morphology of the two phases in the mixture CEG-0.20 Measurement direction sh (S cm1) t La h mh ml (a/c)h (a/c)l In-plane 48.18 2.43 7.46E-04 894.16 2.44 2678.50 1.96 Through-plane 13.73 2.17 8.19E-04 814.27 2.18 2438.80 2.01 In-plane 38.91 3.17 4.97E-04 1341.33 3.18 4020.00 1.89 CEG-0.27 Through-plane 11.00 2.01 7.89E-04 845.63 2.02 2532.90 2.05 In-plane 126.03 5.88 2.29E-04 2907.83 5.89 8719.50 1.83 CEG-0.61 Through-plane 5.87 5.98 2.25E-04 2962.08 5.99 8882.20 1.83

CEG: compressed expanded graphite.

The aspect ratio of the particles can be derived from depolarization factors,2 Lc: 1 e2 Lc e arctan e e3 r a2 1 e c

where e is the eccentricity of the spheroids. In the three series of composites, most of the experimental points may be considered by the generalized EMT in Figure 8. The tting of the electrical conductivity data through the GEM equation and the parama c eters (i.e., sh, t, mh(l), La hl , and c hl ) may provide the morphological information on the conducting and insulating phases. The parameters are shown in Table 3. Adjustable parameters (sh and t) are obtained from the tting of experimental data by Equation (3), and the morphological parameters mh(l) can be obtained c by the methods mentioned in Reference 2. The La hl and the aspect rations of the two phases, a c hl , are calculated using Equations (5) and (6). In EMT, the value of mh ! 1 implies that the insulating particles are coated by the conducting phase in the mixture. When La h 0, the particles will be regarded as at disks. According to the values of the mh and La h, the EG particles in the VE/CEG-based composites are high attened spheroids. With increasing density of the CEG sheets, the aspect ratio increases evidently, indicating that the atness of the particles in the EG phase becomes more remarkable. This nding is in good agreement with the morphology of the composites in Figure 5. Compared with mh in the conducting phase, parameter ml is smaller. Thus, the atness of the insulating particles is correspondingly inconspicuous.

properties were studied as a function of resin content (i.e., ratio y). Given the anisotropy of the CEG sheets matrix, all the series of composites were anisotropic. Although resin impregnation brought amorphous portion to the composites and alters their pore structure, this process could not change the basic constituent unit of CEG sheets. This phenomenon explains why all the series of composites remain with high electrical conductivity. When the resin content increased in the CEG sheet, the density of the composite was enhanced. Meanwhile, the electrical conductivities of the composite on two directions decrease. The layered structure and the attened pores could explain the anisotropy in all the composites. The morphological parameters derived from the GEM equation forecasted the atness of the particles in EG phase and deduced that the phenomena will become more remarkable with the resin content (ratio y) increasing. This conclusion is in agreement with the morphology of the composites.

Funding
This research received no specic grant from any funding agency in the public, commercial, or not-for-prot sectors.

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Conclusion
A VE/CEG-based composite was prepared with CEG sheets by resin vacuum impregnation. The electrical

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