Wonchang Park Kyungwho Choi

Department of Mechanical Engineering, Texas A&M University, College Station, TX 77843

Influence of Nanomaterials in Polymer Composites on Thermal Conductivity

Carbon nanotube- or/and graphite-lled polymer composites were synthesized by using simple mixing and drying methods, and their thermal conductivities and structures were characterized by using a steady-state method (ASTM D5470) and scanning and transmission electron microscopies. In order to investigate the inuence of synthesis conditions on the thermal conductivity of composites, various concentrations of multiwall carbon nanotubes, graphites, surfactants, and polymer matrix materials as well as two different nanoparticles and solvents were tested. Our composites containing both nanotubes (25 wt. %) and graphites (25 wt. %) with sodium dodecyl benzene sulfonate (SDBS) as a dispersant showed the highest thermal conductivity, $1.8 W/m-K at room temperature. The highest conductivity from nanotube/graphite mixtures would be from good adhesion and less voids between nanotubes and polymers as well as excellent thermal conduction from graphite sheets. The thermal conductivities of the composites have been calculated as a function of carbon nanotube concentrations by using a model based on the Maxwells effective medium theory, and the most effective method of improving thermal conductivity was suggested. [DOI: 10.1115/1.4005201] Keywords: thermal interface material, carbon nanotube, graphite, effective medium theory

Khalid Lafdi
Carbon Research Laboratory, University of Dayton, Dayton, OH 45469

Choongho Yu1
Department of Mechanical Engineering, Texas A&M Universiity, College Station, TX 77843; Materials Science and Engineering Interdisciplinary Program, Texas A&M University, College Station, TX 77843 e-mail: chyu@tamu.edu

Introduction

Heat dissipation in electronic devices becomes very important because the power density of the state-of-the-art electronic devices is extremely high due to their highly integrated circuits and small sizes. Effective heat dissipation is also crucial in maintaining the performance of electronic devices [1]. One of the most limiting factors in heat dissipation is thermal contact resistance between different parts. In order to reduce the contact resistance, various materials have been synthesized and tested for a wide variety of applications including microprocessors, optoelectronics, and power electronics [24]. These are typically called thermal interface materials (TIMs) [3,5,6]. The thermal contact resistance is mainly from the surface asperity that prohibits a full contact, which leaves voids between objects in contact. The actual contact area is often only a fraction of apparent contact areas [3]. The void is typically lled with air or vacuum whose thermal conductivity is signicantly lower than those of solid materials. In general, polymeric materials are exible, and thereby suitable for lling highly irregular spaces between surfaces. However, typical polymers have very low thermal conductivity ($0.2 W/m-K [79]), which has been one of the key parameters in the efforts for improving the performance of TIMs [912]. In order to improve the thermal conductivity, carbon nanotubes (CNTs), and graphites have been used because of their high thermal conductivities. The thermal conductivities of an individual nanotube and graphite (in-plane) can reach over 103 W/m-K at room temperature [1315]. For example, vertically aligned nanotube arrays without using a polymer matrix have been synthesized for TIM [11] but they are often inadequate to accommodate highly irregular surfaces for increasing actual contact areas. It is also necessary to use a high temperature synthesis process, prohibiting a direct integration on heat dissipating
1 Corresponding author. Contributed by the Heat Transfer Division of ASME for publication in the JOURNAL OF HEAT TRANSFER. Manuscript received July 22, 2010; nal manuscript received September 27, 2011; published online February 13, 2012. Assoc. Editor: Pamela M. Norris.

devices or structures. These drawbacks could be alleviated by synthesizing free-standing polymer composites made of combining polymers, nanotubes, and graphites. Polymer composites with nanomaterials can be synthesized by solution mixing, melt blending, and polymerization [16]. Hu et al. made composites by mixing Ni metal particles and multiwall carbon nanotubes (MWCNTs) in silicone oil [9]. They found that the thermal conductivity of the composites with a large amount of Ni particles (3040 vol. %, $13.5 lm in diameter) and 23 vol. % of MWCNTs enhanced thermal conductivity. However, a high concentration of Ni particles often makes it difcult to form a solid material with good adhesion and strength. Huang et al. [17] synthesized CNT-polymer composites by injecting polymers into aligned nanotube arrays. Their thermal conductivities were improved due to aligned CNTs perpendicular to the substrate. The thermal conductivity was increased from 0.56 W/m-K up to 1.21 W/m-K. The alignment process is complicated, but yielded only marginal conductivity increments. Moreover, high processing temperatures of the chemical vapor deposition for the direct deposition of nanotubes on a substrate can damage devices/parts such as electronic chips and heat sinks. On the other hand, graphite additives have resulted in better thermal conductivity than carbon nanotubes [8,12]. The higher conductivity may be from the excellent conduction along the in-plane direction of graphite sheets whose lengths are much longer than those of nanotubes. However, the sheet structure often causes void formations and poor mechanical strength, which generally require high pressure pressing or high temperature curing steps. These limitations are not desirable for TIM applications [18]. This work presents simple fabrication methods and thermal conductivities of nanotube- or/and graphite-lled polymer composites. Both nanotubes and graphites were also mixed together in order to seek synergistic effects from two dissimilar shape materials. In addition, metallic nanoparticles were incorporated into nanotubes to study the inuence of the nanoparticles on thermal transport behaviors. Two different polymer matrix materials, Vinnapas 401 and Epon 862 were used in this study. In these composites, nanotube/graphite dispersion is crucial in obtaining good APRIL 2012, Vol. 134 / 041302-1

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thermal and mechanical properties of composites. For better dispersion of nanotubes/graphites in water, sodium dodecyl sulfate (SDS, or sodium lauryl sulfate), or sodium dodecyl benzene sulfonate (SDBS) was employed as a stabilizer [19]. The inuence of the surfactant on thermal conductivity was also investigated by stabilizing nanotubes/graphites in dimethylformamide (DMF) or 1-methyl-2pyrrolidinone (NMP) without using SDS or SDBS. Samples were simply dried at room temperature or relatively low temperature ( $80  C) without applying any external pressure. Our experimental results show that composites containing nanotube/graphite mixtures dispersed with SDBS have the highest thermal conductivity ($1.85 W/m-K at room temperature). The mixture provides better structural integrity from good adhesion between nanotubes and polymers as well as higher thermal conduction from graphites. In addition, nanotubes ll voids between graphites, making composites less porous. The optimum ratio between nanotubes and graphites was also studied in this work. The following describe the detail procedures of sample preparation and characterization as well as the analyses of thermal conductivity measurement results.

Experimental Procedures

Total 20 different composites were synthesized with MWCNTs, exfoliated graphites, metal nanoparticles, and polymer matrix materials, as listed in Table 1. Vinnapas 401 (Wacker chemical) consists of a vinyl acetateethylene copolymer emulsion [7,20] and Epon 862 (Miller Stephenson chemical) diglycidyl ether of Bisphenol F) [21]. The samples made of Vinnapas is exible due to a low glass transition temperature as opposed to stiff Epon samples. A typical synthesis process with a surfactant and MWCNT/ graphite is the following. MWCNTs (Cheaptubes, 95%), exfoliated graphites [8], SDS (Fisher scientic), and SDBS (Acros organics, 88%) with the weight ratios in Table 1 were mixed with deionized (DI) water of 1520 ml. The total weights of the nanotubes/graphites and surfactants ranged from 0.06 to 0.375 g. The concentrations of MWCNTs were varied from 10 wt. % to 40 wt. % except the metal-decorated nanotubes, and the concentrations of graphites from 10 wt. % to 80 wt. %. The weight ratio of conductive llers to surfactants was selected from 3:1, 2:1, and 1:1 except the metal-decorated nanotubes. It should be noted that SDS and SDBS
Table 1

are necessary to effectively disperse/stabilize nanotubes in water [7,19,20,22,23]. The mixture was sonicated with an ultrasonic homogenizer (Misonix XL-2000) for 2030 min until nanotubes/ graphites were well dispersed in water. Water was added to the mixture during the sonication for better dispersion. At the end of the sonication, the total volume of solidliquid mixtures was $40 ml. Then, the polymer matrix material, Vinnapas 401 or Epon 862 was added to the solution followed by another sonication process for 2 $ 3 minutes. The weight of the polymers ranged from 0.08 to 0.4 g. The mixture thickened by the sonication was poured into a plastic container (5.4 cm 5.4 cm 1.7 cm). Subsequently, the mixture was dried in a fume hood at room temperature for 23 days. Finally, the composite was completely dried in an oven at 80  C for $ 1 h in order to remove residual water. For decorating metals on MWCNT surfaces, nanotubes were reuxed in 70% nitric acid with stirring for 20 h at the boiling temperature. The solution was diluted with DI water and subsequently ltered with polytetrauoroethylene (PTFE) membranes (pore diameter: $ 0.45 lm). The nanotubes were thoroughly washed with DI water and dried in a fume hood for 2 days at room temperature. The acid treated nanotubes (0.15 g) were dispersed in 100 ml of DMF (Fisher scientic, 99.9%) at 60  C by stirring. After 30 min, 100 ml of 0.02 M iron nitrate (Acros organics, 99%) in water was added into the mixture of nanotube and DMF. The solution was stirred for 16 h at 60  C. Finally, the nanotubes were ltered and washed with DI water, and then fully dried at room temperature in a fume hood for 23 days. In order to decorate nickel particles on nanotubes, hydrogen reduction was used [24,25]. First, 0.1 g of acid treated nanotubes was mixed with 100 ml of 0.05 M nickel nitrate (Fisher scientic, 99.0%) in water. The mixture was sonicated in an ultrasonic bath (Branson 1510 R-MT) for $ 5 min and then stirred at room temperature for 20 h. The mixture was ltered and dried at $120  C on a hot plate until the tubes were completely dried. The nanotubes were then annealed at 450  C for 2 h with a 4  C/min ramping rate in 2030 sccm Ar in a tube furnace of 23-mm inside diameter. Subsequently, temperature was raised to 500  C and the sample was reduced with 2030 sccm H2 gas for 3 h. Polymer composites with iron- or nickelincorporated nanotubes were synthesized by using the method described above. Due to the high density of the metals compared to

The concentrations of ller, surfactant, and matrix materials, and the thicknesses of polymer composites Filler (wt. %)

Graphite 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 30 50 60 40 25 10 60 30 80 40 80 64 40 50 25

MWCNTs 15 15 30 27.2 (Fe: 12.9) [CNT: 9.3 vol. % (Fe: 2.2 vol. %)] 41 (Ni: 20.5) [CNT: 15.3 vol. % (Ni: 3.6 vol. %)] 10 25 40 30 40 16 40 25

Surfactant (wt. %) SDS SDBS SDS SDBS SDS SDBS SDBS SDBS SDBS SDBS SDBS DMF DMF DMF DMF NMP NMP NMP SDBS SDBS 25 25 5 5 10 36.4 [46.8 vol. %] 20.5% [30.3 vol. %] 30 25 20 25 25 25

Polymer Matrix (wt. %) Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 Vinnapas 401 EPON 862 EPON 862 80 80 60 36.4 [41.7 vol. %] 38.5 [50.7 vol. %] 40 25 20 25 25 25 40 40 20 20 20 20 20 25 25

Thickness (lm) 109.3 6 2.3 122.2 6 5.0 126.2 6 2.2 68.5 6 1.2 94.3 6 16.2 72.4 6 8.0 176.8 6 9.0 221.9 6 6.9 158.4 6 7.1 250.4 6 5.1 155 6 3.4 46.6 6 1.7 194.6 6 15.8 615.5 6 2.5 216.2 6 4.6 192.7 6 5.0 304.5 6 0.5 441.4 6 18.9 285.7 6 5.3 76.6 6 2.7

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other carbon-based materials, the volume fractions were also listed in Table 1. Note that the densities of nickel and iron are, respectively, 8.908 and 7.874 g/cm3 [26]. Composites were also synthesized without using any surfactant. This requires solvents such as DMF or NMP (Alfa aesar, 99%) for better nanotube and/or graphite dispersion [27]. MWCNTs (0.060.112 g) were sonicated in the solvent (5 ml) with a pen type sonicator until they were well dispersed. Subsequently, Vinnapas or Epon was added and then sonicated for additional 10 min. Samples were dried at 50  C for $ 4 h in a vacuum (better than 1 Torr). The structure of the samples was analyzed with scanning electron micrographs (SEMs, taken by using JEOL JSM-7500 F) after the samples were cold-fractured in liquid nitrogen to expose their cross sections. The cross-sectional surfaces were highly uneven due to many graphite particles pulled out from the composites because the sample was too exible to easily fracture the sample (The samples were rather torn apart). Transmission electron micrographs (TEMs, taken by using JEOL 1200 EX) were also taken to inspect the morphology of metal particle-decorated nanotubes. The nickel-decorated nanotubes were also scanned in an X-ray diffractometer (Bruker-AXS D8 VARIO). Thermal conductivities were obtained by using a steady-state measurement (ASTM D5470) setup. The thickness measurements were performed at ten different locations for each sample. The largest errors came from the variation of the thickness, and uncertainty analyses were performed with 95% condence.

Results and Discussion

The thermal conductivity of the nanocomposite is expected to be increased as a function of MWCNT/graphite concentrations since polymers such as Vinnapas 401 typically have relatively low thermal conductivity ($ 0.2 W/m-K) [7,20,22,23]. The polymers are necessary to bind the llers, providing enhanced mechanical strength and thermal conduction. However, the samples with moderate ller ratios only showed conductivities close to those of polymers. For example, the thermal conductivities of 15-wt. % MWCNT composites were measured to be $ 0.2 W/m-K at room temperature (sample 1 and 2; see Fig. 1). This is somewhat surprising because the thermal conductivity of an individual MWCNT was reported to be $ 3000 W/m-K at room temperature [14]. For instance, when a nanotube concentration is $ 10 vol. %, the thermal conductivity of a composite is estimated to be

$102 W/m-K using a parallel resistor model [7]. This implies that phonons do not effectively travel through junctions between the nanotubes as well as across the nanotubes and polymer matrix materials [7,20,23]. The surfactants, SDS and SDBS, which are necessary for dispersing nanotubes in water, did not make signicant differences (samples 1 and 2). SDBS is similar to SDS, but has an additional benzene ring that may slightly reduce conductivity. An increase of the MWCNT concentration to 30 wt. % (sample 3) doubled thermal conductivity ($0.4 W/m-K), but the conductivity is still much lower than expected values. The current recipe, however, was not adequate to synthesize samples with a nanotube concentration higher than 30 wt. % when graphites were not added. Samples with higher nanotube concentrations were cracked into pieces during the drying process. Strongly bundled and/or aggregated nanotubes are likely to inhibit nanotubenetwork structures that are necessary to form composites. We have explored the inuence of the metal nanoparticles on the thermal conductivity of the composites. Iron particles are a few nanometers in size, much smaller than nickel particles whose particles range from several to tens of nanometers, as shown in Fig. 2. The particles in samples 4 and 5 were identied as iron and nickel, respectively, by using energy dispersive spectroscopy. The X-ray diffraction result shown in the inset of Fig. 1 conrmed the presence of nickel. Iron was not identied by the X-ray diffraction. We believe this is because of small particle quantity or/and amorphous structures. The conductivities of the composites are more or less similar to those of other samples without nanoparticles. Nevertheless, the iron-incorporated sample (sample 4) shows a higher conductivity compared to the nickel sample (sample 5). The thermal conductivities of nickel and iron are, respectively, 90.9 and 80.4 W/m-K at 300 K [26]. The relatively high conductivities of the metals compared to polymers ($0.2 W/m-K) may enhance the overall conductivity of composites. Nevertheless, our results indicate that the metal incorporation does not considerably change the conductivity. The density of metal particles is very different from those of nanotubes and polymers, which may impede phonon transport due to their mass differences. In addition, the metal decoration makes nanotubes aggregated during the composite synthesis process, which is likely to reduce thermal conductivity signicantly. When graphites were used instead of nanotubes, high graphite loadings up to 80 wt. % were possible. Such high loadings were feasible when DMF or NMP was used instead of SDS or SDBS. The DMF and NMP solvents were removed by the drying process,

Fig. 1 The thermal conductivities of samples 18 at room temperature. MW, Vin, and Gra represent MWCNT, Vinnapas 401, and graphite, respectively. The inset shows X-ray diffraction of nickel-decorated nanotubes.

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Fig. 2 (a) Iron-incorporated nanotubes and (b) nickelincorporated nanotubes before they were mixed into polymers. Black circular shape objects are the metal nanoparticles. Both scale bars indicate 100 nm.

Fig. 4 The cold-fractured cross-sectional surfaces of (a) sample 7 (50-wt. % graphites) and (b) sample 10 (25-wt. % graphites and 25-wt. % MWCNTs). The inset show a nanotube bundle between graphite sheets. Scale bars indicate 5 lm except the inset scale bar (2 lm).

but SDS and SDBS cannot be eliminated from the composites. The composite with 30-wt. % graphite (sample 6) exhibits higher conductivity than those of the nanotube-lled samples. As graphite concentrations were increased to 50 wt. % (sample 7) and 60 wt. % (sample 8), the thermal conductivity was raised to $ 0.84 and $1.1 W/m-K, respectively. The improved conductivity is likely to come from less thermally resistive paths along graphite sheets than those across tubetube junctions in the nanotube-lled composites. Nevertheless, thermal transport across contacts between the sheets is still not good enough to obtain a graphitelike conductivity. While the polymer matrix can accommodate high-concentration graphites, their anisotropic thermal conductivities (in- and out-ofplane directions) are disadvantageous. When graphite sheets are stacked together, the conduction along the direction perpendicular to the graphite plane is limited. In addition, their sheet structures tend to make voids between the sheets, making composites porous. These could be at least partially overcome by introducing smaller particles such as MWCNTs. Nanotubes may thermally bridge graphite sheets and ll the voids. In this study, MWCNTs were mixed together with three different weight ratios of MWCNTs to graphite (4:1, 1:1, and 1:4). Figure 3 shows the replacement of graphites with MWCNTs increases thermal conductivity, reaching $1.5 W/m-K with 25-wt. % graphites and 25-wt. % nanotubes (sample 10). However, excess MWCNTs such as 10-wt. % graphites and 40-wt. % nanotubes (sample 11) decreased thermal conductivity. Figures 4(a) and 4(b), respec-

tively, show the fractured cross-sections of the composites with and without nanotubes. Graphite sheets are relatively loose from the polymer matrix in the graphite only sample (sample 7, Fig. 4(a)) compared to sample 10 (Fig. 4(b)) that contains both graphites and nanotubes. The inset of Fig. 4(b) also shows nanotubes bridged between graphite sheets. These samples contain a surfactant such as SDBS or SDS that is necessary for dispersing graphites and nanotubes in water. The surfactants do not have high conductivities close to those of graphites and nanotubes. In addition, they typically wrap around the conductive llers, preventing direct contacts between them. The different vibration spectra between the llers and surfactants may also hamper phonon transport. In order to avoid any adverse inuence from the surfactants, solvents (DMF and NMP) were used for the dispersion without adding any additional surfactants. When Vinnapas with DMF was used instead of 20-wt. % SDBS in sample 8, the conductivity was decreased to $0.85 W/m-K (60 wt. % graphite; sample 12) compared to sample 8 ($1.1 W/m-K), as shown in Fig. 5. Replacing 30-wt. % graphites with nanotubes (sample 13) showed a similar conductivity. The composites made of 80-wt. % graphites (sample 14) or a mixture of 40-wt. % graphites and 40-wt. % nanotubes (sample 15) exhibited similar conductivities in comparison to the composite made of 60-wt. % graphites dispersed by 20-wt. % SDBS (sample 8). On the other hand, the conductivity was raised when NMP was used instead of DMF (samples 17 and 18), as shown in Fig. 5. The mixture of graphites and nanotubes (40 wt. % each; 80 wt. % total conductive llers) improved conductivity from $1.1 W/m-K (sample 16) to $1.7 W/m-K (sample 18). The thermal conductivity difference

Fig. 3 Room temperature thermal conductivities (samples 7 and 911) as a function of four different weight ratios (1:0, 4:1, 1:1, and 1:4) of graphites to MWCNTs. The composites contain total 50-wt. % llers and 25-wt. % surfactant.

Fig. 5 The thermal conductivities of samples 8 and 1218 at room temperature. For samples 1218, nanotubes and graphites were dispersed in DMF or NMP without using any stabilizers such as SDBS or SDS.

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  ke km kp km fp ke 2km kp 2km

(1)

Fig. 6 The cold-fractured cross-sectional surfaces of (a) sample 15 (dispersant: DMF) and (b) sample 16 (dispersant: NMP). The inset in (a) shows nanotube bundles between graphite sheets. Scale bars indicate 5 lm except the inset scale bar (2 lm).

between samples dispersed by DMF and NMP can be inferred from SEMs in Fig. 6. Sample 15 (dispersed in DMF) shows polymers coated on graphite sheets, which may prevent direct contacts between nanotubes and graphites. The matrix material for these samples are Vinnapas 401, which has a relatively low glass transition temperature (Tg 15  C). Low Tg polymers typically show lower thermal conductivity than high Tg polymers due to loose interatomic bondings. High Tg polymers, however, are often brittle and tend to break by external impact. Here, thermal transport performance of composites made of Epon 862 (Tg 135  C) [28] was compared to the samples containing Vinnapas as shown in Fig. 7. The matrix replacement from Vinnapas to Epon increased the conductivity of sample 7 (50 wt. %-graphite and 25 wt. %-SDBS with Vinnapas) by $ 180% ($ 1.5 W/m-K, sample 19). By mixing 25-wt. % nanotubes as a substitute for 25-wt. % graphite with the Epon matrix material, the highest conductivity of $ 1.85 W/m-K was obtained (sample 20). However, when Vinnapas was used in stead of Epon (sample 10), the conductivity was similar to that of sample 19 (50 wt. %-graphite and 25 wt. %-SDBS with Epon). The brittle and rigid characteristics of Epon is shown in the inset of Fig. 7. The fractured surface of the Epon sample (sample 20) shows sharp edges, which are different from the samples made of Vinnapas. In order to investigate the inuence of the graphite, CNT, and polymer matrix on the thermal conductivity of the composite, we employed a model based on the Maxwells effective medium theory [29]. When the interactions between constituents in the composites are negligible (e.g., low concentration llers), the following Maxwells model is considered to be valid [9,30]:

where ke, kp, and km, respectively, represent thermal conductivities for the composite, the particles (i.e., graphite or CNT), and the matrix. Here, fp is the volume fraction of the particles. When a composite has high concentration llers whose thermal conductivity is much higher than that of the matrix, the percolated networks of the llers need to be considered. In this case, the Maxwells model underestimates the thermal conductivity of the composite since the model does not take the interaction between the particles into account. In particular, it should be considered for the composites with high aspect-ratio llers like CNTs and graphites rather than spheres (or cubes) since they are easier to make percolated networks. In order to consider the inuence of the ller interactions, the Maxwell model has been modied to a simplied form with different v (a factor that varies depending on literatures) [9,3133] ke 1 v fp km (2)

For example, v 3 underestimated the thermal conductivity of CNT-lled composites [31]. In our study, we modied the Maxwells model under the assumption of kp ) km since our composites contain graphites and CNTs whose thermal conductivities are much higher than the polymer matrix ke 1 afp km 1 fp (3)

where a is a coefcient that accounts for the effectiveness of conductive llers on altering the composite thermal conductivity. The coefcient, a is 2 for the Maxwells model. In our study, a is larger than 2 due to the high concentration and high aspect ratios of the llers. It also depends on the dispersion and connections of the llers in the matrix. It is likely that the factor is a strong function of the ller type (i.e., graphite and CNT) at a ller concentration well above the percolation threshold due to their very different morphologies. Here, we used experimental data for samples 68 to nd a since they contain only graphites as a ller with the same Vinnapas matrix. The graphite concentrations are, respectively, 18.7, 34.8, and 44.5 vol. % (i.e., 30, 50, and 60 wt. %). Note that fp is the volume fraction but Table 1 lists weight ratios since weight is the actual measurable quantity. Therefore, weight percentage was converted into volume percentage. The volume fraction of each constituent (fi) was calculated using the following relation:  mi X mj (4) fi qi qj j where m and q indicate mass and density of the indexed (i or j) material. The densities of MWCNTs, graphites, SDBS, Vinnapas, and Epon are, respectively, selected as 2.1 g/cm3 [9], 2.1 g/cm3 [34,35], 1.06 g/cm3 [36], 1.19 g/cm3 [7], and 1.19 g/cm3 [21,28], respectively. The a values for samples 68 were, respectively, calculated to be 5.52, 5.09, and 4.30 by using Eq. (3). The thermal conductivity of Vinnapas, km, was assumed to be 0.2 W/m K [7]. Figure 8(a) shows the experimental data for samples 68 (black hollow symbols) as a function of graphite vol. % as well as the tting curve with the average value, a 4.97 in Eq. (3). In order to consider the interactions between the conductive materials in the composites with additional CNTs (samples 911) or with a different matrix material (Epon in sample 20), we employed a full-correlation model to calculate the thermal conductivity of the composite, k(fGraphite, fCNT) [9]. APRIL 2012, Vol. 134 / 041302-5

Fig. 7 Room temperature thermal conductivities of samples 7, 19, 10, and 20 to nd the inuence of polymer matrices (EPON vs Vinnapas) on the thermal conductivity of the composites. The inset shows a fractured surface of sample 20. The scale bar indicates 5 lm.

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Fig. 8 (a) Calculated thermal conductivities for the graphitelled composites. The solid line represents calculated thermal conductivities from Eq. (3) with a 5 4.97. The experimental thermal conductivities for sample 6 (hollow circle), sample 7 (hollow triangle), and sample 8 (hollow square) were used for nding a. ke(fgraphite) in Eq. (5) for sample 9 (green lled diamond), sample 10 (red lled circle), and sample 11 (blue lled triangle) were obtained from Eq. (3). (b) Calculated thermal conductivities for sample 9 (green dash line), 10 (red solid line), 11 (blue dashed-dotted line), and 20 (black dotted line) obtained by using Eq. (5). Experimental data for sample 9 (green lled diamond), sample 10 (red lled circle), sample 11 (blue lled triangle), and sample 20 (black hexagon) were plotted together and used for nding b.

synthesizing continuous solid samples without cracks was estimated to be 26 vol. %, and the maximum concentration of the llers was 44 vol. % with minimum 30 vol. % surfactant from the condition of sample 8. Note that the surfactant (SDBS) is necessary to disperse the graphite and CNT in water. Otherwise, they strongly aggregate and result in very low thermal conductivity. Therefore, the maximum CNT concentrations were calculated to be 16, 27, 37, and 27 vol. % (22, 36, 50, and 36 wt. %) for samples 911 and 20, respectively. From the calculation results, when the ratio of CNTs to graphites is slightly higher than unity, the highest thermal conductivity over 3 W/m-K may be achievable (see the plots for samples 10 and 20). The effectiveness of adding CNTs, which can also be identied by the coefcient b, for sample 10 is the highest (b 6.28). The additional CNTs might thermally bridge the graphite sheets, resulting in the conductivity increase. Sample 9 also show relatively large b of 5.76. Nevertheless, the CNT loading is limited, and thereby the maximum achievable conductivity is estimated to be less than 2 W/m-K. On the other hand, when the concentration of the graphite is low (sample 11, graphite:CNT 1:4), the effectiveness of adding CNTs is moderate (b 4.59), as depicted in the slope. The plots for samples 10 and 20 were selected to identify the role of the polymer matrix (Vinnapas and Epon). In order to nd the thermal conductivity of the Epon polymer, we used the experimental result of sample 19. For the given ke in Eq. (3), the matrix conductivity, km was calculated to be 0.346 W/m-K. This value is close to or higher than those of other experiments [8,37]. The polymer made of Epon, which is stiffer than that of Vinnapas, is likely to have higher thermal conductivity than the Vinnapas matrix. It is also possible that Epon may have better thermal contacts with graphites and CNTs than Vinnapas. It has been found that the thermal conductivity can be dramatically improved by adding them into Epon [8,38] rather than Vinnapas matrices [7,20,22,23]. With the Epon thermal conductivity, ke was calculated to be 0.782 for sample 20 from Eq. (3) with a 4.97. Note that we used the same a since the coefcient considers the interactions between the llers, which govern the thermal conductivity of the composites. Then, the model from Eq. (5) was plotted with a matching coefcient b of 4.50. The relatively high conductivity for sample 20 may be attributed to the matrix whose thermal performance in the composite is superior to Vinnapas.

Conclusions

 kfGraphite ; fCNT ke fGraphite

1 1 fCNT

b (5)

where ke(fGraphite) denotes the effective thermal conductivity without containing CNTs, which can be calculated by using Eq. (3), and the coefcient b accounts for the effectiveness of improving composite thermal conductivity by the llers. A larger b value indicates more effective additives on increasing the thermal conductivity of composites. Here, we rst found ke(fGraphite) by using Eq. (3) at 27.8, 17.4, and 7.00 vol. % (40, 25, and 10 graphite wt. % for the use in sample 9, 10, 11) when only graphite llers were considered, as shown in the lled symbols of Fig. 8(a). Then, the thermal conductivity behaviors of the composites (samples 911) were calculated as a function of the CNT concentration by using Eq. (5), as depicted in Fig. 8(b). Here, the maximum CNT concentration was calculated for the plot because there are limited spaces available for the ller, surfactant, and polymer matrix. The minimum concentration of the polymer matrix required for 041302-6 / Vol. 134, APRIL 2012

This study presents thermal transport behaviors of polymer nanocomposites as a function of various synthesis conditions and concentrations, different polymer matrix materials, and different surfactants. Carbon nanotube- or/and graphite-lled polymer composites were synthesized by using simple mixing and drying methods, and their thermal conductivities were measured by using a steady-state technique. Nanoparticle-decorated nanotubes were also incorporated into polymer matrices for investigating their inuence on thermal conductivity. Two different surfactants, SDS or SDBS was used for stabilizing nanotubes/graphites in water. DMF or NMP was also utilized for nanotube/graphite dispersion without using any surfactants. For the matrix materials, exible Vinnapas or stiff Epon was employed. The conductive ller concentrations were varied to nd the optimum synthesis condition for improving thermal conductivity. The experimental results show that the composite containing a mixture of nanotube and graphite llers with the Epon matrix has the highest thermal conductivity, $1.85 W/m-K at room temperature. The composite contain 25-wt. % nanotubes and 25-wt. % graphites with the SDBS surfactant. The nanotube-lled composites are more exible and less porous than graphite-lled samples whereas the graphite-lled composites are stiffer with higher thermal conductivities. The mixture of nanotubes and graphites provides better structural integrity from good adhesion between nanotubes and polymers as well as higher thermal conduction from graphites. In addition, nanotubes ll voids between Transactions of the ASME

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graphites, making the sample less porous. When solvents (DMF and NMP) were used as a surfactant, conductive ller concentrations can be raised to 80 wt. % (40 wt. %-nanotubes and 40 wt. %graphite; or 80 wt. % graphite), resulting in $1.7 W/m-K at room temperature. The thermal conductivity of the composite was also predicted by using a model based on the Maxwells effective medium theory. The most effective method of improving the composite thermal conductivity is to use both graphites and CNTs with a ratio of CNTs to graphites slightly higher than unity. The CNTs may thermally bridge the graphite sheets and improve thermal transport behaviors in the composites.

Acknowledgment
The authors (W.P., K.C., C.Y.) gratefully acknowledge nancial supports from the U.S. Air Force Ofce of Scientic Research (Grant No. FA9550-09-1-0609), the U.S. National Science Foundation (Award No. 1030958 and 0854467), and the Pioneer Research Center Program through the National Research Foundation of Korea (2011-0001645) funded by the Ministry of Education, Science and Technology (MEST). The FE-SEM acquisition in the microscopy imaging center at Texas A&M Univ. was supported in part by the National Science Foundation under Grant No. DBI-0116835. The authors thank H. Yangs assistance in acquiring XRD data.

Nomenclature
f volume fraction k thermal conductivity (W/m-K) m mass (g)

Greek Symbols
a a coefcient that account for the effectiveness of conductive llers on altering the thermal conductivity of a composite (with one kind ller) b a coefcient that account for the effectiveness of conductive llers on altering the thermal conductivity of a composite (with two different kinds of llers) q density (g/cm3) v tting parameter

Subscripts
e effective property m matrix p particle

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