Research Article

Received: 22 November 2010, Revised: 6 January 2011, Accepted: 14 January 2011, Published online in Wiley Online Library: 2011

(wileyonlinelibrary.com) DOI: 10.1002/pat.1940

Improved polyvinylpyrrolidone (PVP)/ graphite nanocomposites by solution compounding and spray drying
Leilei Wang a,b, Liqun Zhang a,b and Ming Tian a,b *
In order to evaluate the roles of graphite dispersion on the functional properties of the composites, PVP/graphite nanocomposites were prepared by blending the aqueous suspension of expanded graphite sheets and polyvinylpyrrolidone (PVP) aqueous solution by ultrasonic treatment, followed by spray drying and direct drying as a comparison individually. The effects of graphite loading and drying method on the dispersion of graphite and the resultant properties of the composites such as electrical and thermal conductivity, friction, and dynamic mechanical properties were studied. The results from transmission electron microscopy (TEM), scanning electron microscopy (SEM), and X-ray diffraction showed that the composites prepared by fast spray drying exhibited a higher degree of exfoliation and a better dispersion of graphite sheets in the PVP matrix than the corresponding composites prepared by direct drying, leading to a conclusion that fast spray drying can effectively prevent from re-stacking of the exfoliated graphite sheets as illustrated. As a result, dynamic mechanical thermal analysis showed signicant increases in the storage modulus and glass transition temperature for the composites prepared by spray drying. Besides, the spray drying as well greatly improved the electrical and thermal conductivity of the composites. It was also found that the electrical and thermal conductivity of the composites strongly depended on the graphite dispersion, while the friction coefcient unexpectedly does not. Increasing graphite loading level might enhance the probability of graphite sheets re-stacking, resulting in poor graphite dispersion. Copyright 2011 John Wiley & Sons, Ltd. Keywords: expanded graphite; polyvinylpyrrolidone; dispersion; spray drying; nanocomposites

INTRODUCTION
It is well known that polymer nanocomposites possess not only excellent mechanical properties but also new functional properties such as electrical, thermal, anti-bacterial, and luminous properties that the pure polymer matrix does not.[1] For the last decades, a plenty of researches on polymer/layered silicate (PLSN)[25] and polymer/carbon nanotube[68] nanocomposites have been reported. It is recognized that superior mechanical properties would be achieved only when the nanoparticles are well dispersed as nano-sized in polymer matrix. Unfortunately, it is still a challenge to explore a simple and efcient method that can make the nanoparticles uniformly disperse in polymer matrix, so polymer nanocomposites are rarely put into use until today.[9] Graphite exhibits a layered structure similar to layered silicates with a very high aspect ratio in its exfoliation state. It is one of the strongest materials per unit weight and has unique functional properties, such as high electrical conductivity (104 S/cm), excellent thermal conductivity, and lubrication performance.[10] The exfoliated graphite nanoplatelets combine low price with the superior thermal and electrical properties of carbon nanotubes.[11,12] More and more attentions have been paid to polymer/graphite nanocomposites.[1317] The dispersion of graphite in polymer matrix, which strongly depends on the preparation method of the composites, plays an important role on the resultant performances. The preparation methods of polymer/graphite nanocomposites generally include in situ polymerization and mechanical blending. In situ polymerization was reported for the rst time in 1958 by Podall

et al.[18] Shioyama and co-workers found that graphite sheets could be fully exfoliated in polymer by using in situ polymerization.[1921] Because of complicated processes, it is difcult for this method to be controlled and not easy to be popularized on a large scale. The mechanical blending method involves polymers compounding with graphite by solution, emulsion or melt. Melt compounding is a common and simple method. Uhl and Wilkie[22] blended graphite intercalation compounds and nylon 6 at 2508C. They found that the graphite could be partially exfoliated and the thermal stability of the composites was enhanced, but with a decrease in mechanical properties. Solution intercalation is a method using a solvent to dissolve the polymer and disperse the graphite, and then the solvent is evaporated once the mixing is completed. For example, polymethyl methacrylate/graphite nanocomposite prepared by solution blending exhibited excellent electrical property.[10] However, the removal of organic solvents is complicated

* Correspondence to: M. Tian, Beijing University of Chemical Technology, No. 15 Beisanhuan East Road, P.O. Box 57, Chaoyang District, Beijing 100029, China. E-mail: tian71402@126.com a L. Wang, L. Zhang, M. Tian The Key Laboratory of Carbon Fiber and Functional Polymers, Ministry of Education, Beijing University of Chemical Technology, Beijing 100029, China b L. Wang, L. Zhang, M. Tian The Key Laboratory of Beijing City on Preparation and Processing of Novel Polymer Materials, Beijing University of Chemical Technology, Beijing 100029, China

Polym. Adv. Technol. (2011)

Copyright 2011 John Wiley & Sons, Ltd.

L. WANG, L. ZHANG AND M. TIAN and expensive. Latex compounding (LCM) is an innovative method for making rubber/graphite nanocomposites by using the nano-dispersed graphite sheets in water to form a suspension, and then mixing with rubber latex particles (typically tens of nanometers in diameters).[23,24] Polymer latex particles release macromolecular chains upon the effect of the coagulant (such as calcium chloride); thereby the nanocomposites with the separated/exfoliated nano-dispersed graphite sheets will be obtained after the removal of water. In our previous study,[23] acrylonitrile-butadiene rubber (NBR)/EG nanocomposites with excellent gas barrier property, electrical property, thermal property and wear resistance were prepared by LCM. This promising method is expected to apply to polymers that can be synthesized by emulsion polymerization or turned into articial latexes. It is simple and easy to be popularized. The issue is how does make polymer macromolecules fully encapsulate nano-dispersed sheets to prevent from re-stacking once polymer macromolecules are immediately released from latex particles and quickly co-coagulate with graphite sheets upon the effect of the coagulant. We found that there were still some agglomerates in NBR/graphite nanocomposites prepared by LCM even at a very low graphite loading. The agglomerates would certainly affect the properties of the composites. The present study aims to explore a novel method for getting better dispersion of graphite, then to evaluate the resultant inuences on the functional properties of the composites as well. Polyvinylpyrrolidone (PVP), a kind of water-soluble polymer, was used as polymer matrix, since it can easily form aqueous dispersion of polymer-coated graphite[25] without worrying about the problem of the removal of organic solvents in solution compounding, and stabilize graphite sheets suspension without need of the surfactant because of its amphiphilic groups (hydrophobic methylene group and hydrophilic amide group). The effects of two different drying methods used to remove water including spray drying and traditional direct drying here on graphite dispersion was compared. Meanwhile, the inuences of the dispersion and the loading level of graphite on electrical and thermal conductivity, friction, and dynamic mechanical properties of the composites were also revealed. Composite preparation by solution compounding EG (EG was added based on 5, 10, 20, and 30 g for every 100 g PVP individually) was mixed with PVP aqueous solutions (1 wt%), and the mixture was stirred for 24 hr. When the graphite sank to the bottom of the beaker upon the role of PVP as a surfactant, the mixture was then subjected to ultrasonic treatment[26] with a power of 1000 W for more than 2.5 hr, and a stable aqueous suspension of graphite nanosheets was formed. Two different drying methods were used in this study: One (namely the traditional method) was to dry the mixture directly at 808C in a drying oven for 24 hr to get PVP/graphite composite; the other was to dry the mixture rapidly by spray drying to get PVP/ graphite composite powder. A B-290 Spray Dryer (Buchi Company, Switzerland) was used here; the air inlet temperature was about 1908C with a pass needle frequency of 4 and feed rate of 20%. Finally, the dried composites were plasticized in a hot press (XQLB-350 350, Shanghai Rubber Machinery Factory, China) at 1808C for 15 min and then molded on another cooled press for 10 min (Shanghai Rubber Machinery Factory, China) for further test.

Characterization and tests X-ray diffraction patterns of the graphite lamellar structure were obtained using a Rigaku D/Max-IIIC X-ray diffractometer (Japan) under a voltage of 40 kV and a current of 50 mA with CuKa radiation. Transmission electron microscopy (TEM) micrographs of ultrathin sections of the nanocomposites were taken with an H-800 transmission electron microscope (Hitachi Co., Japan) at an acceleration voltage of 200 kV. In addition, a JEM 3010 high solution transmission electron microscope (Jeol Co., Japan) was used to determine the thickness of graphite layers in solution and composites. Scanning electron microscopy (SEM) micrographs of the freeze-fractured surfaces of the PVP/graphite composites were taken by using a JSM-6701F scanning electron microscope (JEOL Ltd., Tokyo, Japan). The dynamic mechanical properties: The storage modulus (E0 ) and dynamic loss factor (tan d) were measured as a function of temperature with a DMTA V dynamic mechanical thermal analyzer (Rheometrics Science Corp., USA) under the tension mode at a frequency of 1 Hz. The strain amplitude in the temperature range of 502008C was 0.1%. The heating rate was 38C min1. A precision impedance analyzer (4294A, Agilent Technologies, Ltd., Japan) was used to measure the volume resistivity under a voltage of 220 V and frequency of 404 107 Hz. The thickness of the samples was 2 mm and the surface area was 1 cm2. The thermal conductivity of the composites was measured using a heat ow meter instrument (HC-074, EKO Instrument Trading Co. Ltd., Japan). The thickness of the samples was 2 mm and the diameter of the circular specimens was 20 mm. The friction coefcient of the composites was measured by a BM-III pendulum friction tester (Jiangsu Shuyang Highway Instrument Co., Ltd., China). The surface roughness of the counterpart was 3 mm. The friction tester is basically a pendulum tester used to measure energy loss, together with integral formula of contact forces gives the friction coefcient. The sample size was 76 mm 25.4 mm 2 mm. Each sample was tested ve times to get an average value.

EXPERIMENTAL
Materials Polyvinylpyrrolidone K90 (PVP, Mw  1,300,000) was produced by International Special Products (USA). Expandable graphite (the expansion ratio along the c-axis was ca. 250) was purchased from Pingdu Huadong Graphite Processing Factory (Shandong Province, China).

Preparation of the composites Preparation of expanded graphite The expandable graphite was dried in a vacuum drying oven at 1008C for 24 hr with P2O5. Then expanded graphite (EG) was prepared by microwave irradiation on expandable graphite for about 30 s in a microwave oven (Sanyo EM-183MS1, 750 W).

View this article online at wileyonlinelibrary.com

Copyright 2011 John Wiley & Sons, Ltd.

Polym. Adv. Technol. (2011)

IMPROVED POLYVINYLPYRROLIDONE/GRAPHITE COMPOSITES

RESULTS AND DISCUSSION

Morphology of the composites The structure of the PVP/graphite composites was studied using X-ray diffraction analysis (XRD), TEM, and SEM. XRD can provide quantitative data of the graphite lamellar spacing. According to the position, the shape and intensity of XRD diffraction peak, the change of graphite lamellar spacing during the preparation process was further analyzed. The diffraction peak at 2u 26.68 corresponding to a basal spacing d of 0.335 nm (diffraction plane 002) is characteristic of lamellar graphite.[27] The XRD pattern of expandable graphite is presented in Fig. 1a. The two diffraction peaks (0.346 and 0.337 nm) in Fig. 1a indicate the intercalation structure of expandable graphite as a result of the intercalation of some oxidant in the preparation process. As shown in Fig. 1b and c, the basal spacing of graphite is 0.335 nm, and the diffraction peak does not shift to smaller angles. The results indicated that PVP macromolecules did not intercalate into graphite interlayers. This foresaid structure was named as separated structure,[5] where PVP macromolecules separated the graphite sheets as either exfoliated or agglomerated form rather than intercalated ones. Compared to traditional drying method, graphite was exfoliated more fully by using spray drying when the graphite content was lower than 5 g/100 g PVP, as indicated by the minor diffraction peak at 2u 26.68 in Fig. 1c. The stronger the intensity of the diffraction peak, the higher the degree of graphite stacking and the worse the exfoliation and the dispersion of graphite is suggested. It can be concluded through Fig. 2 that the graphite was exfoliated and dispersed much better by spray drying than it was by direct drying at the same loading of graphite. For spray drying, there were only a few re-stackings (separated structures) even at a higher graphite loading level (30 g/100 g PVP). With the increase of graphite content, graphite sheets increase, leading to a high probability of re-stacking and poor dispersion as well. By direct drying, the re-stacking of graphite sheets increased drastically with increasing graphite content. It is deduced that PVP macromolecules could well encapsulate dispersed sheets to get a good dispersion of graphite during solution compounding rather than

Figure 2. X-ray diffraction patterns of PVP/graphite composites prepared by two different drying methods.

intercalated structure, and the nal dispersion of graphite sheets is mainly controlled by the way of drying. Generally, TEM has to be utilized in combination with XRD to testify the structure of the nanocomposites. Figure 3 shows a representative TEM image of graphite sheets in PVP solution with smooth planar structure and having about six single sheets. The small akes are found randomly embedded in the large ones, which in turn favors the formation of agglomerates. The average thickness of these akes was about 3 nm. The results illustrated that graphite sheets could be broken into smaller pieces upon sonication but could not be exfoliated completely into single graphite sheet. The TEM micrographs of PVP/graphite composites prepared by two different drying methods are displayed in Figs. 4 and 5. The width of the dark line represents the thickness of graphite sheets. It is evident that graphite sheets prepared by spray drying are much thinner than those prepared by direct drying, indicating by the data listed in Table 1. Graphite sheets in the composites prepared by direct drying are composed of about 3050 single sheets, whereas only 1020 sheets for the composites prepared by spray drying. The number of graphite sheets stacking increases with graphite loading

Figure 1. X-ray diffraction patterns: (a) expandable graphite; (b) PVP/ graphite (5 g/100 g PVP) composite prepared by direct drying; (c) PVP/ graphite (5 g/100 g PVP) composite prepared by spray drying.

Figure 3. HR-TEM image of graphite sheets in PVP solution after ultrasonic treatment (the content of graphite was 5 g/100 g PVP).

Polym. Adv. Technol. (2011)

Copyright 2011 John Wiley & Sons, Ltd.

View this article online at wileyonlinelibrary.com

L. WANG, L. ZHANG AND M. TIAN

Figure 4. TEM micrographs: (a) and (b) represent PVP/graphite (5 g/100 g PVP) composites prepared by direct drying and spray drying, respectively; (c) and (d) represent PVP/graphite (10 g/100 g PVP) composites prepared by direct drying and spray drying, respectively.

amount. The results are consistent with XRD. When graphite sheets stack less, the diffraction peak intensity of graphite is weaker.[28] According to the above results, PVP/graphite nanocomposites prepared by solution compounding are of partly exfoliated structure rather than ideal single graphite sheet, in which PVP macromolecules separated the graphite sheets as either exfoliated or agglomerated form with nanosized thickness. It is true that the graphite can be exfoliated and dispersed much better by spray drying than it is by direct drying. Figures 6 and 7 reveal the morphology of the fractured surfaces of the PVP/graphite composites prepared by two different drying methods. It can be seen that graphite could be well exfoliated in the composites with a thickness less than 100 nm by using solution compounding. In the case of the composites prepared by direct drying, the interface between graphite sheets and PVP matrix can be seen clearly with the graphite loading of 5 g/100 g PVP (Fig. 6a). With further addition of graphite, the thickness of the graphite sheets stacking increased markedly, resulting in poor dispersion (Fig. 6b and c). Obviously, graphite sheets were more fully exfoliated and dispersed more uniformly in PVP matrix, even at very high content of graphite up to 20 g/100 g PVP, as shown in Fig. 7. The results of SEM observations reconrm that the way of drying plays a great role in the nal dispersion of graphite. Figure 8 illustrates the principle of solution blending for PVP/graphite composites by two different drying methods. The graphite lamellar spacing is expanded at high temperatures, and the graphite sheets are further exfoliated into nanosheets in water by ultrasonic stirring. Then PVP/nano-dispersed graphite

sheets compounds are obtained by blending soluble PVP macromolecules and aqueous suspension of graphite nanosheets. During the process of water removal, it is very easy for graphite sheets to re-stack because of high specic surface area, so the nal dispersion to a great extent depends on the competition between the re-stacking rate of graphite sheets and the removal rate of water. In the case of spray drying, the drying time is very short (about 1.01.5 s), which could ensure the state of PVP with good graphite dispersion to be stabilized as soon as possible once water as solvent is removed. At the same time, PVP macromolecular chains rapidly re-form glassy state and become immobility, preventing from adhering each other. As a result, the re-stacking occurs only in limited volume, the re-stacking rate accordingly slows down. Powdered PVP/graphite composites are nally obtained with uniform graphite distribution. In the process of direct drying, it takes very long time to remove water, so the re-stacking probability and the formation rate of graphite agglomerates are high. Both are conducive to the re-stacking of graphite sheets, resulting in the poor dispersion of graphite.

Properties of composites Dynamic mechanical properties Figure 9 shows the temperature dependence of the storage modulus of PVP/graphite nanocomposites prepared by different drying methods. It can be seen that the storage modulus of PVP/ graphite nanocomposites at a given temperature increases with increasing graphite content as a result of the reinforcement effect of graphite. The storage modulus is higher for PVP/graphite

View this article online at wileyonlinelibrary.com

Copyright 2011 John Wiley & Sons, Ltd.

Polym. Adv. Technol. (2011)

IMPROVED POLYVINYLPYRROLIDONE/GRAPHITE COMPOSITES

Figure 5. HR-TEM micrographs: (a) and (b) represent PVP/graphite (5 g/100 g PVP) composites prepared by direct drying and spray drying, respectively; (c) and (d) represent PVP/graphite (20 g/100 g PVP) composites prepared by direct drying and spray drying, respectively.

nanocomposites prepared by spray drying than the corresponding composites prepared by direct drying. At 608C, compared with the storage modulus of pure PVP, we observed about 22% improvement for PVP/graphite nanocomposites (at 5 g/100 g loading) prepared by direct drying and over 82% improvement for those prepared by spray drying. The higher modulus means the stronger reinforcement for PVP. The glass transition temperatures ( Tg, taken as the peak temperature of the tan d curve) of PVP/graphite nanocomposites are shown in Table 2. It can be seen that the Tg of PVP increases

signicantly with the addition of graphite. PVP/graphite nanocomposites prepared by spray drying present a higher Tg than the other prepared by direct drying. The higher Tg is an indication that, spray drying results in a more uniform graphite dispersion in the PVP matrix, making the PVP chains stiffer. Electrical properties Figure 10 shows the electrical conductivity of PVP/graphite composites prepared by two different drying methods. There is a correlation between the electrical conductivity and the aspect ratio, the dispersion, and the loading level of the conductive llers, all factors inuencing the particleparticle and particlematrix interactions.[26] It can be seen that the electrical conductivity of the composites prepared by two different drying methods shows the same change with the variation of graphite loading. But the electrical conductivity of nanocomposites prepared by spray drying is higher than the other. The occurrence of electrical conductivity can be attributed to the formation of conductive pathways when the ller content exceeds a critical volume fraction, as called percolation threshold.[29] When the content of graphite is 5 g/100 g PVP, the volume fraction of graphite nanosheets is rather little whatever their dispersions are. The particleparticle distance is too large to contact with each other to form conductive pathways, so the conductivity is

Table 1. Number of expanded graphite layers from HR-TEM images Drying method Direct drying Graphite content (g/100 g PVP) Number of expanded graphite layers 5 30 20 2550 5 10 Spray drying 20 1520

Polym. Adv. Technol. (2011)

Copyright 2011 John Wiley & Sons, Ltd.

View this article online at wileyonlinelibrary.com

L. WANG, L. ZHANG AND M. TIAN

Figure 6. SEM micrographs of PVP/graphite composites prepared by direct drying ((a), (b), and (c) represent composites lled with 5, 10, and 20 g of graphite, respectively, per 100 g of PVP).

Figure 7. SEM micrographs of PVP graphite composites prepared by spray drying ((a), (b), and (c) represent composites lled with 5, 10, and 20 g of graphite, respectively, per 100 g of PVP).

very low. The conductivity of the composites increases rapidly until the loading of graphite up to 10 g/100 g PVP, then decreases at the graphite loading amount of 20 g/100 g PVP (This experiment was repeated several times.), and the electrical conductivity goes up again with increasing graphite content. It can be explained that the conductivity of the composites depends on not only the loading level but also the dispersion of graphite. As discussed above, when the graphite contents are below 10 g/100 g PVP, graphite could be exfoliated into lots of nanosheets uniformly dispersed in PVP matrix, thus increasing graphite content is benecial to the formation of conductive pathway owing to the high aspect ratio of graphite, as illustrated

in Fig. 10a. On the other hand, if graphite contents exceed 20 g/ 100 g PVP, a large amount of graphite agglomerates as well as poor dispersion decrease the number of graphite nanosheets, which is unfavorable to the formation of conductive pathway. When the graphite content reaches 30 g/100 g PVP, graphite sheets are so many that they can touch each other to form conductive pathways, although the dispersion of graphite might be worse, as illustrated in Fig. 10b. At the same graphite loading, the electrical conductivity of the composites prepared by spray drying is signicantly higher than that of the corresponding composites prepared by direct drying because of the better exfoliation and the dispersion of graphite sheets. We conclude

Figure 8. Schematic diagram depicting solution blending for PVP/graphite composites by two different drying methods.

View this article online at wileyonlinelibrary.com

Copyright 2011 John Wiley & Sons, Ltd.

Polym. Adv. Technol. (2011)

IMPROVED POLYVINYLPYRROLIDONE/GRAPHITE COMPOSITES

Figure 9. Temperature dependence of storage modulus of PVP/graphite composites prepared by two different drying methods: (a) direct drying method; (b) spray drying method.

Table 2. Effect of drying methods on glass transition temperature of PVP nanocomposites Graphite content (g/100 g PVP) Drying method Tg (8C) Direct drying Spray drying 0 186 186 5 187 192 10 191 195 20 195 196 30 197 199

that the electrical conductivity depends on the competition between the graphite loading and the dispersion. This indicates that a required electrical conductivity could be by either improving the dispersion of graphite at a low loading amount, or increasing graphite loading that might cause poor dispersion. Thermal properties Figure 11 reveals the thermal properties of PVP/graphite composites prepared by two different drying methods. The
Figure 11. Thermal conductivity versus graphite content of PVP/ graphite composites prepared by two different drying methods.

effect of ller on the thermal conductivity (l) of a composite is a complex function of the llers geometry, the distribution of the ller in the matrix, and the contact between the ller particles.[30] The thermal conductivity of the composites prepared by spray drying increased with the increasing amount of graphite. To understand the mechanism involved, we tted a theoretical model to the experimental data of thermal conductivity versus the amount of graphite. We chose the geometric mean model based on the formation of an internal network of conductive ller within a composite (two phase medium, Eqn (1)).[31] kc kf f km 1f (1)

Figure 10. Electrical conductivity versus graphite content of PVP/graphite composites prepared by two different drying methods and the schematic diagram of graphite dispersion state (a) graphite contents are below 10 g/100 g PVP and (b) graphite contents exceed 10 g/100 g PVP.

where kc is the effective thermal conductivity of the composite, km is the thermal conductivity of the matrix, kf is the thermal conductivity of the ller, and f is the volume fraction of the dispersed phase (ller). From Figure 11, we can see that the thermal conductivity of the composites prepared by spray drying is basically consistent with the results calculated by Eqn (1) (theoretical curve). The agreement indicates that the dispersion state of ller in the composites prepared by spray drying is close to the state of

Polym. Adv. Technol. (2011)

Copyright 2011 John Wiley & Sons, Ltd.

View this article online at wileyonlinelibrary.com

L. WANG, L. ZHANG AND M. TIAN suspension with PVP aqueous solution, followed by spray drying or direct drying. The nal dispersion of graphite is mainly determined by the drying method. Fast spray drying gives ner and more uniformly dispersed graphite sheets than direct drying. The composites obtained by spray drying exhibit much better electrical and thermal conductivity as well as higher storage modulus and glass transition temperature than the corresponding composites prepared by direct drying. As the graphite loading level increases, the probability of graphite re-stacking increases, resulting in poor graphite dispersion. The electrical and thermal conductivity of PVP/graphite composites depend on not only the loading level but also the dispersion of graphite, while the friction coefcient does not seem to depend on the dispersion of graphite.

REFERENCES
Figure 12. Friction coefcient versus graphite content of PVP/graphite composites prepared by two different drying methods. [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28] [29] [30] L. Bokobza, C. Belin, J. Appl. Polym. Sci. 2007, 105, 2056. P. B. Messersmith, E. P. Giannelis, Chem. Mater. 1993, 5, 1064. E. P. Giannelis, Adv. Mater. 1996, 8, 29. S. S. Ray, M. Okamoto, Prog. Polym. Sci. 2003, 28, 1539. Y. P. Wu, Y. Q. Wang, H. F. Zhang, Y. Z. Wang, D. S. Yu, L. Q. Zhang, J. Yang, Compos. Sci. Technol. 2005, 65, 1195. M. A. Pulickel, Z. Z. Otto, Topics Appl. Phys. 2001, 80, 391. L. M. Dai, A. W. H. Mau, Adv. Mater. 2001, 13, 89. J. N. Coleman, U. Khan, Y. K. Gunko, Adv. Mater. 2006, 18, 689. M. E. Mackay, A. Tuteja, P. M. Duxbury, C. J. Hawker, B. V. Horn, Z. B. Guan, G. H. Chen, R. S. Krishnan, Science 2006, 311, 1740. D. D. L. Chung, J. Mater. Sci. 2002, 37, 1475. H. Fukushima, PhD thesis, Michigan State University, Department of Chemical Engineering and Materials Science, 2003. K. Kalaitzidou, PhD thesis, Michigan State University, Department of Chemical Engineering and Materials Science, 2006. T. Ramanathan, S. Stankovich, D. A. Dikin, H. Liu, H. Shen, S. T. Nguyen, L. C. Brinson, J. Polym. Sci. Pol. Phys. 2007, 45, 2010. C. M. F. Calixto, R. K. Mendes, A. Carlos de Oliveira, L. A. Ramos, P. Cervini, E. T. G. Cavalheiro, Mater. Res. 2007, 10, 112. V. Panwar, B. Kang, J. O. Park, S. Park, R. M. Mehra, Eur. Polym. J. 2009, 45, 1779. H. Chen, H. B. Liu, L. Yang, J. X. Li, L. Yang, Int. J. Hydrogen Energ. 2010, 35, 3108. S. R. Dhakate, S. Sharma, N. Chauhan, R. K. Seth, R. B. Mathur, Int. J. Hydrogen Energ. 2010, 35, 4199. H. Podall, W. E. Foster, A. P. Giraitis, J. Org. Chem. 1958, 23, 82. H. Shioyama, Synth. Met. 2000, 114, 1. H. Shioyama, Carbon 1997, 35, 1664. H. Shioyama, K. Tatsumi, N. Iwashita, K. Fujita, Y. Sawada, Synth. Met. 1998, 96, 229. F. M. Uhl, C. A. Wilkie, Polym. Preprints 2001, 42, 176. J. Yang, M. Tian, Q. X. Jia, J. H. Shi, L. Q. Zhang, S. H. Lim, Z. Z. Yu, Y. W. Mai, Acta Mater. 2007, 55, 6372. M. Tian, L. J. Cheng, W. L. Liang, L. Q. Zhang, Macromol. Mater. Eng. 2005, 290, 681. A. B. Bourlinos, V. Georgakilas, R. Zboril, T. A. Steriotis, A. K. Stubos, C. Trapalis, Solid State Commun. 2009, 149, 2172. G. H. Chen, W. G. Weng, D. J. Wu, C. L. Wu, J. R. Lu, P. P. Wang, X. F. Chen, Carbon 2004, 42, 753. Y. Asma, M. D. Isaac, Polymer 2004, 44, 8215. C. N. R. Rao, K. Biswas, K. S. Subrahmanyama, A. Govindaraj, J. Mater. Chem. 2009, 19, 2461. F. H. Gojny, M. H. G. Wichmann, B. Fiedler, I. A. Kinloch, W. Bauhofer, A. H. Windle, K. Schulte, Polymer 2006, 47, 2036. S. A. Mansour, M. E. Al-Ghoury, E. Shalaan, M. H. I. El Eraki, E. M. Abdel-Bary, J. App. Polym. Sci. 2010, 116, 3171. R. C. Progelhof, J. L. Throne, R. R. Rrersch, Polym. Eng. Sci. 1976, 76, 619. J. Yang, M. Tian, Q. X. Jia, L. Q. Zhang, X. L. Li, J. Appl. Polym. Sci. 2006, 102, 4007.

the ller particles assumed in the geometric mean model. Note that when the content of graphite is 10 g/100 g PVP, the experimental value (spray drying) is higher than the calculated value. Since the aspect ratio of graphite is high, it is easier for graphite sheets to touch each other to form conductive networks than the spherical particles assumed in the geometric mean model. With the increase of graphite loading, the calculated value is higher than the experimental value because of the agglomerates of graphite not taken into account in the model. At the same graphite loading, the thermal conductivity of the composites prepared by spray drying is higher than that of the corresponding composite prepared by direct drying, indicating that the thermal conductivity of the composites depends on the dispersion of the thermally conductive ller besides the loading amount. When the content of graphite goes up to 30 g/100 g PVP, the thermal conductivity of the composite prepared by spray drying reaches 0.846 W/mK, which is nearly seven times that of pure PVP (0.131 W/mK). Friction properties The friction coefcient (m) of PVP/graphite composites prepared by two different drying methods is shown in Fig. 12. The friction coefcient of the composites lled with graphite is signicantly lower than that of neat PVP. When the content of graphite is 5 g/ 100 g PVP, the friction coefcient falls to 0.32 from 0.66 for the neat PVP. With increasing graphite content, the friction coefcient decreases slowly. It is also seen that the drying method does not affect the friction coefcient, indicating that the friction coefcient mainly depends on the graphite loading rather than the dispersion of graphite for instant friction mode used in this study. However, good dispersion of graphite would improve the mechanical strength, and the wear resistance of the composites is thereby improved.[32]

CONCLUSION
In this work, polyvinylpyrrolidone (PVP)/graphite composites were prepared by blending expanded graphite sheet aqueous

[31] [32]

View this article online at wileyonlinelibrary.com

Copyright 2011 John Wiley & Sons, Ltd.

Polym. Adv. Technol. (2011)