Carbon 42 (2004) 753759 www.elsevier.

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Preparation and characterization of graphite nanosheets from ultrasonic powdering technique

Guohua Chen *, Wengui Weng, Dajun Wu, Cuiling Wu, Jinrong Lu, Pingping Wang, Xiangfeng Chen
College of Materials Science and Engineering, Huaqiao University, Quanzhou 362011, China Received 11 August 2003; accepted 20 December 2003

Abstract Natural ake graphite was exfoliated into exfoliated graphite via an acid intercalation procedure. The resulting exfoliated graphite was a worm-like particle composed of graphite sheets with thickness in the nanometer scale. Subjecting it to ultrasonic irradiation, the exfoliated graphite was eectively further foliated into isolated graphite nanosheets. SEM, TEM, SAD, laser counting, and BET measurements revealed that the graphite nanosheets prepared with 10 h irradiation were about 52 nm in thickness and 13 lm in diameter. FTIR examination showed that there were oxygen-containing groups presented on the surface of the exfoliated graphite. This result substantiated the statement reported in the literature that acid treatment could result in oxidization of carbon bonds on graphite surface. 2004 Elsevier Ltd. All rights reserved.
Keywords: A. Exfoliated graphite; C. BET surface area; D. Microstructure, Particle size

1. Introduction Nanocomposites of polymers with inorganic materials have been shown to exhibit a signicant increase in the properties of polymers and even generate certain new properties that cannot be derived from their counterparts, as the mixing of phases in them occurs over a much smaller length scale in comparison to the micrometer length scale of conventional composites [14]. Since the pioneer work of Toyota researchers [5,6], and especially the report of Giannelis et al. [7], the eld of polymer/silicate has gained large momentum recently [810]. If layered silicates are well dispersed within the polymers, either intercalated or delaminated nanocomposites are formed, leading to great enhancement of mechanical, thermal and barrier performance in comparison to conventional composites [11]. Unfortunately, silicate reinforced nanocomposites do not exhibit electrical properties as good as those of some conducting composites such as graphite-containing composites. Similar to layered silicates, natural ake graphite is another layered material. The graphite crystal lattice
Corresponding author. Tel.: +86-595-269-2956; fax: +86-595-2686969. E-mail address: hdcgh@hqu.edu.cn (G. Chen). 0008-6223/$ - see front matter 2004 Elsevier Ltd. All rights reserved. doi:10.1016/j.carbon.2003.12.074
*

consists of graphene layers formed by sp2 hybridized carbon atoms, while the carbon sheets are bounded by weak van der Waals forces with each other. Graphite is a good electrical conductor with an electrical conductivity in the range of 104 S/m at room temperature [12]. Therefore, graphite can be a good candidate in fabricating polymer conducting nanocomposites. However, unlike several lamellar silicate solids [13] whose exfoliation can be achieved by ion exchange reactions, exfoliation of graphite cannot be achieved in the same way because it does not bear any net charge. We achieved the nanodispersion composites via an in situ polymerization of monomer in the presence of graphite nanosheets which were made by powdering the exfoliated graphite with ultrasonic irradiation [14,15]. In this paper, characterization of the graphite nanosheets will be presented; the eect of the ultrasonic irradiation on the exfoliation of graphite will be investigated.

2. Experimental 2.1. Materials Natural ake graphite with an average diameter of 500 lm was used for preparing the exfoliated graphite.

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Concentrated sulfuric acid and fuming nitric acid (chemically pure) were used as chemical intercalate and oxidizer to prepare graphite intercalation compounds GICs. 95% (v/v) alcohol (chemical pure) and distilled water were used as solvents for preparation of foliated graphite nanosheets. 2.2. Preparation of exfoliated graphite and foliated graphite Exfoliated graphite (EG) was prepared according to the methods reported in the literatures [16,17]. Briey, the natural ake graphite was rst dried in a vacuum oven for 24 h at 80 C. Then, a mixture of concentrated sulfuric acid and fuming acid (4:1, v/v) was slowly added, under appropriate cooling and stirring, to a three-neck ask containing graphite akes. After 16 h of reaction, the acid-treated natural graphite was ltered and washed thoroughly with deionized water until the pH level of the solution reached 6. After being dried at 100 C overnight, the resulting graphite intercalation compound (GIC) was subjected to a thermal shock at 1050 C for 15 s in a mue furnace to form exfoliated graphite. 1 g EG was mixed and saturated with 400 ml alcohol solution consisting of alcohol and distilled water with a ratio of 65:35 for 12 h. Then the mixture was subjected to ultrasonic irradiation with a power of 100 W for various times. After hours of sonication, EG particles were eectively fragmented into foliated graphite (FG). The FG dispersion was then ltered and dried at 80 C to remove residue solvents. The as-prepared foliated graphite powder, we called graphite nanosheets, was then kept in a dry desiccator for testing and further use. 2.3. Characterization and measurements The distributions of the sizes of foliated graphite particles were determined by a JL-1166 Laser Particle Sizer (Chengdu, China) from the measurements of foliated graphite particles dispersed in water. Scanning electron microscopy (SEM) was performed on a LEO-1530 eld-emitting scanning electron microscope (Germany), at an operating pressure of 105 mbar and an accelerating voltage of 10.0 kV. The adsorption properties were used to analyze the characteristics, i.e. BET specic surface area, micropore volume and pore size distributions of EG and FG. The low temperature (77 K) nitrogen adsorption was recorded by using a Tristar 3000 (Micromeritics, Norcross, GA, USA) adsorption analyzer. Prior to the measurements, the graphite samples were pretreated by outgassing in a vacuum oven at 200 C for 12 h. The apparatus determined the dierence in the volumes of nitrogen delivered to a sample vial and a balance vial. The vials were immersed to the same level in liquid

nitrogen, and identical pressures were applied during the measurements. The measurements of a dierential volume thus compensated for changing temperature gradients in the samples vial. For each determination, three measurements were made in the relative pressure range 0 < P =P0 < 1:0. X-ray diraction (XRD) patterns were obtained using CuKa radiation (k 0:15 nm) at a scanning rate of 2.0 / min. using a voltage of 45 kV and a current of 40 mA. Fourier transform infrared spectroscopy (FTIR) study of the chemical functional groups on the exfoliated graphite was conducted on a Nicolet Magna750 spectrometer.

3. Results and discussions 3.1. Powdering of exfoliated graphite Ultrasonic irradiation has long been a very useful tool in the elds of chemistry and material engineering [18]. It is well known that when ultrasonic wave passes through a liquid acoustic cavitation takes place, and produces localized hot spots with temperature as high as 5000 C and local pressure as high as 500 atm, with heating and cooling rates greater than 109 K/s. Acoustic cavitation near a solid surface can create localized erosion, induce high-velocity interparticle collisions, cause fragmentation of brittle materials, and improve mass transport [19]. Thus, the soft and sticky exfoliated graphite, which is very dicult to be powdered by other mechanical methods, can be eectively powdered by ultrasonic irradiation in aqueous medium. 3.2. Characterization of graphite nanosheets 3.2.1. Electron microscopy Fig. 1 shows the SEM image of foliated graphite sheets prepared upon 10 h ultrasonic irradiation. Clearly, exfoliated graphite worms have been completely torn into foliated sheets of 520 lm in diameter and 30 80 nm in thickness, named graphite nanosheets [14,15]. Image analysis calculation results based on 5080 graphite nanosheets showed that the average sheet diameter is approximately 12 lm. The average thickness of the nanosheets was estimated to be about 50 nm, based on the values of 50 graphite sheets. The powder has an apparent density of about 0.015 g/cm3 , much lower than the mass density of the original natural ake graphite, which is 2.2 g/cm3 . A TEM micrograph showing images of graphite nanosheets imbedded in PMMA resin was presented in [14]. It is clear that foliated graphite sheets of about 10 nm thick, and even thinner sheets with thickness in the range of 25 nm, could be observed. Thus, we speculated that large amount of the as-prepared nanosheets

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12

755

a (10h)
Differential Distribution (%)
10

100

Integral Distribution (%)

80 8 6 4 2 0 0 10 20 30 40 50 60

40 20

Particle Size (m)

Fig. 1. SEM micrographs of foliated graphite.

12

b (16h)
Differential Distribution (%)

were composed of thinner secondary sheets. SAD patterns [14,15] also showed that foliated graphite sheets were polycrystalline in nature.

100

10

Integral Distribution (%)

80 8 6 4 2 0 0 10 20 30 40 50 60

3.2.2. Laser counting Exfoliated graphite was subjected to ultrasonic irradiation for various times in order to investigate the eect of irradiation time on the particle size, the structure and properties of the foliated graphite. Table 1 summarizes the parameters of particles of foliated graphite prepared using various irradiation times. The curves of integral volume distributions and histograms of dierential volume distributions of three typical kinds of foliated graphite are presented in Fig. 2. From Table 1, it is seen that when exfoliated graphite was subjected to ultrasonic irradiation with time less than 10 h, the particle size of the resulting foliated graphite was much larger than that with longer times. The critical ultrasonic irradiation time for the drastic decrease of particle size was thus about 10 h. After 10 h ultrasonic irradiation, both the particle sizes and size distributions change slightly with increasing irradiation times. From Fig. 2, it is seen that all the three samples have similar size distributions, which are obviously not symmetrical but particularly extended to the larger values, up to diameters of about 45 lm. This fact in one aspect leads to the conclusion that after the exfoliated graphite

40 20

Particle Size (m)

12

c (48h)
Differential Distribution (%)
10

100

Integral Distribution (%)

80 8 6 4 2 0 10 20 30 40 50 60

40 20

Size of Particle (m)

Fig. 2. Dierential distributions (histograms) and integral distributions (curves) of the particle size of foliated graphite sonicated with various time as indicated.

Table 1 Parameters of particles of foliated graphite prepared using various irradiation times Type FG6 FG8 FG10 FG12 FG16 FG48 D20 (lm) 18.0 16.0 6.5 6.0 6.0 5.5 D42 (lm) 25.0 21.0 9.5 9.0 9.0 8.0 D63 (lm) 32.0 29.0 13.0 12.0 12.0 11.0 D81 (lm) 42.0 34.0 17.0 17.0 16.0 16.0 D90 (lm) 50.0 38.0 21.0 21.0 19.0 19.0 D99 (lm) 80.0 52.0 36.0 34.0 34.0 34.0

FGi foliated graphite prepared using i h ultrasonic irradiation. Dj j% of volume of particles is smaller than dimension Dj .

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is eectively torn into foliated graphite, the resulting particles will be less sensitive to further ultrasonic irradiation, at least under these same conditions. On the other hand, the asymmetrical distributions of the resulting foliated graphite might be benecial to lower the percolation threshold of the composites lled with those kinds of foliated graphite, since it has been shown [2022] that when the percolation objects have a large aspect ratio, the critical concentration diminishes as the size distribution increases. Fig. 3 shows the mean particle size (diameter) of the foliated graphite. These results together with the values presented in Table 1 show further that at the early stage of ultrasonic irradiation, the particle size decreased with a higher rate. When the critical time was reached, the decrease slowed down as the increase of irradiation time. However, noting the structure of the exfoliated graphite particles, one can imagine the following process for the foliation of graphite sheets from the exfoliated graphite. Since exfoliated graphite particles are very brittle, when subjected to ultrasonic irradiation, most of the particles should be rstly broken into shortened accordion-like particles. When the shortened particles were suciently small, the separation of the component graphite akes from the sub-particles became dominant. Further increase of the irradiation time would result in the breaking of the foliated graphite nanosheets. Therefore, at the early stage of the irradiation, the particles were mostly the accordion-like foliated exfoliated graphite, of which the sizes were much larger than the foliated ones. After the graphite sheets were foliated into separate nanosheets, if the irradiation power is not suciently high, increase of irradiation time would have limited inuence on the particle size, since little nanosheets will be broken. Nevertheless, it should be noted that the above-mentioned three processes could take place simultaneously as the start of ultrasonic irradiation, but with relatively dierent extent as stated above,

and the separated nanosheets might also be composed of several thinner single crystal graphite sheets. 3.2.3. Nitrogen adsorption Fig. 4 shows the low-temperature adsorption isotherms of nitrogen for the exfoliated graphite and two foliated graphite samples with irradiation times of 10 and 16 h, respectively. The isotherms observable in this gure can be considered as typical type II isotherms [23]. The isotherms of the two foliated graphite samples are nearly indistinguishable, indicating that the two samples possess similar structures and adsorption properties. The isotherms are concave in the low pressure region, and convex in the higher pressure region, while approximately linear in the intermediate region. The adsorption volume increases rapidly at low relative pressure due to the interaction of nitrogen gas with the rst energetic region followed by the less energetic region. The monolayer of adsorbed molecules is completed at a relative pressure about 0.01, then the multilayers are formed. The abrupt rise in adsorbed volume at a relative pressure of 0.90 to unity indicates that capillary condensation has occurred during the adsorption process. The experimental data corresponding to the range of relative pressure from 0.05 to 0.25 are plotted in Fig. 5 according to the classical BET Equation [24]. The values of the slopes and intercepts obtained from the leastsquares t of BET equation are used to derive the specic surface area values of the samples using related equations in [24]. The as-obtained results as well as the values of pore volume and mean pore diameter derived from the isotherms are listed in Table 2. The pore volume distributions derived from BJH method [25] for the three samples are also displayed in Fig. 6. According to the literature, pores larger than 300 nm are ignored. This does not deny the existence of larger pores, since pores of size in the lm range can be

35
180

Mean Particle Size (m)

30

160

Vol Adsorbed (cm /g)

140 120 100 80 60 40 20

25

6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 0.00

EG00 FG10 FG16

Low pressure region
0.02 0.04 0.06 0.08 0.10

20

15

10 0 10 20 30 40 50

Irradiation Time (h)

Fig. 3. Mean particle size of foliated graphite prepared using various ultrasonic irradiation times.

0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 Relative pressure, p/p0

Fig. 4. Low-temperature adsorption isotherms of nitrogen for EG and the foliated graphite (FG) sample as indicated.

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757

BET Transformation,p /(v ( p0-p))

0.05 0.04 0.03 0.02 0.01 0.05 0.10 0.15 0.20 0.25

Pore Volume (cm 3/g)

0.06

EG00 FG10 FG16

0.0035 0.0030 0.0025 0.0020 0.0015 0.0010 0.0005 0.0000 0 50 100 150 200 250
EG00 FG10 FG16

300

Relative Pressure, p/p0

Fig. 5. BET plots for the exfoliated graphite and two foliated graphite samples as indicated.

(a)
0.16

Pore Diameter (nm)

Pore Volume (cm 3/g)

0.14 0.12 0.10 0.08 0.06 0.04 0.02 0 50 100 150 200 250

EG00 FG10 FG16

directly observed via SEM. It is clear that the three graphite samples have similar pore structures. The samples possess a reasonable amount of macropores (greater than 50 nm), with small fraction of mesopores (250 nm) and few micropores (less than 2 nm). From Table 2 as well as Fig. 6, it is seen that upon ultrasonic irradiation, both the pore volume and pore diameter for the foliated graphite decrease as compared with the original exfoliated graphite. Since the foliated graphite particles are almost sheet-like, rather than worm-like for the exfoliated graphite, most of the adsorption volume should be attributed to the interparticle voids. Due to the irradiation eects the number of smaller pores is also substantively decreased. The transformation of EG into foliated graphite leads to decrease of the specic surface area, but the magnitude is modest. Furdin [26] found that isolating the composing elements from exfoliated graphite by grinding not only destroys the honey-bomb type open structure but also bring together the walls of the bellows, leading to products with specic areas two times smaller than that of the pristine EG. In the current case, ultrasonic irradiation alone is employed to powdering the EG, there should be many dierences when compared to the procedures adopted by Furdin. Therefore, the results obtained in our lab are plausible. Since a hypothetical monolayer graphite would exhibit a specic surface area close to 2700 m2 /g, by comparing the specic area of the foliated graphite (approximately 17.55 m2 /g) to that of monolayer

300

(b)

Pore Diameter (nm)

Fig. 6. Incremental (a) and cumulative (b) pore volumes of the exfoliated graphite and two foliated graphite samples as indicated.

graphite, one piece of foliated graphite nanosheet can be estimated to consist of 154 graphite layers. If an interlayer spacing of 0.335 nm is assumed for bulk graphite, the average thickness of the foliated graphite nanosheets thus can be readily estimated to be about 52 nm. This value is consistent with that obtained from SEM observations. Then the aspect ratio can be calculated to be as high as 250. 3.2.4. X-ray diraction The foliated graphite nanosheets prepared with different irradiation times exhibited almost identical XRD patterns. In order to make a comparison with the crystalline structures of the natural graphite and exfoliated graphite, the crystalline parameter Lc of the FG, EG and natural graphite samples was calculated using the Scherrer equation. The results are given in Table 3.

Table 2 Textural characteristics of the exfoliated graphite and two foliated graphite samples Type EG00 FG10 FG16 BET specic surface area (m2 /g) 24.11 17.55 17.56 BJH pore volume (cm3 /g) 0.159 0.088 0.091 BJH mean pore diameter (nm) 26.64 19.19 19.83

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Table 3 Crystalline parameters for dierent graphite samples studied in this work Parameter d0 0 2 (nm) Lc (nm) NFG 0.333 34.39 EG 0.334 14.69 FG10 0.334 14.68 FG16 0.334 14.68 FG48 0.335 14.68

NFGnatural ake graphite. FGifoliated graphite prepared with i h irradiation.

From Table 3, it is seen that transformation of natural ake graphite into exfoliated graphite the mean particle thickness decreases, while in the same time a marked decrease in the value of Lc (0 0 2) is observed. The morphological changes ongoing from EG to foliated graphite upon ultrasonic irradiation resulted in little dierence in the thickness direction. This indicates that although foliated graphite nanosheets can be eectively obtained by the formation of exfoliated graphite followed by ultrasonic powdering, aking of graphite does not take place to c-axis in the irradiation process. The mean number of crystallites in a thickness direction of exfoliated graphite and foliated graphite is then estimated to be about 34, which means that all the graphite layers are ideally isolated. This is clearly veried by the electron microscopy, and is not contrasted to polycrystalline nature of the foliated particles. 3.2.5. IR measurement Fig. 7 shows the FTIR spectrum of EG. The band at 3433 cm1 can be attributed to OH stretching vibrations of phenolic or alcoholic functional groups present on the EG sheets [27]. The presence of carboxyl functional groups can also be detected at around 1650 cm1 [28]. These evidences, together with the results of XPS in the literature [29], indicated that during the treatment of natural graphite with acids some carbon double bonds were oxidized, leading to the presence of oxygen-containing functional groups on exfoliated graphite, which will facilitate physical and chemical interactions between EG and polymer (or monomer).

4. Conclusions In this study, natural ake graphite was expanded into exfoliated graphite via an acids intercalation procedure. The resulting exfoliated graphite is a worm-like particle composed of graphite sheets with thickness in the nanometer scale. Subjecting to ultrasonic irradiation, the exfoliated graphite is eectively further foliated into isolated graphite nanosheets. SEM, TEM, SAD, laser counting, and BET measurements revealed that the as-fabricated graphite nanosheets were about 52 nm in thickness. The diameters of the foliated graphite particles decreased as the increase in irradiation time. For FG prepared with 10 h ultrasonic irradiation, the particles were about 13 lm in diameter. These dimensions correspond to a mean aspect ratio of about 250, which will be demonstrated to be very useful in lowering the percolation threshold when the foliated graphite is loaded into nylon 6 matrix [30,31]. Furthermore, the optimum irradiation time used to prepare ideal foliated graphite could be xed at 10 h. FTIR examination shows that there are oxygen-containing groups present on the surface of the exfoliated graphite. This result substantiates the statement reported in the literatures that acids treatment could result in oxidization of carbon bonds in the graphite. The presence of the functional is supposed to be benecial to the interaction between the polymer and the foliated graphite. Acknowledgement This work was sponsored by the National Natural Science Foundation of China, No. 20174012.

References
[1] Vaia RA, Price G, Ruth PN, Nguyen HT. Lichtenhan, polymer/ layered silicate nanocomposites as high performace ablative materials. J Appl Clay Sci 1999;15:6792. [2] Alexandre M, Dubois P. Polymer-layered silicate nanocomposites: preparation, properties and uses of a new class of materials. Mater Sci Eng 2000;28:163. [3] Kawasumi M, Hasegawa N, Kato M, Usuki A, Okada A. Preparation and mechanical properties of polypropylene-clay hybrids. Macromolecules 1997;30:63338. [4] Vaia RA, Giannelis EP. Polymer melt intercalation in organicallymodied layered silicates: model predictions and experiment. Macromolecules 1997;30:80009.

Fig. 7. FTIR spectrum of exfoliated graphite prepared from acids treatment.

G. Chen et al. / Carbon 42 (2004) 753759 [5] Usuki A, Kojima Y, Kawasumi M, Okada A, Fukushima Y, Kurauchi T, et al. Swelling behavior of montmorillonite cation exchanged for x-amino acids by e-caprolactam. J Mater Sci 1993;8:117984. [6] Kojima Y, Usuki A, Kawasumi M, Okada A, Fukushima Y, Kurauchi T, et al. Mechanical properties of nylon 6-clay hybrid. J Mater Sci 1993;8:11859. [7] Vaia RA, Jandt KD, Kramer EJ, Giannelis EP. Kinetics of polymer melt intercalation. Macromolecules 1995;28:80805. [8] Manias E, Touny A, Wu L, Strawhecher K, Lu B, Chung TC. Polypropylene/montmorillonite nanocomposites. Review of the synthetic routes and materials properties. Chem Mater 2001;13:351623. [9] Koo CM, Ham HT, Kim SO, Wang KH, Chung IJ, Kim DC, et al. Morphology evolution and anisotropic phase formation of the maleated polyethylene-layered silicate nanocomposites. Macromolecules 2002;35:511622. [10] Xu R, Manias E, Snyder AJ. New biomedical poly(urethaneurea)layered silicate nanocomposites. Macromolecules 2001;34:3379. [11] Giannelis EP. Polymer layered silicate nanocomposites. Adv Mater 1996;8:2938. [12] King JA, Tucker KW, Vogt BD, Weber E, Quan CL. Electrically and thermally conductive nylon 6,6. Polym Comp 1999;20:64354. [13] Okada A, Usuki A. The chemistry of polymerclay hybrids. Mater Sci Eng C 1995;3:10915. [14] Chen GH, Wu DJ, Weng WG, Wu CL. Exfoliation of graphite ake and its nanocomposites. Carbon 2003;41:61921. [15] Chen GH, Wu CL, Weng WG, Wu DJ, Yan WL. Preparation of polystyrene/graphite nanosheet composite. Polymer 2003;44: 17814. [16] Nakajima T, Matsuo Y. Formation process and structure of graphite oxide. Carbon 1994;32:46975. [17] Herold A, Petitjean D, Furdin G, Klatt M. Exfoliation of graphite intercalation compounds: classication and discussion of the processes from new experimental data relative to graphite-acid compounds. Mater Sci Forum 1994;152/153:2818.

759

[18] Thompson LH, Doraiswamy LK. Sonochemistry: science and engineering. Ind Eng Chem Res 1999;38:121549. [19] Suslick KS. On the origin of sonoluminescence and sonochemistry. Ultrasonics 1990;28:28090. [20] Balberg I, Binenbaum N. Computer study of the percolation threshold in a two-dimensional anisotropic system of conducting sticks. Phys Rev B 1983;28:3799812. [21] Balberg I, Bozowski S. Percolation in a composite of random stick-like conducting particles. Solid State Commun 1982;44:551 4. [22] Celzard A. Phys Rev B 1996;53:620914. [23] Brunauer S, Deming LS, Deming WS, Teller E. On a theory of the van der Waals adsorption of gases. J Am Chem Soc 1940;62:1723 32. [24] Brunauer S, Emmett PH, Teller E. Adsorption of gases in multimolecular layers. J Am Chem Soc 1938;60:30919. [25] Barrett EP, Joyner LG, Halenda PP. The determination of pore volume and area distributions in porous substrates. I. Computations from nitrogen isotherms. J Am Chem Soc 1951;73:37380. [26] Furdin G. Exfoliation process and elaboration of new carbonaceous materials. Fuel 1998;77:479785. [27] Weng WG, Chen GH, Wu DJ, Lin ZY, Yan WL. Preparation and characterizations of nanoparticles from graphite via an electrochemically oxidizing method. Synth Met 2003;139:2215. [28] Ramesh P, Sampath S. Electrochemical and spectroscopic characterization of quinone functionalized exfoliated graphite. Analyst 2001;126:18727. [29] Ramesh P, Sampath S. A binderless, bulk-modied, renewable surface amperometric sensor for NADH and ethanol. Anal Chem 2000;72:336973. [30] Weng WG, Chen GH, Wu DJ. Crystallization kinetics and melting behaviors of nylon 6/foliated graphite nanocomposites. Polymer 44:811932. [31] Chen GH, Weng WG, Wu DJ. Nonlinear conduction in the nylon6/foliated graphite nanocomposites above the percolation threshold. J Polym Sci B Polym Phys Ed 2004;42(1):15567.