Carbon 42 (2004) 2839–2847

www.elsevier.com/locate/carbon

Characterizations of expanded graphite/polymer composites

prepared by in situ polymerization
Genhua Zheng a, Jingshen Wu a,b,*
, Wenping Wang a, Caiyuan Pan a,*

a
Department of Polymer Science and Engineering, University of Science and Technology of China, Jinzhai Road 96, Hefei, Anhui 230026, PR China
b
Department of Mechanical Engineering, Hong Kong University of Science and Technology, Kowloon, Hong Kong SAR, PR China

Received 27 January 2003; accepted 20 June 2004

Available online 14 August 2004

Abstract

Poly(styrene-co-acrylonitrile)/expanded graphite composite sheets with very low in-plane (8.5 · 10!3 X cm) and through-thick-
ness (1.2 · 10!2 X cm) electrical resistivities have been prepared. The expanded graphite was made by oxidation of natural graphite
flakes, followed by thermal expansion at 600 !C. Microscopic results disclosed that the expanded graphite has a legume-like struc-
ture, and each ‘‘legume’’ has a honeycomb sub-structure with many diamond-shaped pores. After soaking the expanded graphite
with styrene and acrylonitrile monomers, the polymer/expanded graphite composite granules were obtained by in situ polymeriza-
tion of the monomers inside the pores at 80 !C. The functional groups and microstructures of the oxidized graphite, expanded
graphite and composites in the forms of particles or sheets were carefully characterized using various techniques, including
X-ray powder diffraction, thermogravimetry, optical and electron microscopy. It was found that the honeycomb sub-structure sur-
vived after hot-pressing, resulting in a graphite network penetrating through the entire composite body, which produces a composite
with excellent electrical conductivity.
" 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon composite, Graphite oxide, Resins; B. Intercalation; D. Electrical properties

1. Introduction monomers can be achieved through ion exchange reac-

tions in the silicate galleries, the intercalation of mono-
The design and manufacture of lightweight polymer mers in graphite cannot be easily done, because
composites with high electrical conductivity have been graphite does not bear any electrical charge. Thus, dif-
a research focus in recent years [1–4]. Since natural ferent methods for intercalating monomers into graphite
graphite (NG) has a high electrical conductivity ("104 have been developed. The first method is the prepara-
S/cm at room temperature [5]) and a unique layered tion of graphite oxide (GO) by oxidation of NG [6,7].
nano-structure, it is considered an ideal candidate for Since GO has a large number of polar groups, such as
manufacturing conductive polymer composites. How- hydroxyl, ether groups, and possibly, carboxylate
ever, unlike layered silicates, in which intercalation of groups on the surface of the graphite layers, intercala-
tion of water-soluble polymers in GO becomes possible.
For example, the GO particles are simply added to
*
Corresponding authors. Address: Department of Polymer Science aqueous solution of the polymers, forming intercalated
and Engineering, University of Science and Technology of China, polymer/GO composites with different c-axis spacing.
Jinzhai Road 96, Hefei, Anhui 230026, PR China. Tel.: +852 2358 Successful examples of these composites include poly-
7200; fax: +852 2358 1543 (J. Wu), tel.: +86 551 360 3264; fax: +86 551
360 1592 (C. Pan).
(vinyl alcohol)/GO [1], poly(ethylene oxide)/GO [3,4],
E-mail addresses: [email protected] (J. Wu), [email protected] poly(diallyldimethyl ammonium chloride)/GO [8] and
(C. Pan). poly(furfuryl alcohol)/GO [9]. For hydrophobic

0008-6223/$ - see front matter " 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.06.029
2840 G. Zheng et al. / Carbon 42 (2004) 2839–2847

polymers, such as poly(vinyl acetate) (PVAc), the inter- be a key to obtain high electrical conductivity in poly-
calated polymer/GO composite was prepared by an mer/graphite composites.
in situ intercalative polymerization, in which a n-octa- In this paper, we report a novel method for the prep-
nol/GO intercalated composite was first formed, vinyl aration of polymer/graphite composites with greatly im-
acetate monomer was then absorbed into the interlayer proved electrical conductivity very close to that of
of the modified GO, followed by thermally polymeriza- natural graphite. Various characterization techniques
tion. Thermal stability of the nano-composite was high- were used to reveal the microstructure of the composites
er than that of pure PVAc, and its electrical conductivity and the structure-property relationship, which may be
was 0.14 S/cm at room temperature [10]. responsible for the high conductivity.
A more effective method of preparing the polymer/
GO composite is to expand the GO by rapidly heating
the pre-treated graphite to a high temperature. The ex- 2. Experimental
panded graphite (EG) with high expansion ratio, gener-
ally ranging from 200 to 300 in c-axis [11,12], has much 2.1. Materials
larger inter-planar spacing. It can be easily filled by, for
example, e-caprolactam and n-aminocaproic acid Natural graphite in particle form with an average
through physical adsorption because of the porous fea- diameter of 500 lm was obtained from Shandong Guyu
tures of the EG and the polar interactions between the Co. (China). Two monomers, styrene (St) and acrylonit-
monomers and the polar groups on the EG layers [2]. rile (AN) purchased from the First Shanghai Chemical
After the EG was filled with monomers, in situ polymer- Reagent Plant, were distilled before use. The initiator,
ization was carried out under heat to form a Nylon-6/ 2,2 0 -azobis(isobutyronitrile) (AIBN) was bought from
EG composite. Microstructural study [2] showed that the same reagent plant, and purified by recrystallization
the graphite in the Nylon-6/EG composite had an exfo- from its ethanol solution. Concentrated nitric acid, ace-
liated structure. The thickness of exfoliated graphite lay- tic anhydride and KMnO4 were of analytical grade and
ers was about 10 nm and the interlayer spacing was used as received.
about 30 nm. Due to the exfoliated structure, the electri-
cal conductivity of the Nylon-6/EG composite with 2 2.2. Preparation of expanded graphite
vol.% graphite was rather low (10!4 S/cm) [2].
There are other methods for the preparation of poly- EG was prepared by a modified method based on a
mer/GO composites with good physical, chemical and previous work [16]. NG (1.0 g) and KMnO4 (0.7 g) were
mechanical properties. For example, ultra-thin films were added into a mixture of acetic anhydride (8.0 g) and 65%
prepared using layer-by-layer self-assembly of oppo- nitric acid (5.0 g) at 30 !C while stirring. After 40 min
sitely charged polyelectrolytes and exfoliated GO nano- reaction, the graphite oxide (GO) obtained by filtration
plates [13–15]. Kovtyukhova et al. prepared multi-layer was washed with distilled water until neutralization, and
films by alternating adsorption of anionic GO sheets then dried in a vacuum oven at 50 !C. The resulting GO
and cationic poly(diallyldimethyl ammonium chloride). was subsequently heated to 600 !C and kept at this tem-
The resistivity of the multi-layer films was in the order perature for 90 min in nitrogen atmosphere. The expan-
of 106 X cm [15]. sion ratio of the EG obtained was about 30, which was
From the above literature review, it is quite clear that obtained based on the volume change of graphite before
the microstructure and electrical properties of the poly- and after the expansion.
mer/graphite composites vary with the method used in
the composite preparation. Use of highly oxidized and 2.3. Preparation of composite
expanded graphites may result in an exfoliated graphite
structure with very high electrical resistance. It is also St (13.6 g), AN (2.4 g) and AIBN (0.08 g) were mixed
noted that the polymer/GO composites reported previ- thoroughly and added into a 250ml two-necked flask
ously showed a much lower electrical conductivity than containing EG (2.0g). To ensure the complete absorp-
that of the NG. The poor electrical performance of the tion of the monomers into the pores of EG particles,
polymer/GO composites may be attributed to the fact the closed flask was kept at room temperature for 12
that the polymer intercalation process will inevitably h, and the mixture was shaken occasionally until no
damage the structural integrity and conduction mecha- monomer appeared on the surface of EG particles.
nism of the graphite that, in turn, will affect the electrical The in situ polymerization of St and AN inside the pores
conduction of the composites. Moreover, the oxidation of EG particles was first carried out at 60 !C for 12 h,
reactions of graphite may also have influences on its followed by polymerization at 80 !C for another 12 h.
conduction mechanism, leading to a reduced conductiv- The residual monomers were removed at 90 !C under
ity. Therefore, avoiding excessive oxidation and severe reduced pressure. The resultant poly(St-co-AN)/EG
structural change during graphite pre-treatment may (PSAN/EG) composite was obtained in the form of
 G. Zheng et al. / Carbon 42 (2004) 2839–2847 2841

irregular cylindrical particles with an average diameter 3. Results and discussion

of 450 lm and height of 800 lm.
The composite particles were transferred to a pre- As mentioned, deep oxidation will destroy the crystal
heated compression mould and hot-pressed into rectan- structure of NG [7], resulting in a nearly amorphous GO
gular sheets of 40 · 40 · 5 mm3 at 150 !C under 10–15 with different physical, chemical and mechanical proper-
MPa. The composite sheets were later cut into different ties, particularly a deteriorated electrical conductivity.
sizes and geometries for the measurements of different In addition, for getting the EG with low expansion ratio
properties. in the next step, it is necessary to avoid excessive oxida-
tion in graphite treatment. However, the oxidation of
2.4. Characterization NG is a necessary process because it introduces func-
tional groups on the layer surface of the graphite and
Information on nano-scale structures of the NG, EG the intercalated molecules, which will help to prepare
and the PSAN/EG composite was obtained by X-ray the EG. Obviously, an optimization of the oxidation
diffraction using CuKa radiation; (k = 1.54178 Å). The process plays a key role in the preparation of polymer/
FT-IR spectra of the materials were recorded on a Nic- graphite composites with good electrical properties. In
olet NAGNA-IR 750 spectrometer using a KBr Pellet. the present study, we found that the degree of oxidation
The composition and thermal stability of the PSAN/ could be easily controlled via change of reaction condi-
EG composite were tested by thermal gravimetric anal- tions. The expected results were achieved when the NG
ysis (TGA) on a Rheometric TGA 1000 M at 10 !C/min was oxidized for about 40 min.
in a nitrogen atmosphere.
Both optical (OM) and electron microscopes were 3.1. Characterization of expanded graphite
employed to examine the microstructures of the EG
and the PSAN/EG composite. In the optical microscope To obtain the EG with a low expansion ratio, the
study, composite blocks of 5 · 5 · 20 mm3 were cut expansion temperature of 600 !C and time of 90 min
from the hot-pressed composite sheet and embedded in were selected. The elemental analysis results of the dried
an optical clean epoxy resin. After curing at room tem- EG by EDAX listed in Table 1 shows that the atomic
perature for about 8 h, the epoxy cylinder with a PSAN/ ratio of carbon to oxygen in the EG obtained is approx-
EG block at the center was cut using a diamond saw to imately 104:5. Compared with an GO, C8O2(OH)2, re-
bring the PSAN/EG block to the surface of the cylinder. ported by Touzain et al. [17], the oxidation degree of
This surface was then ground by sand paper of different graphite in this study is much lower. Further expansion
grades and polished by diamond paste (3 and 1 lm) and of GO at 600 !C for 90 min produced EG with an appar-
Al2O3 (0.05 and 0.03 lm) until a scratch-free, mirror ent density of 3.3 · 10!2 g cm!3 and the expansion ratio
surface was obtained. In the electron microscope study, of "30.
both the scanning electron microscope (SEM) and trans- The oxidation of graphite can be further confirmed
mission electron microscope (TEM) were used. The by the FT-IR spectrum of the EG in Fig. 1A. The
SEM images were obtained from samples without a con- stretching vibrations of hydroxyl (–OH) are clearly seen
ductive coating at 5 kV in order to avoid charging. Ele- at 3242 and 1380 cm!1. The peak at 1112 cm!1 indicates
mental analysis of the samples was obtained by energy the existence of the oxygen-containing functional groups
dispersive analysis of X-rays (EDAX). To enhance the on EG, which were formed during oxidation reactions.
topographic contrast, the polished surface was etched Despite of the treatment of GO at higher temperature,
with tetrahydrofuran (THF) to remove the polymer ma- these functional groups are not completely decomposed.
trix for exposing the embedded graphite phase. TEM For filling monomers and in situ polymerization in
images were obtained with a JEOL 100 CXII micro- the following steps, understanding the shape and size
scope at 100 kV using 20 nm thick samples prepared of pores formed in the EG is very important. Thus the
using an ultra-microtone with a diamond knife. SEM images of the resultant EG particles were meas-
The electrical resistivity of the PSAN/EG composites ured, and are shown in Fig. 2. Interestingly, each EG
was measured at room temperature by a standard four- particle has a ‘‘bean pod’’ structure (Fig. 2a). Each of
probe method. The four electrodes with indium as probe the pods represents an expanded graphite domain. The
contact (very fine spot) were fixed on any four locations width and length of the pods are on the order of
(keeping the distances between the two locations as equal
as possible) of the testing samples by hot-pressing. The
specimens were 7 · 3 · 0.5 mm3 rectangle bars. An aver- Table 1
The contents of carbon and oxygen in EG
age resistivity was deduced from four repeated measure-
ments at different locations on the testing sheet. The Element wt.% Atom% Relative atom number
resistivities at various temperatures were measured after C 93.99 95.42 104
keeping the sample at those temperatures for 10 min. O 6.01 4.58 5
2842 G. Zheng et al. / Carbon 42 (2004) 2839–2847

EG(A) neighboring pores can be measured, and ranges from

170 to 510 nm.
In order to identify whether the ligament areas
remain the layered nano-structure of NG, the XRD

1112
3242
patterns of the NG, GO, EG and EG/PSAN were

1380
3412

1630
measured and are shown in Fig. 3. The sharp reflec-
EG/PSAN(B)
tion peak at 2h = 26.7!, corresponding to a c-axis
spacing of 3.34 Å, appears in all curves, which

1124
1387
suggests that the oxidation, expansion, polymerization
3240

1634
3435

and hot-pressing did not alter the nano-scale structure

4000 3500 3000 2500 2000 1500 1000
of the NG. The un-expanded graphite ligaments most
(cm-1)
likely have the same crystal structure and interlayer
spacing, hence, the same physical, especially, electrical
Fig. 1. Reflective IR spectra of (A) EG and (B) the surface of a test and thermal properties as that of the NG. Since the
sheet prepared from EG/PSAN composite. thickness of the un-expanded graphite ligaments
ranges from 170 to 510 nm and the interlayer spacing
hundreds of micrometers. An enlarged SEM micrograph is 3.34 Å, each of the graphite ligaments in Fig. 2
of such a pod is shown in Fig. 2b. It is clear from the pic- should consist of 500–1500 graphite monolayers after
ture that the expanded domain has a honeycomb sub- a simple calculation. The broad peak from 17.5! to
structure with many diamond-shaped pores. A further 25.5! in the curve c of Fig. 3 may be attributed
enlarged picture in Fig. 2c shows that the size of the dia- to the interlayer spacing change of those graphite
mond-shaped pores varies from 0.6 to 3 lm. The thick- domains that had been expanded to different
ness of the un-expanded graphite ligaments between the degrees.

Fig. 2. (a–c) SEM micrographs of an expanded graphite particle with different magnifications: (a) ·250; (b) ·1000; (c) ·6000. (d) SEM micrograph of
PSAN/EG composite particle.
 G. Zheng et al. / Carbon 42 (2004) 2839–2847 2843

EG/PSAN (d)
100 A (414,96)

EG/PSAN
80

Weight loss(%)
EG (c)
60

40
GO (b)
20
B (466,16)
NG (a) 0
0 100 200 300 400 500 600
ο
Temperature ( C)
5 10 15 20 25 30 35 40 45 50
2 (degree) Fig. 4. TGA curve of PSAN/EG composite particles.

Fig. 3. XRD patterns of (a) NG, (b) GO, (c) EG and (d) PSAN/EG.
show white (Fig. 2d), and dark parts correspond to the
PSAN filled in the pores of EG.
3.2. Microstructure of the PSAN/EG composite granules The XRD pattern of the PSAN/EG composite gran-
ules is shown in Fig. 3d. The sharp reflection at
To maintain the resultant structure of EG and to 2h = 26.7! is once again observed, which implies that
make applicable devices, filling an appropriate polymer the monomer filling and polymerization processes had
or copolymer in the diamond-shape pores is very impor- no influence on the nano-structure of the un-expanded
tant. This was performed by absorption of monomer St graphite ligaments. Their crystal structure is retained
or co-monomers, St and AN, into the pores, followed by and the interlayer spacing in c-axis is kept at 3.34 Å.
thermal polymerization. The results are listed in Table 2. These results are the same observed by Chen et al. [18].
The contents of polymer in EG were estimated by the
weight difference of EG and EG/polymer composite
granules, and also can be determined by TGA. As dem- 3.3. Microstructure of the PSAN/EG composite sheet
onstrated in Fig. 4, a sharp weight loss, indicating the
decomposition of polymer matrix, occurred in the tem- If the sample sheets made from the polymer/EG
perature range from "400 to 475 !C. The weight loss composite granules are covered by polymer material,
due to the PSAN matrix decomposition is about 85%, the electrical conductivity will decrease dramatically.
which is similar to the content of PSAN in the compos- Therefore, processing the composites particles into
ite measured by weight method (No. 2 in Table 2). These testing sheets must be carefully carried out to prevent
facts confirm that the PSAN/EG composite with the the filled polymer going out to the surface of the
weight ratio of 86/14 was really formed. For PSt/EG sheet. The reflective FT-IR instrument was used to
composite (No. 1 in Table 2), it has the similar structure identify whether the polymer exists on the surface of
and properties except slight brittleness. Thus, all data testing sheets. Fig. 1B is its typical IR spectrum. Com-
and pictures in this paper were obtained from the pared with IR spectrum of EG in Fig. 1A, we will
PSAN/EG composite granules. find that there is no absorption peak ascribed to
Fig. 2d is a SEM micrograph of the PSAN/EG com- PSAN. At least, the amount of polymer on the sur-
posite granules received right after the in situ polymeri- face is too small to be detected. Possibly, under press-
zation but before the hot-press process. The same ing and heating, the fluid polymer in the pores will
honeycomb structure as observed with the EG (Fig. push the graphite granules together, forming flat
2a) is also found here. It is clearly seen that the cross- sheets after cooled to room temperature, while the
section surfaces of graphite ligaments between the pores surface ligaments of the composite granules are joined

Table 2
Filling monomers and in situ polymerizationa
No. Recipe Weight ratio of polymer/EG Conversion (%)
EG (g) St (g) AN (g) AIBN (g)
1 3.0 27.0 0 0.085 88/12 81 ± 4
2 2.0 13.6 2.4 0.08 86/14 77 ± 3
a
Polymerization conditions: see experimental part.
2844 G. Zheng et al. / Carbon 42 (2004) 2839–2847

together. In order to verify this idea, reflective light rounded by other graphite granules. The ligaments at
optical microscopic photos of the tested sheets made the border between the neighboring granules are called
from the PSAN/EG composite granules were taken as borderline ligaments. They are thicker compared to
and are shown in Fig. 5a–f. The white stripes in these those graphite ligaments within a particular particle,
figures are the graphite phase, while the black contin- and may result from mergence of the shells of two pods
uous phase is the PSAN matrix. The dark dots in the (Fig. 2a and b) under higher temperature and pressure.
pictures are voids due to the air bulbs trapped in hot- A similar phenomenon can also be seen in Fig. 5b and
press and/or defects formed during polishing. c, though they were taken from the different hot-pressed
Fig. 5a–c show the cross-sections of those graphite sheets. It seems that the higher temperature and pressure
‘‘bean pods’’, first observed in Fig. 2a, in the hot-pressed in the sheet forming process did not make significant
sheets. As shown in Fig. 5a, there are two particles changes to the microstructure of the EG in the compos-
joined together with a clear border. They are further sur- ites, except the shape of the graphite domains was dis-

Fig. 5. Microscope photos of cross-sections of the PSAN/EG test pieces with different magnifications: (a–c) ·200; (d–f) ·500.
 G. Zheng et al. / Carbon 42 (2004) 2839–2847 2845

Fig. 7. High resolution TEM of the PSAN/EG composites plate.

Ultra-thin samples with about 20 nm thickness were held on copper
net.

Processing the composite granules into a test sheet

does not affect the structure of graphite ligaments. This
can be verified by XRD and a high resolution TEM. Fig.
Fig. 6. SEM photograph of the PSAN/EG block cross-section. The 3d shows a reflection peak at 2h = 26.7! corresponding
test sample was made by removing the polymers from the sample with to a c-axis spacing of 3.34 Å. A typical TEM micro-
3.0 · 3.0 mm using THF as etching solvent.
graph is shown in Fig. 7. The parallel lines, as indicated
by arrows a, are the cross-sections of the graphite layers.
The distance between two adjacent layers is 3.35 Å,
torted, probably because the pores filled with polymer which is the same as that in the NG. This observation
are less compressible. confirms, once again, that the crystal structure of the
A closer observation at higher magnifications shows NG in the graphite ligaments survives after oxidation,
that all the white graphite ligaments are well-con- high temperature expansion, in situ polymerization,
nected (Fig. 5d–f). Fig. 5d shows obviously that many and hot-press sheet formation.
graphite ligaments are connected to the Y shaped bor- As a summary, a flowchart describing the microstruc-
derline ligaments. All these graphite ligaments inside ture formation of the PSAN/EG composite during the
each of graphite granules are aligned in one direction processing is presented in Fig. 8. When a NG flake
although their oriented direction in the different com- (Fig. 8a) is mixed with oxidizing chemicals, localized
posite granules is different in the same hot-pressed oxidation occurs and some chemicals are intercalated
sheet (Fig. 5e and f). Therefore, a picture of the in the certain locations of the graphite flake (Fig. 8b).
hot-pressed sheet can be described as follows: the bor- When the GO is heated, expansion takes place in the
derline ligaments are looked like connected large ‘‘riv- locations where oxidation occurred, resulting in many
ers’’, and there are ‘‘streams’’ and ‘‘brooks’’ diamond-shaped pores and the formation of a honey-
originating from the ‘‘rivers’’ passing through the en- comb structure in the graphite flake (Fig. 8c). When
tire domain. It is not difficult to imagine that the the EG is mixed with monomers, the monomers will
graphite ‘‘rivers’’ and ‘‘streams’’ have formed a net- be absorbed and trapped in the pores (Fig. 8d), due to
work throughout the entire composite, in other words, good affinity of St and AN with graphite materials.
the composite has a graphite-interpenetrating network When the monomer-filled graphite is heated, in situ
structure. polymerization will take place, resulting in a polymer/
To confirm the network structure established with EG composite with an interpenetrated graphite network
the OM investigations, a polished surface of a THF (Fig. 8e).
to remove the PSAN to expose the graphite phase.
After THF etching, the surface was examined by 3.4. Electrical properties
SEM. Fig. 6 is a typical SEM micrograph taken on
the etched surface. Clearly, the honeycomb structure As mentioned at the very beginning of this paper, the
remains and the diamond shaped pores are preserved. ultimate goal of making polymer/EG composites is to
Thus the network structure of the composites is develop lightweight highly conductive materials. To
confirmed. determine the electrical performance of the PSAN/EG
2846 G. Zheng et al. / Carbon 42 (2004) 2839–2847

Fig. 8. Schematic diagram of structure change in the graphite particles during the processing.

composites prepared in the present study, both the elec- faces of the testing sheets are well-connected by many
trical resistivities between upper and bottom surfaces graphite ligaments, which is different from the layered
(through-thickness) and in the same surface (in-plane) structure of NG.
of the testing sheet made from PSAN/EG composite The effects of temperature on the resistivity of the
granules were measured at room temperature using the PSAN/EG composite were investigated. The typical
four-probe technique. The results are listed in Table 3. curves of in-plane and through-thickness resistivities
For comparison, the through-thickness and in-plane against temperature are shown in Fig. 9. In the temper-
electrical resistivities of the NG and the compressed ature range from 300 to "370 K, slight decreases of the
EG are also listed. resistivities were observed. An abrupt decreases in both
To our surprise, though the in-plane electrical resis- resistivities occurred at "370 K, which is close to the
tivity of the composite (8.5 · 10!3 X cm) is still higher glass transition temperature of PSAN copolymer (Fig.
than that of NG (4 · 10!5 X cm), however, it is excellent 9A and B). When temperatures were above 370 K, we
when compared with the data published [2,10,15,19,20]. found that the in-plane resistivity increased, while the
For example, a sample prepared from blending 9 parts through-thickness resistivity continued to decrease with
of NG with 20 parts of polyethylene by weight ratio the increase of temperature. All these phenomena must
had a resistivity of 106 X cm at 20 !C [19]; The room
temperature resistivity of the composites based on A A: Through-thickness
0.012
high-density polyethylene and 15 wt.% of carbon black, B: In-plane
or 15 wt.% of carbon fiber, or 50 wt.% of NG were 16.7,
or 0.13, or 10 X cm [20]; For a nylon-6/EG composite, it
Resistivities( Ω .cm)

was reported that there was a percolation threshold at 0.010

about 0.75 vol.% EG, the electrical resistivity reached B
104 X cm at an EG content of 2.0 vol.%, and then leveled
off with further increase of EG content [2]. We must 0.008
point out that the in-plane electrical resistivity of
8.5 · 10!3 X cm for the PSAN/EG composite is much
lower than that (0.11 X cm) of the compressed EG with
the density = 0.03 g cm!3 [21]. The through-thickness 0.006
300 320 340 360 380 400 420
electrical resistivity (1.2 · 10!2 X cm) of the composite
temperature (K)
is lower than that (1.2 · 10!1 X cm) of the NG, and also
lower than that (0.1 X cm) of the compressed EG [21]. Fig. 9. Variations of (A) through-thickness resistivity and (B) in-plane
The possible reason is that the upper and bottom sur- resistivity of PSAN/EG composite sheets with temperature.

Table 3
Resistivities of NG, compressed EG and PSAN/EG composites at room temperature
Directions Nature graphite (X cm) [5] Expanded graphite (X cm) [21] Composites (X cm)
Through-thickness 1.2 · 10!1
1.1 · 10 !1
1.2 · 10!2 ± 0.1 · 10!2
In-plane 4.0 · 10!5 1.0 · 10!1 8.5 · 10!3 ± 0.4 · 10!3
 G. Zheng et al. / Carbon 42 (2004) 2839–2847 2847

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