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Carbon 45 (2007) 13301339

www.elsevier.com/locate/carbon

Preparation and characterization of carbon lms prepared


from poly(vinyl alcohol) containing metal oxide
and nano bers with iodine pretreatment
Yuezhen Bin *, Qingyun Chen, Yumiko Nakamura, Kumiko Tsuda, Masaru Matsuo

Graduate School of Humanities and Sciences, Nara Womens University, Japan


Received 4 September 2006; accepted 11 January 2007
Available online 24 January 2007

Abstract
This research focused on the combination of catalyst eect of metal oxide, thermal conductive eect of carbon nano bers and iodine
pretreatment during carbonization of polymer precursor in order to prepare tough carbon lms. Poly(vinyl alcohol) (PVA) composites
containing metal oxide (Fe3O4) and vapor-grown carbon bers (VGCFs) were prepared by gelation/crystallization method with the
freezing/thawing technique. The dry gel lms as precursor were pretreated in the atmosphere of vapor iodine, and then heat-treated
at 6001200 C. The combined eect of iodine, Fe3O4 and VGCF on the carbonization of PVA was analyzed with thermo-gravimetric
analysis, X-ray diraction, and scanning electron microscope in details. Iodine pretreatment for 24 h signicantly promoted the dehydration of PVA, and resulted the carbon lm with a high crystallinity. Fe3O4 as catalyst facilitated the carbonization of PVA at a
low temperature of 800900 C. The addition of VGCFs was found to play an important role to prepare tough lms by mild carbonization due to its high thermal conductivity. The degree of graphitization in the carbon lm depended on the ller contents, pretreatment
conditions and carbonization conditions. The graphitization degrees for G- and T-components in the lm were investigated on the basis
of X-ray diraction intensity distribution from the (0 0 2) plane.
 2007 Elsevier Ltd. All rights reserved.

1. Introduction
Among the various types of lm materials, carbonaceous materials are widely utilized for the application, such
as energy storage, catalyst and air purication [1]. To date,
poly(furfuryl alcohol) [2], poly(vinylidene chloride) [3],
phenolic resin [4], and polyimide [513] etc. have been used
to produce carbon materials. Among the polymeric precursors, poly(vinyl alcohol) (PVA) is also known to be easy to
prepare the lm by the gelation/crystallization method
from dimethyl sulfoxide (DMSO) solution due to its
water-solubility [14,15]. As a member of vinyl polymers,

Corresponding authors. Tel./fax: +81 742 20 3462.


E-mail addresses: yuezhen@cc.nara-wu.ac.jp (Y. Bin), m-matsuo@
cc.nara-wu.ac.jp (M. Matsuo).
0008-6223/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2007.01.007

PVA has been used to produce carbon materials because


of its high carbon content.
However, a large mass loss will take place if PVA carbonization is in air directly [16]. Hence, some additional
treatment to enhance the thermal stability must be done
prior to carbonization, and this treatment was usually
called stabilization [17]. Since most of vinyl polymers are
thermal decomposed only at the temperature slightly
higher than their melting points, it is dicult to stabilize
them by heat-treatment at low-temperature in air [16]. As
reported by Sashio and Tanaka [18], the treatment with
chemical agents can improve its stabilization. In this
research, the iodine treatment was carried out as the stabilization process.
Inagaki et al. investigated the catalyst eect of metal
oxide such as Fe2O3, Fe3O4 and NiO in pyrolysis and
carbonization of polymer in details [19,20], and they

Y. Bin et al. / Carbon 45 (2007) 13301339

2. Experiment
2.1. Preparation of samples
PVA (polymerization of 2000 and 98% hydrolyzed) was used as
matrix. Fe3O4 black (093-01035) was purchased from Wako pure chemical
industries, Ltd. VGCFs with average diameter (D) of ca. 150 nm and with
the length (L) of 1020 lm were kindly furnished by Showa Denko Co.
Ltd. The llers and PVA were used as-received without further
purication.
PVA/Fe3O4/VGCF lm was prepared by gelation/crystallization from
dimethyl-sulfoxide (DMSO) and water mixture [23,24]. The DMSO/water
ratio was set to be 60/40. The concentration of PVA against the mixed solvent was xed to be 10 g/100 mL. To ensure the high crystallinity of the
resultant lms after carbonization, the mass ratio of PVA to Fe3O4 was
set to be 8 to 2, based on the result of Inagaki et al. [19]. The contents
of VGCFs in the composite lms were 2, 5 and 10 wt%. VGCFs in mixed
solvent of DMSO/H2O were treated with a sonicator (100 W) for 3 h at
room temperature to get a well dispersion. During sonicating, the networks of VGCFs were swollen, and a lot of solvent was absorbed. The
solution became highly viscous. After then, the PVA and Fe3O4 powders
were put into the solution, and the mixture was stirred and heated up to
105 C under nitrogen, and maintained for 30 min at 105 C. The hot
homogenized solution was poured into a Petri dish controlled at 120 C
and made the air bubbles gone. After 15 min, the solution was moved into
a refrigerator controlled at 30 C, thus generating a gel. The freezing/
thawing technique was adapted to take DMSO away [2427]. After ve
cycles of freezing and thawing, the solvent was evaporated at room temperature. The nearly dry lms were dried in vacuum for one day. The
thickness of dry gel lms was ca. 0.5 mm. The resultant lm were cut into
strips with 1 cm width and 5 cm length, and put into a desiccator to evacuate air. After then the lm was treated in saturated iodine vapor at 80 C

for a certain time, and cooled down to 30 C in 30 min. The doped lms
were picked out, washed in ethanol for 1 h and vacuum-dried for 24 h.
One day later, these doped lms were sandwiched in graphite plate with
725 Pa pressure and treated in argon atmosphere to promote carbonization. The specimens were heated from room temperature to the set temperature with a heating rate of 400 C/h, and maintained at the set
temperature for 5 h. After then, the specimen was cooled down to room
temperature naturally.

2.2. Measurements
Thermogravimetric analysis (TGA) measurement of carbonized lms
was done using TG/DTA 6300 (SII Nano Technology Inc.); the sample
was heated from room temperature to 1500 C at a heating rate of
10 C/min under nitrogen. X-ray measurements were carried out with a
12 kW rotating-anode X-ray generator (Rigaku RDA-rA) operated at
150 mA and 40 kV with monochromatic Cu Ka radiation (wavelength
of 0.154 nm). The intensity distribution was measured with a step-scanning device at a step interval of 0.05o, each at a xed time of 100 s, in
the given range of twice the Bragg angle. Wide angle X-ray diraction
(WAXD) patterns were detected with a at camera. The micro structures
were observed by SEM (JSM-6700F, JEOL) at accelerating voltage of
5 kV, which was equipped with EDS.

3. Results and discussion


3.1. Pretreatment and carbonization
The iodine amount doped into the lm is plotted with
the doping time as showed in Fig. 1, in which the iodine
amount was estimated by measuring the weight dierence
before and after doping. The weight of the doped lms
was measured after being washed by ethanol till the solvent
was colorless and transparent, and then dried for 24 h. As
preliminary experiment, we conrmed no weight change of
PVA/Fe3O4/VGCF lms when the lms were heat-treated
at 80 C for several hours without vaporized iodine. The
weight of the lm increased with increasing doping
time, and the weight increase attained the maximum at

VGCF
160

Weight change (wt%)

succeeded to produce a well-crystallized graphite from


PVA powder at low temperature of 11001200 C. In the
previous work, Fe3O4 was also introduced into the PVA
lm in accordance with the method reported by Inagaki
et al. However, the resultant PVA lms were very loose
and brittle. In order to maintain the lm shape, we tried
to introduce the vapor-grown carbon bers (VGCFs) as
skeleten to the PVA lm on the basis of the previous report
that the addition of VGCFs could promote the graphitization degree of precursor smoothly by heat-treatment at low
temperature because of their high thermal conductivity
[21].
In doing so, we prepared the PVA/Fe3O4/VGCF composites as precursor to produce carbon lm. The combined
eect of iodine-pretreatment, admixture of Fe3O4 and
VGCFs on carbonization and/or graphitization was investigated mainly in terms of morphological aspects by using
thermo-gravimetric analysis (TGA), X-ray diraction
(XRD), scanning electron microscope (SEM) equipped
with energy dispersive spectroscopy (EDS). The graphitization degrees for G- and T-components in the carbonized
lm were analyzed on the basis of X-ray diraction intensity distribution from the (0 0 2) plane. The analysis was
done in terms of the comparison between the experimental
and theoretical diraction intensity curves. The theoretical
calculation was carried out by using a concept concerning
the para-crystalline theory proposed by Hoseman and Bagchi [22] from the viewpoint of the lattice uctuation of the
c-axis.

1331

2%
5%
10%

140

120

100
0

10

20

30

40

50

Iodine-doping time (h)


Fig. 1. Weight change of PVA/Fe3O4/VGCF lms as a function of iodine
doping time.

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Y. Bin et al. / Carbon 45 (2007) 13301339

24 h doping. The surface of lm lustered like metal after


iodine doping. At the same time, the amount of doped
iodine was aected by the content of VGCF. As shown
in Fig. 1, the weights of lm with 10 and 2 wt% VGCF
reached 167% and 152%, respectively. The weight increase
depended on the content of VGCFs, indicating that
VGCFs adsorbed iodine. However, at doping time of
50 h, the weight increase of the doped lms decreased
and the lms became brittle. The large movement of amorphous PVA chains was reported to be active around
7585 C [28]. Because of the movement, the embrittlement
of PVA was accelerated on long time treating at 80 C.
X-ray diraction intensity distributions for iodinedoped PVA/Fe3O4/VGCF lms carbonized at 1200 C
were shown in Fig. 2 with the dierent iodine-doping time.
Generally, the appearance of diraction peak from the
(0 0 2) plane indicated that graphite crystal began to form.
Namely, as shown in Fig. 2, the diraction peak from the
(0 0 2) plane of carbonized lms began to appear when
the precursor lm was iodine-doped for 6 h. The peak magnitude became more intense with doping-time increase,
which suggests that the doped iodine promoted the formation of graphite crystal. For the lm doped with iodine for
10 h, the peak from the (0 0 2) plane became more obvious
but the prole was anti-symmetric. The anti-symmetry
indicates the formation of unstable turbostratic structure
with large lattice uctuation between the (0 0 2) planes.
When the lm was iodine doped for 24 h, the diraction
peak of the (0 0 2) peak became more intense, although
the peak still remained the anti-symmetrical prole. For
the 50 h-doped lm, the intensity of peak from the (0 0 2)
plane suddenly decreased and broadened indicating that
over doping is not protable for the carbonization of
PVA lm.
Here it may be noted that the diraction peak intensity
of the (0 0 2) plane for the lms carbonized at 1200 C is less
intense than that reported by Inagaki et al. [19,20], and also
the peak prole is not symmetric. In preliminary experiments, the lm by using PVA and Fe3O4 (except VGCFs)

Fig. 2. X-ray diraction intensity distributions for the PVA/Fe3O4/VGCF


lms carbonized at 1200 C after treatment of iodine-doping for the
indicated time: (a) 0 h, (b) 2 h, (c) 6 h, (d) 10 h, (e) 24 h and (f) 50 h.

were prepared in accordance with the same condition


reported by Inagaki et al. for PVA powders. However,
X-ray diraction peak was less intense than that reported.
Hence the dierent peak intensity is thought to be due to
the dierent characters of PVA and the structure of Fe3O4.
Judging from the curves of Fig. 2e, it maybe conrmed
that the peak prole was strongly aected by the content of
VGCFs for the 24 h iodine-doped composite. The diraction intensity from the (0 0 2) plane suggested that the
graphitization degree of the 24 h-doped lm containing
10 wt% VGCF is higher than that of the lm containing
5 wt% VGCF, indicating that the introduction of VGCFs
plays an important role in promoting carbonization. As
reported before [21], this tendency was essentially signicant for the precursors with large cross-section. This is
probably attributed to the high thermal conductivity of
the VGCF ensuring uniform heat transformation to the
whole cross-section of the specimen during the carbonization. In this research, the degree of the graphitization was
obviously inuenced by the iodine doping. There exists
the best condition to combine the eect of VGCF and
iodine doping, and then the 24 h doped lm with 10 wt%
VGCF was investigated in detail. On the other hand, the
lm with 2 wt% VGCF was too brittle to maintain the lm
shape after carbonization. Thus it is evident that the
VGCFs also acted as skeletons to improve the shape-stability of the lms. Incidentally, it is impossible to nd the
relationship between internal stress, arising during carbonization which resulted from the constraint of the volume
reduction of the matrix by the ller, and the development
of a high crystallized structure as been reported by some
papers [29,30].
3.2. Analysis of the reaction process
Fig. 3 shows the WAXD patterns for the PVA/Fe3O4/
VGCF lms containing 10 wt% VGCFs. For the original
lm, the diraction rings from the (1 1 0) and 1 1 0 planes
of PVA crystallites appeared, but after iodine doping the
diraction rings from (1 1 0) and 110 could not be distinguished by comparing Fig. 3a and b. This suggested that
iodine caused the structure change of PVA during the pretreatment. On the contrary, the strong diraction rings of
Fe3O4 (3 1 1) and (2 2 0) planes showed no change. In comparing with PVA/VGCF composite in our previous report
[15], the diraction intensity from the (1 1 0) and 1 
1 0
crystallites became weak and the diraction from the
(0 0 2) plane of VGCF disappeared by adding Fe3O4. For
the lm carbonized at 800 C, the diraction ring of the
(0 0 2) plane of carbon appeared, indicating that the carbon
had formed. When the lm was carbonized at 1200 C, the
diraction ring from the (0 0 2) plane of carbon became
strong. This means the development of high graphite structures. In addition, as shown in Fig. 3c, diraction rings
from Fe3O4 disappeared and the diraction ring from the
(1 1 0) plane of a-Fe appeared. Following Inagaki et al
[19], the change of Fe3O4 to a-Fe occurred at the tempera-

Y. Bin et al. / Carbon 45 (2007) 13301339

1333

Fig. 3. WAXD patterns for the PVA/Fe3O4/VGCF (10 wt%) lms: (a) original, (b) 24 h-doped, (c) carbonized at 800 C and (d) carbonized at 1200 C.

Weight (%)

-20
-40

24h
o

180 C

-60

240 C

0h
o

380 C

-80

450 C

-100

200

400

600

800 1000 1200

Exo

Temperature (C)

0h

328 C

Endo

ture range from 580 to 800 C during the carbonization of


PVA powder. This was probably thought to be due to the
transition from Fe3O4 to a-Fe completely in this case.
To pursue the further eect of doped iodine, TGA and
its dierentiation (DTA) for PVA/Fe3O4/VGCF lms were
detected, and the proles for the original lm (0 h-doped)
and 24 h-doped one were shown in Fig. 4 as representative
examples. For original (0 h-doped) lm, there exist two
thermal decompositions. One is the thermal decomposition
of PVA which started from around 300 C and completed
below 500 C. The other is the abrupt change in weight
around 620640 C mainly due to the presence of Fe3O4,
relating to the reduction of Fe3O4 to a-Fe [19,20]. A similar
prole was observed as in the case of PVA powder with
Fe3O4 [19]. For the corresponding DTA curve, there are
two main peaks: decomposition of PVA and the reduction
of Fe3O4.
The thermo-gravimetric behavior of the iodine dopedlm is quite dierent from that of the original lm. A slight
decrease of the weight under the heating up to ca. 180 C
may be due to the sublimation of some amount of iodine
adsorbed in the lm. The decomposition in the temperature
range of 180450 C could be divided into three parts; the
steep weight loss up to ca. 240 C, the gentle weight loss
over a region of 240380 C, and the further steep weight
loss at temperature above 380 C. Iodine is known to act
as a catalyst for dehydration of alcohols, especially for tertiary alcohols [28]. The weight loss at the rst stage resulted

24h

220 C
o

172 C

200

400

600

800 1000 1200

Temperature (C)
Fig. 4. TGA (a) and DTA (b) curves measured for the PVA/Fe3O4/VGCF
(10 wt%) lms with 24 h iodine-doping and without iodine-doping (0 h).

from the dehydration of PVA and the thermal reaction of


PVA were assumed as following [18]:

1334

Y. Bin et al. / Carbon 45 (2007) 13301339

The hydrogen iodide formed as an intermediate also can


act as the catalyst. Thus the doped iodine played the significant role of catalyst during dehydration of PVA. Also
from the corresponding DTA curves, two peaks of DTA
curve appeared around 172 and 220 C, due to the sublimation of iodine and dehydration of PVA. The strong peak
concerning decomposition of PVA at around 328 C
became weak indicating the change of thermal stability of
the lm. But this change led to an improvement of the carbonization of PVA. At the same time, it may be noted that
the peak deriving from the change of Fe3O4 became weak.
This was conrmed by the WAXD pattern for the PVA/
Fe3O4/VGCF (shown in Fig. 3). On the other hand, the
total weight loss of precursor at 1200 C was 83% for original (0 h-doped) lm, but only 66% for 24 h doped sample.
Therefore, the combination eect of iodine doping and
addition of Fe3O4 could increase the carbon yield.
In order to pursue the further detailed analysis, the EDS
was used to analyze the elements in the heat-treated lms.
Fig. 5 showed the EDS elemental analysis results of carbon, iodine and iron for the 24 h-iodine doped PVA/
Fe3O4/VGCF (10 wt%) lms carbonized at 600, 800 and
1200 C. The data were collected by scanning a square
area of 1 lm 1 lm of the cross-section. At 600 C, the
intensity of carbon is lower because of the less pronounced
carbonization, while the intensities of iron and iodine
were signicantly higher. With heat-treated temperature
increase, the intensity of carbon increased and the intensities of iodine and iron decreased. Finally, the iodine disappeared while some iron still existed at 1200 C. The
quantitative elemental analysis was listed in Table 1
together with the results at 900 and 1000 C. As listed in
Table 1, the mass of iron decreased gradually from
600 C to 800 C. For the EDS analysis, the reected
X-ray signal was collected. As discussed above, the Fe3O4
reduced to a-Fe in this temperature range. This mass
decrease of iron was assumed that the structure of the carbonized lms at dierent temperature inuenced the reection signal of iron. The mass of iodine also decreased
dramatically from 800 C to 900 C and gradually
disappeared.
3.3. Structure analysis of the carbonized lms
Fig. 6 showed X-ray diraction intensity for the 24 hiodine doped PVA/Fe3O4/VGCF (10 wt%) lm carbonized
at the indicated temperature. The experimental diraction
results were obtained by the correction for air scattering,
polarization and absorption, which were shown as circles.

Fig. 5. Qualitative analysis of EDS for the 24 h-iodine doped PVA/Fe3O4/


VGCF (10 wt%) lms carbonized at dierent temperature for 5 h:
(a) 600 C, (b) 800 C and (c) 1200 C.

The diraction peak was classied into three components


as amorphous region (A), T-component (T) at ca. 26.0
and G-component (G) at ca. 26.5 by curve tting with
three kinds of Gauss function. The intensity from the
respective crystal and amorphous components are shown
as dotted curves and the total intensity from the three components is shown as a solid curve. The total intensity curves
of the three components are in good agreement with the
experimental intensity. G-component is associated with
the graphite structures [31,32] that were not inuenced by
heat-treat temperature. T-component is well known to be
due to turbostratic structures. By carbonization at
1200 C, the formation of G-component becomes more
obvious.
The dotted curves in Fig. 7a and b show the real peak
prole for the G-component in the lms carbonized at
1200 and 800 C, respectively, and those in Fig. 8a and b
show the proles of the corresponding T-component.

Y. Bin et al. / Carbon 45 (2007) 13301339


Table 1
Quantitative elemental analysis of EDS for the 24 h-iodine doped PVA/
Fe3O4/VGCF (10 wt%) lms carbonized at dierent temperature
600 C

800 C

900 C

1000 C

1200 C

C(K)
O(K)
Fe(K)
I(L)

83.57
3.82
5.42
7.19

89.31
2.54
1.10
7.05

98.15
0.36
0.99
0.50

98.42
0.27
1.00
0.23

98.52
0.31
1.12
0.05

Experimental
Calculated
g =0.00001
g =0.01
g =0.03
g =0.04
g =0.06

2.4x104

Intensity

Weight (%)

1335

(1)
(2)
(3)
(4)
(5)

1.6x104

8.0x103
(4) (3)
(5)
(1,2)

0.0

22 23 24 25 26 27 28 29 30 31
2 (o)

Total (A+T+G)

Experiment
A-component
T-component
G-component

Experimental
Calculated
g =0.00001
g =0.01
g =0.03
g =0.04
g =0.06

Intensity

6.0x103

Relative intensity

1200 C

(1)
(2)
(3)
(4)
(5)

4.0x103

2.0x103
(3)
(4)

(5)

(1,2)

0.0

1000 C

22 23 24 25 26 27 28 29 30 31
2 (o)
Fig. 7. Real peak curves for the G-component in the lms carbonized at
(a) 1200 C and (b) 800 C.

900 C

800 C

20

22

24

26 28
2 ()

30

32

34

Fig. 6. X-ray diraction intensity for the 24 h-iodine doped PVA/Fe3O4/


VGCF (10 wt%) lms carbonized at dierent temperature for 5 h.

Intensity

4.0x103
18

(2)

2.0x10

Experimental
Calculated
g =0.00001
g =0.010
g =0.030
g =0.045
g =0.060

(1)
(2)
(3)
(4)
(5)

(1)

(4)
(5)
(3)

22 23 24 25 26 27 28 29 30
2 (o)
3

4x10

(1)
(2)
(3)
(4)
(5)

Intensity

The experimental dotted curves were obtained by using


convolution of two intensity distributions obtained for
quartz particles and each test specimen in order to analyze
the lattice uctuation of the G- and T-components. This
method was described elsewhere [33].
Table 2 showed approximate crystal size and the average
length of the c-axis of the G- and T-components within the
lm carbonized at a certain temperature. The approximate
crystal size was calculated roughly by Scherrers equation,
in which the constant value of K is 0.9.
The obtained values contain experimental error because
of the lm thickness of ca. 150 lm. Because, the diraction
peak is obliged to shift to higher or lower value of the twice
Bragg angle with the lm thickness increase, since the number of the crystal planes deviated from the real reection
point of the optical system increases [33]. Therefore the
ideal analysis must be done by using a very thin lm with
high crystallinity [34]. The crystal size was smaller than that
in the carbon lm derived from polyimide and nickel composites by heat-treatment at 1600 C, and also much smaller than the reported value (300 nm) for natural graphite
crystal [35].

0.0

3x10

Experimental
Calculated
g =0.00001
g =0.010
g =0.030
g =0.045
g =0.060

2x10

(1)
3

1x10

(2)

(5)
(4)
(3)

0
22

23

24

25

26 27
2 (o)

28

29

30

Fig. 8. Real peak curves for the T-component in the lms carbonized at
(a) 1200 C and (b) 800 C.

Here it should be noted that Scherrers equation cannot


be essentially applied to imperfect crystallites but it was
used to estimate the size of imperfect crystallites approximately, to obtain the number of unit cell along the c-axis
needed as a parameter in order to pursue the theoretical

1336

Y. Bin et al. / Carbon 45 (2007) 13301339

Table 2
The result of XRD peak tting
800 C 900 C 1000 C 1200 C

G-component Crystal size (A)


63.7
67.4
68.7
70.8
) 6.73
Average length (A
6.73
6.73
6.73
T-component

)
Crystal size (A
38.6
) 6.86
Average length (A

33.4
6.86

28.2
6.86

27.6
6.86

calculation (see Appendix). The accurate sizes of the imperfect crystallites in the carbonized lms were estimated by
curve tting between the experimental and theoretical
curves by considering the lattice uctuation along the
c-axis, as discussed below.
To pursue the further detailed analysis, the graphitization degrees for the G- and T-component in the lms carbonized at 1200 and 800 C were investigated on the
basis of X-ray diraction intensity distribution from the
(0 0 2) plane. The analysis was done in terms of the comparison between the experimental and theoretical diraction
intensity curves. The theoretical calculation was carried
out by using a concept concerning the para-crystalline theory proposed by Hoseman and Bagchi [22] from the viewpoint of the lattice uctuation of the c-axis. The outline of
the mathematical derivation and the physical meaning of
the parameters used are described in Appendix.
The solid curves in Fig. 7 shows the experimental and
calculated curves of the G-component appeared at 26.5,
while those in Fig. 8 correspond to the T-component
appeared at 26.0. The curve proles for the two components mean the independence of the heating temperature.
The calculation was pursued for the G- and T-components

by changing g-value associated with the lattice uctuation


along the c-axis and N 3 . A suitable value of N 3 was simulated by using an initial value obtained from the crystal size
in Table 2 and the average length c of c-axis. The g-values
were much more sensitive to the peak prole in comparison
with N 3 . As can be seen in these two gures, the peak prole is strongly dependent upon the disordered parameterg Dc=c. A suitable g-value gave the best t
between experimental and calculated intensity curves. The
curves calculated at g < 0.01 for the G-component showed
almost the same proles and also the curve calculated at
g = 0.03 gave the best t to the experimental result for
the lms carbonized at 1200 and 800 C. This means that
the peak for the G-component had small lattice uctuation
and did not provide perfect graphite crystals. Accordingly,
the broad prole for the G-component is found to be
mainly attributed not to the imperfectness (uctuation of
lattice distance) but to the few number of crystal unit. That
is, the curve calculated at g > 0.04 deviates from the experimental result.
Fig. 8a and b shows the comparison between experimental and calculated results of the T-component for the lms
carbonized at 1200 and 800 C, respectively. It is seen that
the curves calculated at g < 0.03 are in poor agreement with
the experimental (dotted) curve, while the curves calculated
at g = 0.06 and N 3 5 for the lms carbonized at 1200 C
and g = 0.045 and N 3 6 for the lms carbonized at
800 C gave the best t. Incidentally, the curves calculated
at N 3 12 were conrmed to provide large derivation from
the experimental (dotted) curves in spite of the selection of
any g values. The calculated results pointed out an increase
in the lattice uctuation along the c-axis with increasing

Fig. 9. SEM images of cross-section of the 24 h-iodine doped PVA/Fe3O4/VGCF (10 wt %) lms carbonized at dierent temperature for 5 h: (a) 600 C,
(b) 800 C, (c) 1200 C and (d) 1200 C (enlargement of the milled lm).

Y. Bin et al. / Carbon 45 (2007) 13301339

1337

Fig. 10. SEM images of cross-section for the 24 h-iodine doped PVA/Fe3O4/VGCF lms carbonized at 1200 C with dierent VGCF content: (a) 0 wt%,
(b) 5 wt% and (c) 10 wt%.

carbonized temperature and these results supports the


decrease of the crystal size in Table 2. Anyway, the results
in Fig. 8 demonstrate that the T-component has small turbostratic structure with the large lattice uctuation.
Based on the X-ray analysis, the microstructures of carbonized lm of PVA/Fe3O4/VGCF (10 wt%) were
observed. Fig. 9 shows the SEM images of cross-section
for the 24 h-iodine doped PVA/Fe3O4/VGCF (10 wt%)
lms carbonized at dierent temperatures. Image (a) indicates that the morphology of the lm carbonized at
600 C was similar to the original lm (not shown in this
paper) with smooth matrix indicating the compact properties in bulk. But the matrix became rough with carbonization process at 800 C, and this tendency was more
considerable at 1200 C. Image (d) with large magnitude
shows the milled fragments in the 24 h-iodine doped
PVA/Fe3O4/VGCF lm heat-treated at 1200 C. Obviously, the layered structure can be seen clearly in the white
frame, indicating that the aky graphite crystals are formed.
Fig. 10 showed the eect of VGCF content on the microstructure of carbonized lm at the same pretreatment and
carbonization conditions. The lm carbonized in the
absence of VGCFs became too brittle to keep lm shape
indicating that lm was composed of aggregation of carbon
powders. As shown in image (a), the cross-section of lm
without VGCF split shows a very few carbonaceous structures. The lm containing 5 wt% VGCFs shows a uniform
cross-section of carbon, and the image (c), VGCF content
being 10 wt%, indicates denser cross-section and some
higher graphitization degree in comparison with image (b).
The dispersion of VGCFs played a signicant role as reinforce bers to maintain the lm shape. Of course, the carbonization improved as supported by X-ray curve in Fig. 2.
4. Conclusion
Carbon lms were obtained by the pyrolysis of iodinetreated PVA/Fe3O4/VGCF lms that were prepared by
gelation/crystallization method from the DMSO/H2O
solution. The combination eect of pretreatment with
iodine doping, addition of metal oxide as catalyst and
VGCFs with high thermal conductivity on the carbonization of PVA precursor was studied in terms of morphological aspects. 24 h-iodine-doping before carbonization was

proved to be very helpful to thermal stability of PVA


and to make a high carbon yield. Iodine acted as a catalyst
for dehydration of PVA. The addition of Fe3O4 as a catalyst for carbonization provided the formation of graphite
crystal by the carbonization at 800 C, and its eect was
inuenced by doped iodine. The addition of VGCFs played
an important role to prepare the carbonized lm by the
mild carbonization. Results from X-ray diraction indicated that the form-ability of graphite structures is sensitive
to the amount of doped iodine and heat-treatment temperature. The turbostratic structures, at least, were formed by
the carbonization at 800 C for 5 h, and were developed
with the carbonized temperature increase. For 24 h-doped
lm with 10 wt% VGCF carbonized at 1200 C, the layered
structures associated with graphite were observed clearly
under SEM.
Appendix
Model (a) in Fig. 11 shows the two-dimensional schematic diagram of lattice arrangement along the c-axis of
graphite crystal, and the model (b) shows the crystal unit
cell. In model (a), cj is a displacement vector denoting the
length of the c-axis of the jth unit cell. Rj denotes a vector
from the center (O) to a carbon atom within the jth unit cell
represented as a solid circle. Judging from that the atom
structure factor fj is only for carbon.
Following Hoseman and Bagchi [22], the function H(c)
for the possibility of nding the nearest-neighbor chain at
a distance of the c-axis is represented as follows:


1
c  c
H c p exp 
1
2Dc2
2pDc2
where c is the average length of the c-axis and Dc2 is the
mean square uctuations of the displacement of the c-axis.
Following the previous mathematical treatments, the normalized diraction intensity is given by
"
Ih

8fc2

 2 
2 # 

1 Dc
2pc
I C h
sin h cos a  l
Zh 
1
2 c
k
N3

2
where h and l are diraction and azimuthal angles, respectively, of the diraction beam, and a is the polar angle between X1 and Z axes. In actual calculation for the curve

1338

Y. Bin et al. / Carbon 45 (2007) 13301339

Here it is of reasonable to consider that the number of


graphite crystal units has distribution. Since the crystallite
size of graphite is much smaller than the irradiated area by
X-ray beam, there exist graphite crystallites with several
sizes within the irradiated area [3638]. In the present paper, the distribution for the number of crystal units is given
by a Gaussian distribution as follows:


N 3 N 3
exp  2r2
N
 3

7
P N 3
P2N 3 1
N 3 N 3
exp

N 3 1
2r2
N3

where N 3 and rN 3 are the average twice number of crystal


units and its standard deviation. Then the average diraction intensity may be given by
hIhi

2N
3 1
X
N 3 1

P N 3

I h
N 23

To give the same peak top between experimental and calculated curves, Eq. (8) is modied as follows:
I cal h

Fig. 11. Model (a) shows the schematic diagram of lattice arrangement
along the c-axis of graphite crystal and model (b), the crystal unit cell.

prole of the (0 0 2) plane, N3 was set to be the twice of the


number of crystal unit (Nc) along the c-axis.
In Eq. (2), Z(h) and Ic(h) are described as follows:


1F
Zh Re
1F

1  2jF j cos

2pc
k

1  jF j

sin h cosa  l jF j2

and
I c h n
where

1  2jF j cos

2pc
k

o2

sin h cosa  l jF j2

2 #
 2 
1 Dc
2pc
sin h cosa  l
jF j exp 

2 c
k
and

"




2pc
2
sin h cosa  l  2jF j
A 2jF j 1 jF j cos
k


2pN 3 1c
N3
 jF j cos
sin h cosa  l
k


2pN 3
N 3 1
2jF j
sin h cosa  l
cos
k


2pN 3  1c
N 3 1
 jF j
sin h cosa  l
6
cos
k

hIhi
I ept
hIhtop i

where hI(h)topi is the peak top intensity of the calculated


intensity hI(h) i and Iexp is the peak top intensity of the corrected experimental intensity. Of course, hI(h)i/hI(h)topi becomes unity at twice the Bragg angle giving the peak top of
the calculated intensity. In the present system, the crystallites are oriented randomly within the lm. Accordingly,
the crystallites oriented at a = 90 can be detected by scanning X-ray counter in the horizontal direction (l = 90).
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