www.elsevier.com/locate/carbon
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,
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.
VGCF
160
1331
2%
5%
10%
140
120
100
0
10
20
30
40
50
1332
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
Exo
Temperature (C)
0h
328 C
Endo
24h
220 C
o
172 C
200
400
600
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).
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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
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
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.
1336
Table 2
The result of XRD peak tting
800 C 900 C 1000 C 1200 C
)
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
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).
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%.
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
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.
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
1339