J O U R N A L OF M A T E R I A L S S C I E N C E L E T T E R S 13 (1994) 3 7 4 - 3 7 7

Effect of sulphur on formation of vapour-grown carbon fibre

T. KATO, K. KUSAKABE, S. MOROOKA*

Department of Chemical Science and Technology, Kyushu University, 6-10-1, Hakozaki, Higashi-ku, Fukuoka
812, Japan

The formation of vapour-grown carbon fibre

(VGCF) has been investigated by several groups
[1-11]. They have reported that the yield of VGCF
is greatly promoted in the presence of ion catalyst
and sulphur species [4, 10, 11]. Egashira and colleagues [8-10] found that sulphur-containing carbon
beads were useful as the substrate for VGCF
growth. They also obtained VGCF from hydrogenbenzene-hydrogen sulphide mixture at a dense
population (104-105 mm -2) on an activated carbon
surface [10]. Matsumoto et al. [3] and Kato et al. [4]
prepared VGCF at up to 69 wt% yield using an
aerosol reactor in the presence of thiophene. Matsumoto et al. [11] investigated the effect of sulphur
compound on the morphology of fibres and products
yields. They reported that sulphur was effective over
a range of S/Fe ratio from 0.17 to 0.52. However,
the role of sulphur in fibre formation has not been
elucidated.
In this study, we prepared VGCF by pyrolysis of
benzene in the presence of sulphur and iron catalyst
particles and considered the role of sulphur. The
seeding of catalyst particles was performed by two
methods: aerosol seeding and substrate seeding.
The aerosol reactor used was a 6 cm diameter and
1 m long mullite tube. Reactants were benzene as
the carbon source, ferrocene as the iron source, and
thiophene or hydrogen sulphide as the sulphur
source. The concentration of iron in the liquid
mixture was 1.0-1.72 wt %. The liquid was vaporized in an evaporating chamber and was carried by
hydrogen into the reactor, which was heated to
1150 C. The concentration of benzene in hydrogen
was 4.2-7.4 vol %. The iron catalyst particles were
generated in situ by the cracking of ferrocene, and
the ratio of S/Fe was 0-1.05.
When a granular activated carbon (GAC) pellet
was used as the substrate, On the other hand, a
mullite tube of 35 or 24 mm inside diameter and 1 m
length was used as the reactor. The reaction temperature was 1000-1150 C. Reactants were benzene
as the carbon source and thiophene or hydrogen
sulphide as the sulphur source. The concentration of
benzene in hydrogen was 5-12 vol% and that of
thiophene or hydrogen sulphide was 0-2.6 vol%.
G A C pellets approximately 5 mm in diameter,
pretreated with concentrated nitric acid, were impregnated with haematite (ol-Fe203) particles [12]
approximately 70 nm in size. Six impregnated GAC
pellets were placed in the reactor and were heated to
800 C in a nitrogen atmosphere. Then nitrogen was
* A u t h o r to w h o m all correspondence should be addressed.

374

replaced by hydrogen, the temperature was raised to

1000-1150 C, and iron was reduced. The reaction
was started by introducing the carbon source into the
reactor. Details of the experimental set-up and
procedure were described earlier [4, 13, 14].
Light tar was collected in a tar trap cooled with
dry ice-ethanol, while heavy tar deposited on the
walls of the reactor was washed out with tetrahydrofuran and collected by evaporating the solvent.
Exhaust gas passing through the tar trap was
collected in a gas sampling bag. Gas and tar samples
were analysed with a gas chromatograph. Solid
products were characterized using scanning electron
microscopy (SEM) (Hitachi S-2300), transmission
electron microscopy (TEM) (Jeol JEM-200BS)
and analytical TEM (Jeol JEM-2000FX) equipped
with an energy dispersive X-ray analyser (EDXA)
(Tracor-Northern TN-2000).
Fig. 1 shows TEM micrographs of solid products
obtained with the aerosol reactor. The morphology
of the product was affected by the S/Fe ratio and did
not depend on the sulphur source. With no feed or
sulphur source, the major products were globular
soots containing ultrafine iron particles. When the
S/Fe ratio was increased to 0.35, VGCF was formed
preferentially. As shown in Fig. 2, the presence of
sulphur greatly increased the VGCF yield based on
the total mass of carbon supplied. The yield of
VGCF was independent of Sulphur source and did
not increase with increasing S/Fe ratio. However,
the fibre diameter at S/Fe = 1.05 was approximately
50 nm, which was smaller than that at S/Fe = 0.35.
This suggests that there is an optimum S/Fe ratio for
VGCF formation.
To investigate the effect of sulphurization, ultrafine iron catalyst particles were formed in the
presence of sulphur in a hydrogen atmosphere at
800 C. The reactants were ferrocene as the iron
source and hydrogen sulphide as the sulphur source.
The ferrocene was dissolved in benzene and pumped
into the inlet tube, which was equipped with an
evaporating chamber. The concentration of ferrocene in hydrogen was 0.2 vol %, and the S/Fe ratio
was changed in the range of 0-0.35. Fig. 3 shows
TEM micrographs of ultrafine iron particles. The
average diameter of iron particles produced without
sulphur was around 21 nm, and that with hydrogen
sulphide
(S/Fe = 0.35) was around
67 nm.
T E M - E D X A analysis reveals that iron particles
formed with hydrogen sulphide contain a small
quantity of sulphur, similarly to an iron particle
trapped in a fibre tip [4]. Thus, sulphur reduced the
melting point of the iron catalyst and accelerated the
0261-8028 1994 Chapman & Hall

60
50

4O

"O

a0
2O

10
0

0.2

0.4

0.6

0.8

1.0

1.2

Atomic S / Fe ratio

Figure2 Relationship between VGCF yield and S/Fe ratio.

Reaction temperature 1150 C, Fe concentration in liquid mix and
sulphur source: (), 1.72 wt %, C4H45and (0) 1.72 wt %, H~S.

Figure I T E M micrographs of solid products formed with aerosol

reactor at 1150 C. Sulphur source H2S, S/Fe ratio: (a) 0, (b) 0.35
and (c) 1.05.

diffusion of active species through the catalyst. A t

the same time, the n u m b e r of iron catalyst particles
decreased with increasing S/Fe ratio, owing to an
increase in the melting rate.
The kinetics of V G C F formation on the G A C
substrate surface is fundamentally the same as in the
aerosol reactor [4, 13], but the effect of the sulphur
source is quite different. Fig. 4 is an SEM micrograph of V G C F grown at 1050 C with hydrogen
sulphide of 2.3 vol % in hydrogen. No carbon fibres

Figure 3 TEM micrographs of ultrafine iron particles produced

with aerosol reactor at 800 C. S/Fe ratio: (a) 0 and (b) 0.35.

were formed without sulphur source. As shown in

Fig. 5, the substrate surface was generally covered
with soots and filamentous carbon when thiophene
was used as the sulphur source, and V G C F was only
formed under the following conditions: reaction
temperature=ll50C,
benzene gas concentration = 10-16 vol %, and thiophene gas concentration = 1.7-2.5 vol %. The population density of the
375

Gas

Light tar

Heavy tar

Coke and soot

0

Figure 4 SEM micrograph of VGCF produced with hydrogen

sulphide. Reaction temperature 1050 C, reaction period 15 min.

20

40
Yield (wt%)

60

80

Figure 6 Distribution of pyrolytic product yield at 1100 C: ([]),

benzene + HzS; (11)benzene.

TAB LE I Conversionof benzene

Figure5 SEM micrograph of products formed on a substrate

surface with thiophene. Reaction temperature 1050 C, reaction
period 15 rain.

fibre was very low compared to that with hydrogen

sulphide. This suggests that thiophene is not a
suitable sulphur source for VGCF production by the
substrate method.
The above-mentioned effect of sulphur source on
VGCF formation was not observed for the aerosol
method. In an aerosol reactor, a vaporized ferrocene
is injected together with benzene and sulphur
source, and iron catalyst particles formed by the
cracking of ferrocene react with gaseous reactants
immediately. T E M - E D X A analysis reveals that
iron catalyst particles directly sampled upstream of
the fibre growing zone already contained sulphur. In
the substrate method, on the other hand, a certain
time period is needed for gaseous reactants to
encounter iron catalyst particles on the substrate
surface. Thus, the timing of contact between reactants and iron catalyst particles seems to be an
important factor.
Fig. 6 illustrates the distribution of pyrolysis
products of benzene in the presence of sulphur in a
hydrogen atmosphere at 1100 C. The reactor was
the same as above, and the residence time of the gas
in the heated zone was 4.2 s. The atomic ratio of
carbon to sulphur was fixed at 9.6, and no iron
source was fed. Major gas components were methane, ethane, ethylene and acetylene. Light tar
consisted of C6-C16 hydrocarbons such as benzene,
376

Reactant

Conversion(%)

C6H6+ H2S
C6H6(S-free)

38.7
46.6

toluene, xylene, naphthalene, methylnaphthalene,

biphenyl, fluorene, phenanthrene, fluoranthene and
pyrene. Acetylene was detected only in the presence
of sulphur. The conversion of benzene is listed in
Table I. These results indicate that excess pyrolysis
of benzene was inhibited in the presence of
hydrogen sulphide.
In conclusion, the formation of vapour-grown
carbon fibres was greatly promoted in the presence
of sulphur and was affected by sulphur species. It
was understood that sulphur accelerated the diffusion of active species through iron catalyst particles
and retarded the formation of coke.

Acknowledgements
We thank Dr K. Murata of Mitsui Engineering and
Shipbuilding Co., Ltd, and Dr H. Katsuki of the
Ceramics Research Institute of the Saga Prefectural
Government for valuable discussion. The experiment was partially carried out by Mr K. Haruta. We
are also indebted to the Research Laboratory of
High Voltage Electron Microscope of Kyushu
University.

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Received 30 June
and accepted 5 October 1993

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