Fuel Processing Technology 87 (2006) 919 925

www.elsevier.com/locate/fuproc

Deoiled asphalt as carbon source for preparation of various

carbon materials by chemical vapor deposition
Xuguang Liu a,b , Yongzhen Yang a,c , Xian Lin a,b , Bingshe Xu a,c,, Yan Zhang a,c
a
Key Laboratory of Interface Science and Engineering in Advanced Materials of Taiyuan University of Technology, Ministry of Education, Taiyuan 030024, China
b
College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China
c
College of Materials Science and Engineering, Taiyuan University of Technology, Taiyuan 030024, China
Received 21 April 2006; received in revised form 24 June 2006; accepted 29 June 2006

Abstract

Various carbon materials, including vapor grown carbon fibers (VGCFs) and carbon trees, were synthesized by chemical vapor deposition in
argon atmosphere, using deoiled asphalt as carbon source and ferrocene as catalyst. Pure carbon microbeads (CMBs) were also obtained by this
method in the absence of ferrocene. The influence of different growth parameters, such as ferrocene content, reaction temperature, retention time
and argon flow rate, was investigated, with respect to morphology and product yield. The products were characterized by field emission scanning
electron microscopy (FE-SEM), high resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD) and Raman spectroscopy.
2006 Elsevier B.V. All rights reserved.

Keywords: Deoiled asphalt; Chemical vapor deposition; Carbon materials

1. Introduction decomposition of hydrocarbons, such as benzene, toluene,

methane, acetylene, ethane, cyclohexane, hexane and so on [119].
Deoiled asphalt (DOA) with resins, asphaltenes, a small For the preparation of carbon materials by CVD method with
quantity of saturates and aromatics, is a carbon-rich by-product DOA as the carbon source, the formation of products depends on
of petroleum processing. With carbon dominating in its the thermal cracking gases from DOA. The species of thermal
elemental composition (C, H, S, O and N), DOA will release cracking gases might take part in the formation process of
CH4, CO, H2, N2, CO2, H2S and low molecular hydrocarbons products through a kind of synergic effects [12,20]. Recently,
upon heat-treatment. Converting DOA into carbon materials our group has reported the preparation of VGCFs from DOA
with high added value is an economically competent route. [20]. The objective of this paper was to give a systematic des-
Chemical vapor deposition (CVD) results in carbon materials cription of the effect of synthesis parameters on carbon materials
with different conformations and microstructures, including vapor by CVD. Ferrocene content, reaction temperature, growth time
grown carbon fibers (VGCFs) [111], carbon nanotubes (CNTs) and argon flow rate were varied in order to study their effect on
[1215], carbon microbeads (CMBs) [1618], carbon trees [19] the morphologies of the products and to find their relationships
and so on, which have attracted much attention due to their special with product yield. The morphology and structure of the pro-
atomic configurations and important applications in engineering, ducts were investigated by field emission scanning electron
such as hydrogen storage, field emission devices and electrode microscopy (FE-SEM), high resolution transmission electron
materials. So far, various carbon materials have been grown by the
Table 1
The analytical data of deoiled asphalt (DOA)
Elemental analysis (wt.%) H/C Softening Carbon
Corresponding author. College of Materials Science and Engineering, (mol mol 1) point residue
C H N S
Taiyuan University of Technology, 79, West Yingze Street, Taiyuan 030024, (C) (wt.%)
China. Tel./fax: +86 351 6010311.
88.11 9.05 1.35 0.42 1.23 199 41.12
E-mail address: xubs@public.ty.sx.cn (B. Xu).

0378-3820/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2006.06.007
920 X. Liu et al. / Fuel Processing Technology 87 (2006) 919925

Table 2 outside the furnace. After the reaction zone was heated in argon
Effect of ferrocene content on form of the products at 900 C for 30 min in argon atmosphere to growth temperature, the reaction was proceeded by
atmosphere of 150 ml/min
moving the quartz tube to make the boat into the reaction zone.
Sample The percent of Mass of products (g) Products' The products were collected from the inner wall of the quartz tube
ferrocene in morphologies in
raw material (%)
Reaction Outlet Residue
reaction zone a
after reaction was finished.
zone of tube in boat The process parameters were varied in the following range:
1 0 0.06 0.06 0.73 CMB ferrocene ratio in the total mass of ferrocene and DOA from 0 to
2 5 0.13 0.13 0.72 VGCF 40%, reaction temperature from 700 to 1200 C, growth time
3 10 0.19 0.11 0.70 VGCF + few AC
from 20 to 50 min, Ar flow rate from 40 to 480 ml/min.
4 20 0.45 0.06 0.58 CNP + CNTs + VGCF
5 30 0.65 0.08 0.57 CNP + CNT
6 40 0.80 0.01 0.48 CNP + CNT 2.3. Characterizations of VGCFs
a
CMB represents carbon microbead; VGCF represents vapor grown carbon
fiber; AC represents amorphous carbon; ACNP represents agglomerated carbon JSM-6700F field emission scanning electron microscopy (FE-
nanoparticles; CNT represents carbon nanotube. (Observed through FE-SEM). SEM) was used to characterize and analyze the morphology of the
products, D/max-3C automatic X-ray diffraction (XRD, CuK)
was used to analyze the phases. Laser Raman spectrum was
microscopy (HRTEM), Raman spectroscopy and X-ray diffrac- performed in Raman spectroscopy instrument (JY-T64000, 488 nm
tion (XRD) techniques. Ar ion laser).

2. Experimental 3. Results and discussion

2.1. Raw materials 3.1. Effect of ferrocene content

Deoiled asphalt was supplied by China University of
Petroleum-Beijing. Ferrocene (A.R.) was chosen as catalyst.
Some analytical data of DOA are shown in Table 1.
2.2. Synthesis
The synthesis of products was conducted in a cylindrical
furnace composed of a horizontal quartz glass tube with an inner
diameter of 32 mm and a length of 1000 mm. 2.0 g of mixed
powder of DOA and ferrocene was placed in a small quartz boat,
which was located at first in the cool zone of the quartz tube
The change of the morphology and yield of the products with
ferrocene content is shown in Table 2 and Fig. 1. Product yield
increased with the increase of ferrocene content from 0 to 40 wt.%.
Fig. 1 shows the FE-SEM images of carbon materials obtained at
different ferrocene contents. CMBs with diameters of 400600 nm
were produced in the absence of ferrocene (Fig. 1a), but the yield
was very low (Table 2). As the content of ferrocene increased up to
5%, VGCFs were obtained with relatively uniform diameters of
150200 nm, smooth surface and high purity, as shown in Fig. 1b.
Fig. 1c is similar to Fig. 1b, but VGCFs were shorter and a small
quantity of amorphous carbon (AC) attached to VGCFs when

Fig. 1. FE-SEM images of the products from DOA-ferrocene mixtures with the content of ferrocene (a) 0, (b) 5%, (c) 10%, (d) 20%, (e) 30%, and (f) 40% in the
reaction temperature zone.
 X. Liu et al. / Fuel Processing Technology 87 (2006) 919925 921

Table 3
Effect of the reaction temperature on the products (reaction time: 30 min, Ar:
150 ml/min, 1.8 g DOA + 0.2 g ferrocene)
Sample Reaction Mass of products (g) Products'
temperature morphologies in
Reaction Outlet of Residue in
(C) reaction zone a
zone tube boat
1 800 0.04 0.01 0.68 ACNP
2 900 0.19 0.11 0.70 VGCF + fewer AC
3 1000 0.35 0.09 0.63 VGCF + fewer AC
4 1100 0.35 0.07 0.66 VGCF + fewer AC
5 1200 0.68 0.04 0.65 VGCF
a
See footnote in Table 2.

ferrocene content changed from 5 wt.% to 10 wt.%. When
ferrocene content reached 20 wt.%, agglomerated carbon
nanoparticles (ACNPs), nanotubes (CNTs) and bulky carbon
fibers were coexistent (Fig. 1d). After that, further increasing
ferrocene induced larger quantity of agglomerated CNPs and a few
of short CNTs (Fig. 1e and f).
It is known that among various factors, which determine the
growth of the VGCFs, catalyst seems to be one of the key
factors [11]. Early studies indicated that the size of metal
particles is one of the important criteria for VGCFs growth and
carbon fibers grown on smaller diameter catalyst particles have
higher growth rate than those grown on larger particles [13].
Carbon atoms from thermal cracking gases of DOA only
deposited on the inner wall of quartz tube to form CMBs in the
absence of catalyst, which is in agreement with Ref. [18]. As
catalyst content increased, the amount and sizes of Fe particles
from ferrocene pyrolysis became appropriate to form VGCFs.
When the content of ferrocene was over 20%, Fe particles
formed in very rapid rate and easily reunited to form less active
agglomerates while the amount of active iron particles became
less, so a part of carbon atoms deposited on iron agglomerates to
Fig. 3. XRD patterns of VGCFs at different temperatures.
form a few of short and thick VGCFs and a lot of ACNPs.
Simultaneously, the rest of carbon atoms deposited on the
surface of highly active iron nanoparticles to form CNTs.
3.2. Effect of reaction temperature
From Table 3, it can be seen the total yield of products
increased with temperature increasing from 800 to 1200 C. Fig. 2
shows the effect of different reaction temperatures on the
morphology of products in reaction zone. In Fig. 2a, ACNPs
were formed at 800 C almost exclusively but with very low yield.
Typical FE-SEM images of VGCFs with varying diameters can
be observed in Figs. 1c and 2bf. VGCFs with central hollow
cores were relatively uniform for different temperatures (Figs. 1c
and 2bc). They did not change obviously in diameters from 900
to 1100 C but their purity became lower with the increasing
temperature. The length of VGCFs at 1000 C was longer than at
other temperatures. When the temperature was further increased

Fig. 2. FE-SEM images of the products from DOA at different temperatures (a) 800 C, (b) 1000 C, (c) 1100 C, and (d) 1200 C. (e) Oriented VGCFs grown on Fe
film at 1200 C, the pinhole of Fe as an arrow shows. (f) The cross-section of a broken fiber in (e).
922 X. Liu et al. / Fuel Processing Technology 87 (2006) 919925

Table 4 Table 5
Effect of argon flow rate on the products (temperature: 900 C, reaction time: Effect of the reaction time on the products (temperature: 900 C, Ar: 150 ml/
30 min, 1.8 g DOA + 0.2 g ferrocene) min, 1.8 g DOA + 0.2 g ferrocene)
Sample Argon Mass of products (g) Products' Sample Reaction Mass of products (g) Products'
(ml/min) morphologies time morphologies in
Reaction zone Outlet of Residue in Reaction Outlet of Residue in
in reaction zone a (min) reaction zone a
tube boat zone tube boat
1 40 0.26 0.09 0.65 VGCF + AC 1 20 0.17 0.08 0.73 VGCF + fewer AC
2 80 0.23 0.11 0.68 VGCF+AC 2 30 0.19 0.11 0.70 VGCF + fewer AC
3 150 0.19 0.11 0.70 VGCF + fewer AC 3 40 0.26 0.09 0.65 Nanofiber
4 300 0.13 0.09 0.69 VGCF + fewer AC 4 50 0.25 0.06 0.65 Carbon microtree
5 480 0.08 0.05 0.71 VGCF + AC a
See footnote in Table 2.
a
See footnote in Table 2.

Moreover, XRD result also reveals the structural feature of

to 1200 C, there were, at least, two types of VGCFs that had quite
different lengths but similar diameter of about 1 m. The shorter
VGCFs with a few micrometres in length are shown in Fig. 2d
while the longer oriented VGCFs, with circular cross-section and
the length of about 2 cm, are shown in Fig. 2ef.
Fig. 2e is a low-magnification micrograph showing that the
oriented fibers, with high purity and very narrow diameter distri-
bution around 1 um, were grown on porous Fe film formed by Fe
atoms from ferrocene pyrolysis. This indicates that the peripheries
of the pinholes of underlying Fe film possibly confined the growth
of oriented fibers. This can be further verified by the fact that
fibers grew perpendicularly from pinholes. This may suggest a
similar mechanism as oriented micro-sized carbon fibers on a
nickel-coated silicon substrate by CVD [9]. In Fig. 2f, the cross-
section of a broken fiber displays concentric, layered structure of
deposited carbon layer. In this work, it is not clear whether fibers
are completely hollow or not, because it is difficult to characterize
fibers via HRTEM due to relatively large dimension of fibers.
Thus, further investigation is needed to clarify the detailed
microstructure of aligned VGCFs.
VGCFs. The higher sharp peak of (002) reflections centered at
26 indicated that graphene layers were regularly stacked and
the degree of graphitization varied indistinctly with the increase
of reaction temperature (Fig. 3).
These results suggest that reaction temperature also had an
important effect on the nucleation and growth process of
VGCFs. The effect can be catalyst particles and the concentra-
tion of pyrolytic gases generated from the precursors. At low
temperatures, catalytic cracking reaction was so difficult that the
yield was very low. Not only was the deposited rate of carbon
atom lower than the formation rate of tubular structure because
of low concentration of pyrolytic gases, but the catalyst was also
unable to play its role at temperatures lower than 800 C, so
carbon fibers couldn't be formed. When the temperature
reached 900 C, iron particles for VGCFs growth began to
exhibit catalytic activity. Small quantities of long and
homogeneous VGCFs were synthesized. Furthermore, in-
creased reaction temperature resulted in improved yield of
VGCFs following enhanced growth rate. At higher reaction
temperatures, the concentration of pyrolytic carbon became

Fig. 4. FE-SEM images of the products from DOA at different argon flow rates (ml/min) (a) 40, (b) 80, (c) 300, and (d) 480.
 X. Liu et al. / Fuel Processing Technology 87 (2006) 919925 923

Fig. 5. FE-SEM images of the products from DOA at different times (a) 20 min and (b) 40 min. (c) The enlarged image in (b). (d) 50 min. (e) The enlarged image in (d).

supersaturated and led to the deactivation of the active surface
of catalyst particles. On the other hand, the overhigh
temperature could induce the agglomeration of catalyst
particles, thus reducing the activity of catalyst and inducing
the formation of VGCFs with low aspect ratio.
3.3. Effect of argon flow rate
The flow rate of carrier gas, argon, directly controls the
duration time of cracking gases and growth of catalyst particles
in the reaction zone. Therefore, the influence of the flow rate of
argon on the yield and morphologies of products was
investigated through changing argon flow rate and fixing
other factors (shown in Table 4 and Fig. 4). Table 4 shows that
the yield of products decreased with increasing gas flow. A
group of FE-SEM images are shown in Fig. 4. It can be found
that VGCFs of 500600 nm in diameter were curled and dumpy
at 40 ml/min argon flow rate (as shown in Fig. 4a). Straight
VGCFs with diameters of 300 nm were obtained and
amorphous carbon particles were also found at 80 ml/min
argon flow rate (as shown in Fig. 4b). The average diameters of
obtained VGCFs with high purity decreased to about 180 nm
when the flow rate was increased to 150 ml/min (as shown in
Fig. 1c). As shown in Fig. 4c and d, though the diameter of
VGCFs became smaller, they had relatively low purity.
When appropriate argon flow rate was used, the residence
time of the pyrolysis gases in the reaction zone was suitable to
enhance collision probability between Fe atoms/clusters and
carbon clusters, thus forming a large quantity of uniform Fe
particles, which provided the sites of nucleation for the inner
core of carbon fibers. It can be deduced that a suitable level of
carrier gas can provide more space for mass growth of VGCFs
with good quality in the reaction zone. However, when the argon
flow rate was very small, the excessive carbon atoms, which
were formed by decomposing pyrolysis gases with high density,
deposited on the surface of catalyst particles to form amorphous

Fig. 6. HRTEM images of VGCFs from DOA (10% ferrocene, 1000 C, 150 ml/min Ar, 30 min). (a) HRTEM images of VGCFs. (b) The enlarged images of the walls of the
VGCFs in (a).
924 X. Liu et al. / Fuel Processing Technology 87 (2006) 919925
Fig. 7. Raman spectrum of VGCFs from DOA (10% ferrocene, 1000 C, 150 ml/min
Ar, 30 min).
carbon layer, resulting in short and thick VGCFs. If the argon
flow rate was high enough to carry the pyrolysis gas out of the
reaction zone too quickly, the catalyst Fe particles do not have
enough time to catalyze the growth of VGCFs despite that the
high flow rate prohibited the aggregation of catalyst particles.
3.4. Effect of deposition time
The experiments were carried out for 20 min, 30 min, 40 min
and 50 min, respectively, and the other conditions were kept the
same. The relationship between products and deposition time is
shown in Table 5. It can be seen that the total yield of products
increased with deposition time prolonged from 20 min to 40 min
and changed vaguely when the deposition time was over 40 min.
There was no sufficient growth period when the experiment went
on for 20 min, thus resulting in lower yield of products. Although
the absolute yield of products increased with increasing depo-
sition time, the concentration of pyrolysis gases became lower.
Therefore, the yield no longer increased when deposition time
reached a certain degree.
The products at various deposition times were observed by FE-
SEM (Fig. 5). Fig. 5 shows that the morphologies of products
varied with increasing deposition time. VGCFs with an average
diameter of 180 nm were obtained and there was not much
difference between the shapes for the two samples obtained with
deposition time of 20 min and 30 min, respectively, as shown in
Figs. 5a and 1c. With the increase of the deposition time, the
appropriate ratio of pyrolysis gases to Ar made smaller Fe
nanoparticles appear. Many curled and wrapped carbon nanofi-
bers (VGCNFs) of 45 nm in diameter are found in Fig. 5bc. As
shown in Fig. 5de, carbon microtrees were obtained when the
experiment was performed for 50 min. The root and branch of the
trees were composed of many carbon nanobeads, as shown in Fig.
5e. On the other hand, the elucidation of the growth model of
carbon microtrees needs further research.
3.5. HRTEM and Raman analysis of VGCFs
Fig. 6 shows HRTEM images of VGCFs using 10% ferrocene
in 150 ml/min argon atmosphere at 1000 C for 30 min. It can be
found that the walls of VGCFs with hollow cores (Fig. 6a) can be
divided into two different structures (Fig. 6b), that is, the high-
graphitized inner layer shells and low-graphitized outer layer
shells. It can be also observed that shuttle-like catalyst particles
are encapsulated in the tips of VGCFs (as an arrow denoted in
Fig. 6a). This result agrees with the general structures of VGCFs
and obeys the vaporliquidsolid growth mechanism [11].
The structure of the samples was also verified by Raman
spectrum, which is shown in Fig. 7. Raman spectrum has two
peaks centered at 1354 cm 1 (D-band) and 1583 cm 1 (G-band).
The G-band is assigned to one of the two E2g modes cor-
responding to stretching vibrations in the basal-plane of graphite.
The D-band may be attributed to the disorder and imperfection of
the carbon crystallites. The high relative intensity of G- to D-band
(IG/ID = 1.08) implies that the obtained VGCFs are mainly
composed of microcrystalline graphite full of defects, in agree-
ment with HRTEM observation.
4. Conclusion
In summary, four experimental parameters evidently influ-
enced the growth of carbon materials, including ferrocene
content, reaction temperature, deposition time and argon flow
rate. An effective mass production of pure VGCFs could be
achieved in argon atmosphere by CVD method using DOA as
carbon source and ferrocene as catalyst under optimized
preparation parameters, that is, 10 wt.% of ferrocene, reaction
temperature of 1000 C, deposition time of 30 min, and argon
flow rate of 150 ml/min. The obtained VGCFs with about
180 nm in diameter were pure, uniform and relatively straight.
Pure CMBs were formed in the absence of ferrocene. VGCNFs
and carbon trees were also produced by this method.
Acknowledgements
This research work was supported by National Basic Research
Program of China (Grant No. 2004CB217808), National Natural
Scientific Foundation of China (Grant No. 20471041, 90306014),
Natural Science Foundation of Shanxi Province (Grant No.
20051018) and Shanxi Research Fund for Returned Scholars
(Grant No. 200428).
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