Vacuum xxx (2015) 1e6

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Vacuum
journal homepage: www.elsevier.com/locate/vacuum

Carbon nanomaterials synthesized using a spray pyrolysis method

Wen-Ko Huang a, Kun-Ju Chung a, Yih-Ming Liu b, *, Ming-Der Ger b, Nen-Wen Pu c,
Meng-Jey Youh d
a
School of Defense Science, Chung Cheng Institute of Technology, National Defense University, 335 Taiwan, ROC
b
Department of Chemical & Materials Science, Chung Cheng Institute of Technology, National Defense University, 335 Taiwan, ROC
c
Department of Photonic Engineering, Yuan Ze University, 335 Taiwan, ROC
d
Department of Information Technology, Hsing Wu University, 335 Taiwan, ROC

a r t i c l e i n f o a b s t r a c t

Article history: Carbon nanomaterials were synthesized using a spray pyrolysis chemical vapor deposition system
Received 29 June 2014 (SPCVD). By varying the reaction temperature or flow rate of the carbon source, the structure or
Received in revised form morphology of the synthesized carbon nanocoils (CNCs) can be controlled. A vertical chemical vapor
1 February 2015
deposition (CVD) furnace with a three-stage heating zone was employed to synthesize carbonaceous
Accepted 4 February 2015
nanomaterials using nano-Pd catalysts at growth temperatures of 600, 700, and 800
C. The morphology
Available online xxx
of the synthesized carbon products and the relationship between the carbon source concentration and its
yield were evaluated. The results showed that CNCs formed at a lower temperature (600
C), whereas
Keywords:
Carbon nanomaterials
straight carbon nanotubes were obtained at a higher temperature (700 or 800
C). The structure and
Spray pyrolysis morphology of the carbonaceous samples were observed using scanning electron microscopy (SEM) and
Carbon nanocoil (CNC) transmission electron microscopy (TEM). Their graphite crystallinity was analyzed using Raman spec-
Octopus-tentacle structure troscopy. When the three heating zones of the vertical CVD chamber were set to different temperatures,
a unique nano-carbonaceous material with a special morphology similar to an octopus tentacle was
formed.
© 2015 Elsevier Ltd. All rights reserved.

1. Introduction
Carbon nanocoils (CNCs) and straight carbon nanotubes (CNTs)
have attracted considerable attention in recent years because of
their unique mechanical and electrical properties [1e9]. Due to
their special helical structure, CNCs have the potential for appli-
cations in different fields such as hydrogen storage media [1], mi-
crowave absorbers [2], field emitters [3], microsensors [4], elastic
materials [5], composite materials [6], electrode materials [7], and
catalyst supports [8,9].
CNCs were first synthesized by Motojima and coworkers [10].
Using a nickel substrate or nickel powder as a catalyst, they syn-
thesized coiled carbon microfibers [11] and suggested a growth
mechanism based on the anisotropic extrusion of carbon over a
catalyst particle [10,11]. Tang et al. synthesized helical CNTs and
helical carbon nanofibers (HCNFs) on Fe nanoparticles and per-
formed systematic experiments to investigate the specific effect of
* Corresponding author.
E-mail address: takululiu@gmail.com (Y.-M. Liu).
catalyst particle size on the selective growth of CNCs [12]. In 2001,
Wen et al. successfully used acetylene as the carbon source and
NiePeCl composite catalysts to grow helical CNCs; they fabricated
several CNC structures including solid and hollow coils [13]. Qin
et al. used copper nanocrystals as a catalyst and acetylene as the
source gas at a low temperature of 195
C [5].
According to the literature, CNCs were generally synthesized
using thermal chemical vapor deposition (TCVD) with metal par-
ticles as catalysts, methane or acetylene as the carbon source, and
argon as the carrier gas. The common metal catalysts used for
growing CNCs include iron (Fe) [12], nickel (Ni) [13], cobalt (Co)
[14], and copper (Cu) [5].
In recent years, precious-metal catalysts, such as silver (Ag) [15],
gold (Au) [16], titanium (Ti) and palladium (Pd) [17], have also been
used for growing CNCs. Chiu and coworkers used liquid-phase
metallic K with Ag or Au as the catalyst to grow amorphous CNCs
from acetylene on Si substrates; they proposed a vapor-liquid-
solid-growth mechanism for explaining the CNC growth [15,16].
Nitze et al. used C60-supported Pd-catalyst particles at 550
C to
grow HCNFs [17]. Using Pd nanoparticles, they could grow homo-
geneous CNCs with a highly periodic pitch and diameter.

http://dx.doi.org/10.1016/j.vacuum.2015.02.003
0042-207X/© 2015 Elsevier Ltd. All rights reserved.

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2 W.-K. Huang et al. / Vacuum xxx (2015) 1e6

Although the traditional TCVD method is a simple and inex-

pensive process for producing high purity CNCs effectively, the CNC
yield of this method is poor and unfavorable for industrialization.
Baddour et al. have grown CNTs on stainless steel particles with
CVD in a fluidized bed system (FBCVD) to increase the yield [18].
However, compared with the traditional TCVD methods and
FBCVD, the spray pyrolysis method (SPCVD) has many advantages
such as the possibility of a substrate-free, continuous reaction, and
shorter heating or cooling time for the furnace [19e22]. This
method can be easily applied for the mass-production of nano-
carbonaceous materials and is therefore more favorable for
industrialization.
Aguilar-Elguezabal et al. successfully used spray pyrolysis of a
ferrocene/benzene mixture to produce aligned, multiwalled carbon
nanotubes (MWCNTs) [22]. Su et al. demonstrated a simple tech-
nique that involved dissolving ferrocene in alcohol and sprayed the
solution into the reaction zone for the continuous production of
high-purity, single-walled carbon nanotubes (SWCNTs) [20]. Zhang
et al. used spray pyrolysis of ethanol to synthesize carbon nano-
fibers from carbon particles [23].
However, using the SPCVD method to produce pure CNCs has
yet to be reported. In this study, we used poly(styrene-co-NIPAAm)/
Pd nanoparticles [24] as a catalyst to synthesize carbonaceous
samples with the spray pyrolysis method in a vertical CVD reactor.
The morphologies of the synthesized carbon products were Fig. 1. Schematic of our vertical spray pyrolysis CVD reactor.
observed and their yield was evaluated.

2. Experiments
2.1. Spray-liquid preparation
We added a typical poly(styrene-co-NIPAAm)/Pd catalyst solu-
tion into ethanol and sonicated the mixture for 10 min to disperse
the Pd catalysts homogeneously. The Pd nanoparticles then
exhibited satisfactory dispersion in the ethanol without any
surfactant.
20e30 nm, as shown in Fig. 2c, d. When the growth temperature
was increased to 800
C, thinner CNTs with a diameter of approx-
imately 15e20 nm were obtained, as shown in Fig. 2e, f.
According to Baker's theory [25], carbon atoms decomposed
from a carbon source gas diffuse into the catalyst particles and
precipitate on the surface to form carbon fiber, due to the

2.2. Synthesis of carbonaceous samples by using spray pyrolysis

chemical vapor deposition

Fig. 1 shows the schematic of our SPCVD reactor, which com-

prises a spray nozzle, a vertical heating furnace, a quartz tube, and a
powder collector. The Pd/C2H5OH-mixed liquid was pumped into
the vertical CVD chamber with compressed argon gas, hydrogen,
and acetylene, to grow carbonaceous products at a temperature of
600e800
C. The synthesis period was 1 h. The synthesized
nanocarbonaceous products on the Pd catalysts were then
observed using scanning electron microscopy (SEM) and trans-
mission electron microscopy (TEM). Their graphite crystallinity was
analyzed using Raman spectroscopy.

3. Results and discussion

3.1. Effect of growth temperature on the morphology of synthesized

CNCs

Fig. 2 shows the SEM and TEM images of the carbonaceous

products synthesized on Pd nanoparticles at various temperatures
(i.e., 600, 700, and 800
C). The gas flow rates of Ar, H2, and C2H2 are
5000, 100, and 25 sccm, respectively. The samples synthesized at
600
C is mainly CNCs (Fig. 2a), with very few straight CNFs, as
indicated by the arrows. The CNCs grown at 600
C have a solid
helical structure and their diameter is approximately 100e150 nm, Fig. 2. SEM and TEM images of the nano-carbon samples synthesized at different
as shown in Fig. 2a, b. By contrast, the curly CNTs grown at 700
C growth temperatures: (a) (b) 600
C, (c) (d) 700
C, and (e) (f) 800
C with vertical
have a hollow structure and a diameter of approximately SPCVD reactor. The arrows in (a) indicate the few CNFs as the minority type of material.

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 W.-K. Huang et al. / Vacuum xxx (2015) 1e6
temperature gradient in the catalyst particles. Because the
decomposition of the carbon source and the diffusion of carbon
atoms in the catalyst particles are thermally activated reactions,
they obey the Arrhenius equation and are sensitive to the reaction
temperature. Our results indicated that the acetylene decomposed
more slowly at a lower temperature and the carbon diffused and
deposited more slowly at 600
C to form helical CNCs mostly and a
few straight CNFs; at a higher temperature (700 and 800
C), the
acetylene decomposed quickly to provide a greater abundance of
carbon atoms and a quicker diffusion and deposit rate to form curly
and thin CNTs.
The HR-TEM images in Fig. 3a and b show the microstructures of
the CNTs and CNCs, respectively. Unlike the crystalline structure of
CNTs, our CNCs showed a composite structure with some nano
graphite crystallites (indicated with arrows and circles) embedded
in the amorphous matrix.
In recent years, several research teams, including us, have used
CNCs as the cathode material to fabricate field emission lamp (FEL)
devices [26,27]. The results of these previous studies have indicated
Fig. 3. The HR-TEM micrographs of the CNT (a) and CNC (b) structures in this work.
The arrows and circles in (b) indicate the nano-graphite crystallites embedded in the
amorphous matrix.
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3
that CNC cathode materials can effectively increase the lighting
uniformity and light-spot density of FELs. In this work, the CNTs
and CNCs synthesized at 800
C and 600
C had high aspect ratios
and low turn-on electric fields (as low as approximately 1.1 V/mm
and 2.1 V/mm, respectively).
The Raman spectroscopy analysis of the aforementioned
carbonaceous samples is shown in Fig. 4. There are two main peaks
in the figure: the peak at 1324 cm-1 is the D-band due to structural
defects or disorders in the carbonaceous nanomaterials; the peak at
1580 cm-1 is the G-band, which is related to the graphite lattice.
When the temperature increased from 600
C to 800
C, the ratio of
ID/IG was increased from 0.63 to 0.67, implying that the graphite
crystallinity of the CNTs is superior to that of the CNCs.
3.2. Relationship between CNC yield and acetylene flow rate
Fig. 5a and b shows the morphologies of CNCs grown at the C2H2
flow rates of 50 and 100 sccm, respectively; the gas flow rates of Ar
and H2 were kept at 5000 and 100 sccm, respectively. Compared
with the CNCs shown in Fig. 2a, which were grown using 25 sccm
C2H2, no apparent morphological difference was observed among
these three samples, except that some straight CNFs were present
in the 25 sccm C2H2 sample, as indicated by the arrows in Fig. 2a.
The results indicated that a change in the concentration of the
carbon source gas did not alter the fundamental morphology of the
CNCs. However, the growth rate (mg/hr) of nanocarbonaceous
materials increased when the C2H2 flow rate increased, as shown in
Fig. 6. Also note that the fractions of CNCs in the synthesized
carbonaceous materials with the C2H2 flow rates of 25, 50, and 100
sccm were 85, 94, and 96%, respectively. This fraction was calcu-
lated from the ratio of the total area of CNCs to that of all nano-
carbonaceous materials on the SEM images. As mentioned in
Fig. 4. Raman spectra of the carbonaceous samples synthesized at different
temperatures.
4 W.-K. Huang et al. / Vacuum xxx (2015) 1e6
Fig. 5. The SEM images of the nano carbon samples synthesized at different C2H2 gas
flow: (a) 50 sccm and (b) 100 sccm.
Sec.3.1, CNCs (coiled shape; diameter ~ 100e200 nm) can be easily
distinguished from CNTs (straight; diameter ~ 20e30 nm) and CNFs
(straight; diameter >100 nm) by the shape and diameter.
Fig. 6 shows that the growth rate of CNCs increased from
approximately 1 mg/h (25 sccm C2H2) to approximately 3.5 mg/h
(50 sccm C2H2), and then to approximately 4.5 mg/h (100 sccm
C2H2). The growth rate exhibited a larger increment when the C2H2
flow rate increased from 25 to 50 sccm. The reason for the larger
increment of the growth rate between the 25 and the 50 sccm C2H2
Fig. 6. Growth rate vs. the flow rate of acetylene: (a) 25, (b) 50, and (c) 100 sccm.
Please cite this article in press as: Huang W-K, et al., Carbon nanomaterials synthesized using a spray pyrolysis method, Vacuum (2015), http://
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flow rates may be attributed to the lower quantity of decomposed
carbon atoms at the 25 sccm flow rate, which was not sufficient for
all of the Pd catalysts passing through the heating zones to react.
When the flow rate of C2H2 increased to 50 and 100 sccm, more Pd
catalysts could participate in the reaction with the abundant carbon
atoms, resulting in an increased growth rate. Because the limit of
our C2H2 controller in the TCVD system was 100 sccm, we could not
identify the optimal value of the C2H2 flow rate. However, we ex-
pected the growth rate to increase with the C2H2 flow rate, ac-
cording to the exponential function.
The spray pyrolysis method has many advantages such as the
possibility of a catalyst support-free, continuous reaction, and
shorter heating or cooling time for the furnace [19e22]. We have
compared the yield of our method to those using similar tech-
niques, as shown Table 1. The “yield”, in compliance with the
commonly adopted definition in other works, should be calculated
from the following equation:

.
yield ¼ mtotal  mcatalyst mcatalyst  100%;
where mtotal and mcatalyst are the total material mass (including
catalysts) after CVD and the catalyst mass, respectively.
In Table 1, Nitze et al. used C60-supported Pd-catalyst particles to
grow HCNFs at 550
C [17]. Using Pd nanoparticles, they could grow
homogeneous CNCs with a highly periodic pitch. However, their
yield was limited to that allowed by a typical CVD method. Corrias
et al. [28] produced CNTs by a fluidized bed method in a vertical
CVD furnace. They used Fe/(Al2O3) as the catalyst particles while
mesoporous alumina (Al2O3) particles were introduced as the
initially fluidized powder. The carbon yield often exceeded 95%
with close to 100% selective growth of nanotubes.
Su et al. [20] used a simple technique that involved dissolving
ferrocene in alcohol and sprayed the solution into the horizontal
CVD reaction zone for the continuous production of high-purity
SWCNTs. Their method offered a yield of nanocarbonaceous ma-
terials up to 50%. In contrast, the yield of our vertical CVD geometry
with Pd catalysts and the spray pyrolysis method reached about
128%.
3.3. The special carbonaceous products synthesized in the vertical
three-temperature-zone CVD chamber
To enhance the CNC yield further, we set the temperatures of the
three heating zones of the vertical CVD chamber to 700
C, 650
C
and 600
C, from the top to the bottom, to synthesize carbonaceous
samples. Compared with the isothermal process, this method can
facilitate the pyrolysis of ethanol and acetylene to provide more
decomposed carbon atoms in the top heating zones. Before Pd
catalysts exit the heating zone (middle and bottom stage), the
carbon atoms have more time to diffuse and precipitate to form
CNCs in the Pd catalysts. In our research, using the new heating
method achieved a CNC yield that was eightfold than that from
using the traditional heating method.
In addition, an interesting nanoscale carbon structure with a
special morphology similar an octopus tentacle was found, as
shown in Fig. 7a, b. The TEM observation shown in Fig. 7c, d reveals
that this structure contains two parts; the inner part is a hollow
structure that looks like the CNTs grown at 700
C, as shown in
Fig. 3d; the outside part looks like amorphous carbon deposit,
which surrounds the inner tube.
This structure was rarely reported in the literature. Mishra et al.
demonstrated that gas-flow fields, associated heat, and mass
transfer were not homogeneously distributed during CNF-growth
in a vertical CVD reactor [30]. They proposed a model for solving
 W.-K. Huang et al. / Vacuum xxx (2015) 1e6 5

Table 1
Comparison of catalyst, growth temperature (Tgrowth) and maximum yield (Yieldmax) of synthesis methods in this study and other works.

Type of synthesis methods Products Catalyst Catalyst support Tgrowth Yieldmax Ref.

Typical horizontal CVD CNCs Pd C60 550
C e [17]

Spray pyrolysis (Horizontal CVD) MWCNTs CoeFe silica gel 700
C 33% [19]
Spray pyrolysis (Horizontal CVD) SWCNTs Ferrocene none 1000
C about 50% [20]
Spray pyrolysis (Horizontal CVD) vertically aligned MWCNTs Ferrocene none 750
C e [21]
Spray pyrolysis (Horizontal CVD) MWCNTs Ferrocene none 900
C e [22]
Fluidized bed reactor (Vertical CVD) MWCNTs Fe A12O3 650
C exceeded 95% [28]
Fluidized bed reactor (Vertical CVD) SWCNTs CoeMo MgO 900
C 92% [29]
Spray pyrolysis (Vertical CVD) CNCs Pd none 600
C 128% This work

this problem. It can be inferred that the gas-flow fields, associated
heat, and mass transfer in the vertical CVD reactor were more
complex than in the horizontal CVD reactor.
We speculated that the appearance of this octopus-tentacle-like
structure was due to the following mechanism: some straight CNTs
were preformed at the 700
C zone in the chamber; when they fell
into the lower zones with lower temperatures, the decomposed
carbon atoms at 650
C or 600
C deposited on the surface of the
preformed CNTs, thus forming this special octopus-tentacle-like
structure. We have yet to determine the optimal application for
this carbon structure. However, the hollow center and the rough
and wavy wall surfaces of the octopus-tentacle-like structure can
provide a specific surface area substantially larger than those of
CNTs and CNCs, which suggests various potential applications such
as hydrogen storage media, microwave absorbers, microsensors,
and catalyst supports.
4. Conclusion
In this work, we used a poly(styrene-co- NIPAAm)/pd catalysts
and the SPCVD method with a vertical furnace to synthesize
nanocarbonaceous materials. By adjusting the growth temperature,
we could control the morphology and structure of the nanocarbon
products. Our results indicated that a higher temperature (700 or
800
C) was more conducive to the formation of CNTs, while a
lower temperature (600
C) was more favorable for the synthesis of
CNCs. The growth rate of nanocarbonaceous materials increased
with the increase of the flow rate of the carbon source gas. More-
over, separately setting the temperatures of both the vertical CVD
Fig. 7. The special structure of the octopus-tentacle-like carbonaceous material: (a),
(b) the SEM images; (c), (d) the TEM images.
chamber and heating zones enabled synthesizing a new and
distinctive octopus-tentacle-like carbonaceous material.
Acknowledgments
This work was sponsored by the National Science Council
Taiwan under Grant No. NSC 102-2221-E-606 -005 and by the
Ministry of Economic Affairs, R.O.C., under Academic TDP No. 100-
EC-17-A-07-S1-167.
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