Synthesis of Carbon Nanotubes by CVD and Spray Pyrolysis and Their

Characterization by Scattering Techniques

J. Bahadur, J. Prakash, D. Sen, S. Mazumder, and D. Sathiyamoorthy

Citation: AIP Conf. Proc. 1349, 275 (2011); doi: 10.1063/1.3605841

View online: http://dx.doi.org/10.1063/1.3605841
View Table of Contents: http://proceedings.aip.org/dbt/dbt.jsp?KEY=APCPCS&Volume=1349&Issue=1
Published by the American Institute of Physics.

Additional information on AIP Conf. Proc.

Journal Homepage: http://proceedings.aip.org/
Journal Information: http://proceedings.aip.org/about/about_the_proceedings
Top downloads: http://proceedings.aip.org/dbt/most_downloaded.jsp?KEY=APCPCS
Information for Authors: http://proceedings.aip.org/authors/information_for_authors

Downloaded 12 Apr 2013 to 180.149.51.69. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://proceedings.aip.org/about/rights_permissions
 Synthesis of Carbon Nanotubes by CVD and Spray
Pyrolysis and Their Characterization by Scattering
Techniques
J. Bahadur1*, J. Prakash2, D. Sen1, S. Mazumder1, D Sathiyamoorthy2
1
Solid State Physics Division, 2Powder Metallurgy Division, Bhabha Atomic Research Centre
Trombay, Mumbai, India, 400085

Abstract. Carbon nanotubes have been synthesized by catalytic chemical vapor deposition and spray pyrolysis methods.
Synthesized nanotubes were characterized by Small-angle neutron scattering, X-ray diffraction and Raman spectroscopy.
Scattering data reveals the aggregated nature of nanotubes, the average diameter and average length have also been
estimated. It has been observed that the nanotubes, synthesized by spray pyrolysis methods, possess fewer defects in
their graphitic nature of wall. The X-ray diffraction data reveals that the nanotubes possess metal oxide impurities.
Keywords: CNTs, SANS, XRD, Raman spectroscopy
PACS: 61.05.C, 61.05.fg, 61.46.Fg, 61.46.Np, 61.48.De

INTRODUCTION length of CNTs.

With the rapidly growing demands of carbon SAMPLE PREPARATIONS

nanotubes (CNT) in applications such as hydrogen
storage and fuel cells [1], there is a major need to To synthesize the CNTs, catalytic CVD and spray
produce bulk CNT and their composites. The major pyrolysis were used. In first case, 10% nickel formate
synthesis techniques which are used basically are was dispersed activated alumina. The nickel formate
electric arc discharge (EAD), laser ablation (LA), dispersed alumina (1gm) was taken in a ceramic boat
chemical vapor deposition (CVD). These methods and kept inside the horizontal quartz tube. Initially, the
involve the reorganization of the carbons released boat with the supported catalyst was allowed to pass at
from carbon source in a tube shape using a nano the flow rate of 1 lpm in order to create the inert
transition metal catalyst. The yield and quality of the atmosphere inside the tube as soon as the desired
nanotubes is the major concerns in the synthesis temperature (750oC) is obtained, the boat is pushed
processes. Synthesis route mostly decides the into the effective heating zone and the acetylene
morphology of CNT. EAD and LA methods to (C2H2) gas was allowed to flow at the rate of 100cc/m
produce CNTs are high temperature processes and can for 15 min in order to synthesize CNTs. After the
produce high quality nanotubes. The CNTs growth of CNT the residue was purified by acid
synthesized by these methods are highly graphitic in treatment process. CNTs were also synthesized by
nature and have random orientation. However, the spray pyrolysis process, which is a special kind of
yields are poor and hence not adoptable for large scale CVD. The experiments where carried out using
production. The CVD and spray pyrolysis methods are benzene as a precursor and ferrocene powder as a
mostly used for the synthesis of CNTs of different catalyst for the growth of CNT. In brief, ferrocene was
morphology. dissolved in benzene to form a solution of 0.06 g/ml
In the present study we have synthesized CNT by which was pumped continuously using peristaltic
catalytical CVD method and spray pyrolysis method. pump into a tubular quartz reactor. The reactor was
These CNTs of different morphology have been cooled down after the deposition and the residue was
characterized by different techniques such as SANS, collected. To obtain self standing tubular architecture
Raman spectroscopy and XRD. SANS technique have with CNTs aligned in the radial direction.
been used to find out the fractional diameter and
Solid State Physics, Proceedings of the 55th DAE Solid State Physics Symposium 2010
AIP Conf. Proc. 1349, 275-276 (2011); doi: 10.1063/1.3605841
© 2011 American Institute of Physics 978-0-7354-0905-7/$30.00

275

Downloaded 12 Apr 2013 to 180.149.51.69. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://proceedings.aip.org/about/rights_permissions
 Characterizations I(q)  CPc (q, r0 , L)Sc (q, r0 )
SANS experiments have been carried out by using where, Pc (q, r0, L) is the form factor of cylinder, r 0 is
a double crystal based medium resolution SANS the average cross section radius of the CNTs, L is the
instrument (MSANS) at the Guide Tube Laboratory of length of the cylinder Sc (q, r0) is the structure factor
the Dhruva rector at Trombay, India [3]. The scattered [4, 5] due to mass fractal type correlation. The
intensities have been recorded as a function of wave parameters obtained by SANS analysis are shown in
vector transfer q [=4πsin (θ)/λ, where 2θ is the Table 1.
scattering angle and λ is the incident neutron
TABLE 1. Parameters obtained by SANS and Raman
wavelength for the present experiment]. SANS profiles
measurements
of the specimens were corrected for transmission and
instrument resolution prior to further analysis (Fig. 1). Specimens Diameter (2 Length Ratio of D and G
r0) (L) band intensities
(nm) (nm) (D/G)
CNT_CVD 40 657 1.273
CNT_spray 21 555 0.804

It is evident form the Fig. 1 that the slopes of the linear

region of SANS profiles are same indicating similar
morphology. However, the diameters of the CNTs of
CNT_spray specimens are smaller than that of the
CNT_CVD. The Raman data show that the defects in
the walls of the CNTs of CNT_spray are less as
compared to that of CNT_CVD.
FIGURE 1. SANS profiles of the CNT specimens prepared
by two synthesis method. Solid lines depict fit to the curve.
To measure the extent of the graphitization of the
nanotubes walls, Raman spectroscopy has been
performed on the both the specimens (Fig.2).
XRD patterns of the powders were recorded using
a rotating anode x-ray generator equipped with Mo
source (Fig. 3) to characterize the phase purity of the
samples.

FIGURE 3. X-ray diffraction data of the CNTs

specimens.

Fig. 3, show the XRD patterns of the pure graphite and

the two CNTs specimens. The data show the presence
of metal oxide impurities in addition to the CNTs. In
case of CNT_CVD specimens, Nickel oxide impurity
and in case of CNT_spray, Iron oxide impurities are
one of the possibilities.

FIGURE 2. Raman spectra of the CNT specimens REFERENCES

prepared by two different synthesis techniques.
RESULTS AND DISCUSSION
SANS profiles in log-log plot in Fig. 1, show a
linear region over a wide q-range for the specimens
implying a network of CNTs. Thus, we envision a
fractal network of CNTs model to explain SANS data.
Scattering intensity I (q) from mass fractal
agglomerate [5, 6] is given as,
1. Y.-H. Chung, S. Jou, Mater. Chem. Phys. 92, 256
(2005).
2. S. Mazumder, D. Sen, T. Sarvanan, P. R. Vijayraghavan,
J. Neutron Research, 9, 39 (2001).
3. J Bahadur, D Sen, S Mazumder, Jyoti Parkash, D
Sathiyamoorthy, and R Venugopalan, J. of Nanosci. and
nanotech., 10, 2963–2971 (2010).
4. D. Sen, K. Dasgupta, J. Bahadur, S. Mazumder and D.
Sathiyamoorthy; PRAMANA-journal of physics, 71, 971-
977 (2008).

276

Downloaded 12 Apr 2013 to 180.149.51.69. This article is copyrighted as indicated in the abstract. Reuse of AIP content is subject to the terms at: http://proceedings.aip.org/about/rights_permissions