Carbon 41 (2003) 26132617

The evaluation of the gross defects of carbon nanotubes in a

continuous CVD process
Weizhong Qian*, Tang Liu, Fei Wei, Zhanwen Wang, Guohua Luo, Hao Yu,
Zhifei Li
Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
Received 29 August 2002; accepted 24 July 2003

Abstract

Carbon nanotubes (CNTs) were prepared by ethylene decomposition on an Fe /Al 2 O 3 catalyst in a fluidized bed reactor.
Their gross defects at different growth periods are evaluated by using a combination of SEM, TGA and Raman spectroscopy.
The initially grown CNTs have a much lower thermal stability and more defects as compared to the fully-grown ones. The
difference in the defects of CNTs at different reaction times is attributed to the lift up of CNTs with the gradually crashing
texture of catalyst and the increasing volume of CNTs in a limited reactor space.
2003 Elsevier Ltd. All rights reserved.

Keywords: A. Carbon nanotubes; B. Chemical vapor deposition; C. Raman spectroscopy; D. Defects

1. Introduction scale. Especially, the evaluation lacks the time-dependence

Carbon nanotubes (CNTs) consisting of a single carbon
layer or multiple coaxial carbon layers seemingly are ideal
perfect structures [1] with ultra-high mechanical strength,
high electrical and thermal conductivity etc. [2,3]. How-
ever, there are always many defects when the nanotubes
are prepared in a practical process [47]. The defects of
the CNTs, including pentagonal, heptagonal defects and
the pentagonheptagon pairs or even line defects etc.
[810], destroy the symmetry of the carbon layer and
hence decrease its mechanical strength and other properties
and, in consequence, influence their applications seriously.
So far, the following factors have been reported to be
related to the formation of the defects of nanotubes: high
energy (i.e. laser or arc discharge) [5,6], large force
buckling the tubes [7], the kinetic driving force for the
formation of helix-shaped CNTs [11] or zigzag tubes [12]
and the impurities of the catalyst influencing the carbon
diffusion and precipitation in a CVD process [13]. How-
ever, these studies on a micro-scale are unable to provide a
direct indication of the quality of CNTs on a macroscopic
*Corresponding author. Tel.: 186-106-278-9041; fax: 186-
106-277-2051.
E-mail address: qwz@flotu.org (W. Qian).
of defects in the CNTs prepared in a CVD process, which
is important for the quality control of the CNTs. In this
contribution, the combination of SEM, TGA and Raman
spectroscopy is used to evaluate the gross defects of the
CNTs grown in a continuous CVD process. The result is
useful for the understanding of the defect formation and
the quality control of CNTs.
2. Experimental
The CNTs are prepared in a continuous ethylene de-
composition process by an Fe /Al 2 O 3 catalyst [14] in a
fluidized bed reactor. The fluidized bed reactor, described
elsewhere, favors the continuous production of CNTs on a
large scale [14]. To prepare CNTs, 10 g of catalyst
precursor are packed into the reactor and first reduced with
hydrogen at 823 K for 2 h. Then a mixture of nitrogen and
ethylene (99.99% pure, 2:3 volume ratio of nitrogen to
ethylene) is fed into the reactor. The experiment is
conducted at 823 K, atmospheric pressure and an operating
gas velocity of 0.1 m / s for 56 h. The total yield of CNTs
is about 100200 g. CNTs are sampled at certain intervals
of time. The fluidized CNT samples, assumed to be

0008-6223 / 03 / $ see front matter 2003 Elsevier Ltd. All rights reserved.
doi:10.1016 / S0008-6223(03)00341-5
2614 W. Qian et al. / Carbon 41 (2003) 26132617
distributed uniformly in the reactor [14], are sufficiently
repetitive to reflect the change of CNT growth.
The unpurified CNT samples are characterized by
scanning electron microscopy (SEM, LEO1530), HRTEM
(JEOL-2010), Raman spectroscopy (Renishaw, RM2000;
514.5 nm, 1.2 mW) and TGA (TA instruments, TGA 2050;
temperature: 2931273 K; heating rate: 20 K / min; air
atmosphere). The SEM, TGA and Raman characterization
[15,16] can reveal the morphology, thermal stability and
microstructures of CNTs in a relatively large amount as
compared to HRTEM.
3. Results and discussion
The first order Raman spectrum is sensitive to the
change in microstructure of carbon materials [15]. Gener-
ally, the CNTs consist of an ordered graphitic structure
(peak at 15701610 cm 21 , G line) and a disordered
structure or lattice defects (peak at 13201360 cm 21 , D
line). The CNTs sampled at different periods have been
characterized by Raman spectroscopy [14]. In the initial
growth period (06 min), there is no obvious peak found
in the Raman spectrum, indicating that the carbon content
is small and the carbon form is far from perfect. When the
growth time is longer than 16 min, the D line and G line
can be clearly seen for all samples. The intensity ratio of D
line to G line is generally used to evaluate the quality of
CNTs [15]. A high ratio means relatively more defects
inside the carbon layers. As shown in Fig. 1, the ratio is
very high and there is an obviously increasing tendency of
the ratio in the initial period, indicating the CNTs contain
serious defects and there is a significant change in the
initial growth period. When the reaction time is longer than
16 min, the ratio decreases gradually and approaches a
minimum value at 50 min, indicating the microstructure of
Fig. 1. Time dependence of the intensity ratio of D line to G line
in Raman spectra of CNTs (cited from Ref. [14]).
the CNTs at this time is the most perfect. However, the
ratio increases somewhat again when the time is longer
than 100 min. Then it maintains a stable value in the
following period.
Meanwhile, it is found that the CNTs sampled at
different periods have different thermal stability, character-
ized by TGA. As shown in Fig. 2, the burning tempera-
tures for all samples are all higher than 700 K. The result
indicates there is nearly no amorphous carbon, the burning
temperature of which is generally lower than 673 K [16].
Since the peaks characteristic for SWNTs and fullerene are
not observed in the Raman spectra, these results suggest
that the carbon deposited on the catalyst should be all in
the form of MWNTs. The burning temperature of the
initially grown tubes (06 min) is only 774 K. It is far
lower than that of the fully-grown tubes when the reaction
time exceeds 16 min. The burning temperature of the
samples after 16 min remains at a stable level of 850880
K, in a normal range for MWNTs [16]. Also, the tendency
of the carbon content of the products to change with
reaction time is nearly the same as that of their burning
temperature (Fig. 2). The result suggests that the fully-
grown CNTs have a relatively high thermal stability.
The above characterization clearly shows that the initial-
ly grown CNTs have a low thermal stability and more
defects as compared to the fully-grown tubes. Considering
the relationship between the microstructures of CNTs and
its thermal stability, the result of TGA is in agreement with
that of the Raman spectra. Further, these findings are in
agreement with the result of XRD characterization of
CNTs in a fixed-bed reactor [17]. The above results all
indicate that the significant change of the properties of
CNTs mainly occurs in the initial growth period. Here the
SEM images of CNTs are used to understand what occurs
in the different CNT growth periods. Using a relatively
large amount of CNTs without ultrasonic dispersion, the
difference in length of CNTs and the particle size of the
Fig. 2. Time dependence of the carbon content and the initial
burning temperature of the solid products (carbon and catalyst) in
TGA analysis.
 W. Qian et al. / Carbon 41 (2003) 26132617
Fig. 3. SEM image of the initially grown CNTs (sampled at 16
min).
catalyst are observed for different periods. Fig. 3 shows the
initial growth period of CNTs. The bright large spots are
catalyst particles. The catalyst particle at the right side of
Fig. 3 is about 500700 nm in diameter. It can be seen that
many CNTs grow from it. Meanwhile, other particles seem
to be fragmented by the CNTs and have a rather small size.
All the CNTs are relatively short (2001500 nm). How-
ever, the CNTs become very long after full growth (308
min, Fig. 4). Catalyst particles with relatively small size
are found at the tip of the CNTs, as compared with those in
Fig. 3. Most of the catalyst particles are smaller than 20
nm. The largest (but very few) particles are around 200
nm. Since the particle size of the initial catalyst agglomer-
ate is about 50 mm, it suggests that the catalyst particles
are gradually fragmented by the deposited carbon and
become increasingly smaller with increasing reaction time.
Since the lift-up of CNTs in a tip growth mode needs to
Fig. 4. SEM image of the fully-grown CNTs (sampled at 308
min).
2615
overcome the metalsupport interaction [18] in this pro-
cess, much stress is produced in the carbon layers when the
texture of the catalyst is gradually destroyed (Figs. 3 and
4), which may cause the same defects as the intentional
buckling of CNTs [7]. With the catalyst particles decreas-
ing from 50 mm to about 1020 nm in the first 16 min, the
defects in the CNTs reach a maximum value. After that,
the catalyst particles are embedded in carbon layers [19],
thus no significant change occurs in the following process.
In this period, the carbon atoms deposit at the interface of
carbon and metal particles. Probably due to the relatively
weaker interaction of the metalcarbon (as support) inter-
face as compared with that of the metalalumina interface,
the stress may be relatively weak and the defects may be
diminished significantly.
Though the above result does not exclude the possibility
that the annealing may favor the graphitization of CNTs
with increasing time [17], the effect may be insignificant in
the present work considering the relatively low tempera-
ture (823 K). This conclusion is supported by the fact that
the intensity ratio of the D line to the G line for the CNTs
does not always increase monotonously with reaction time
(Fig. 1). As to the minor increase of the defects of CNTs
after 50 min in the Raman spectra (Fig. 1), it is directly
related to the volume of the CNTs. The bulk density of
CNTs is about 0.075 g cm 23 [14]. The volume of CNTs in
the reactor increases sharply with reaction time. In the
initial growth period, the volume of CNTs is small. The
space of the reactor is large enough for the free growth of
CNTs after lift up from the catalyst support. Therefore,
possibly growing in a rather straight direction, relatively
concentric parallel carbon layers are formed, which have a
symmetric structure and few defects (Fig. 5). However,
there will not be sufficient space for free growth in the
final period and a congestion of CNTs will be unavoidable.
The congestion and collision of CNTs with each other may
hinder their straight growth. Thus, distorted tubes appear
and the defects may increase to some degree. The result is
in agreement with the result of Hernadi et al. [20] using a
relatively small fluidized bed reactor where the collision of
CNTs with the reactor wall is frequent and broken tubes
are observed. In the present case, the effective suspension
of CNTs by gases in a fluidized bed reactor favors the
formation of CNTs with few defects, and CNTs with
minimal defects can be obtained by the in time trans-
portation of CNTs out of the reactor after nearly 50 min
(Fig. 1). This observation calls also for a more effective
reactor design or control to maintain the CNT suspension
in a relatively dilute condition. Further investigation is
needed.
It is noted that our result is contrary to that of Yasuda et
al. [21], who observed that the carbon atoms in the initial
growth period have the ability to self-assemble to an
ordered structure. Its defects may be relatively few. The
reason for this difference may be that, in their in-situ
observation, carbon atoms are easily evaporated on expo-
2616 W. Qian et al. / Carbon 41 (2003) 26132617
Fig. 5. HRTEM image of CNTs (sampled at 50 min).
sure to the laser. Laser irradiation may favor the re-
construction of the carbon layers. In the present work,
where the temperature is only 823 K and any high-energy
source is absent, the deposited carbon atoms have no
ability to re-arrange themselves. The above comparison
has the implication that the introduction of a relatively
intense high-energy source may favor the decrease of the
defects in the CNTs in a CVD process [22]. Such
investigation is underway.
It is noted that the above comparison using ID /IG values
of the Raman spectra aims to understand the time-depen-
dent growth of CNTs. The absolute crystallinity of CNTs
is relatively poor, as prepared at 823 K. The ID /IG values
of CNTs in the present work are in the same range as those
in other previous results [13,15,23]. Though the high
temperature favors the increasing graphitization of CNTs
[15,24], it does not influence the tendency of the time-
dependent defects of CNTs in their growth period. This has
been confirmed by our further work, using propylene as
carbon source, which is decomposed by an Fe / Mo /Al 2 O 3
catalyst at 923 K (this work is mainly done by Dr. Yu
Hao). These results indicate that the fragment of catalyst is
mainly caused by the deposited carbon, and is independent
of the high temperature.
Our work also implies that, though the control of
reaction time can lead to CNT products with different
lengths, their microstructures are somewhat different. To
obtain relatively short tubes for specific applications, an
after treatment at high temperature is recommended to
decrease the defects [15].
4. Conclusions
In summary, the time-dependent evaluation of gross
defects of CNTs was monitored by applying SEM, TGA
and Raman spectroscopy to a continuous CVD process.
The initially grown CNTs have a low thermal stability and
serious defects as compared to the fully-grown tubes, due
to the overcoming of the metalalumina support inter-
action (larger than carbonmetal interaction) in the lift-up
of CNTs. Also, the congestion of CNTs with each other
brings some increase of their defects. Suspension of CNTs
by gases in a fluidized-bed reactor favors the decrease of
their defects to some degree. The control of the volume of
CNTs in the reactor or a more rational reactor design is
needed in view of the effect of increasing volume of the
CNTs on their structural defects.
Acknowledgements
This work was supported by the Natural and Scientific
Foundation of China (no. 20236020).
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