Carbon 44 (2006) 267–275

www.elsevier.com/locate/carbon

Prediction of carbon nanotube growth success by the analysis

of carbon–catalyst binary phase diagrams
Christian P. Deck, Kenneth Vecchio *

Materials Science and Engineering Program, University of California, San Diego, La Jolla, CA 92093-0411, USA

Received 20 April 2005; accepted 21 July 2005

Available online 1 September 2005

Abstract

The growth of carbon nanotubes (CNTs) was attempted using a vapor-phase CVD method, and a wide variety of transition met-
als, in the form of metallocenes and chlorides, were used as potential growth catalysts. Well-aligned mats of multi-walled carbon
nanotubes were observed in samples catalyzed with iron, nickel, and cobalt. Nanotube lengths could be varied between 3 lm
and 3 mm, and diameters ranged from 20 nm to 60 nm. X-ray diffraction, energy dispersive X-ray spectroscopy, and Mossbauer
spectroscopy were used to determine the compositions of the nanotube products. None of the other elements studied, consisting
of Cr, Mn, Zn, Cd, Ti, Zr, La, Cu, V, and Gd, were able to successfully catalyze the growth of CNTs. A study was performed
of the respective metal–carbon binary phase diagrams to understand why the catalytic ability of different elements varied. Successful
catalysts had carbon solubility limits of 0.5 wt.% to 1.5 wt.% carbon, followed closely by nanotube growth through graphite pre-
cipitation. Unsuccessful catalysts were found to have either nearly zero carbon solubility, or to form numerous intermediate car-
bides, making it difficult for the diffusion required for graphite precipitation to occur. These findings were then used to look for
other potential CNT catalysts by examining the phase diagrams of a wide variety of metals.

2005 Elsevier Ltd. All rights reserved.

Keywords: Carbon nanotubes; Chemical vapor deposition, Pyrolysis; X-ray diffraction; Phase transitions

1. Introduction field emission sources [11], and hydrogen storage [12].

Carbon nanotubes (CNTs) are a recently discovered
form of carbon with a graphitic lattice and a long, tubu-
lar structure [1]. They have been the subject of much
interest in recent years, due to their attractive mechani-
cal properties (1000 GPa YoungÕs modulus) [2,3], tun-
able electronic behavior (conducting or semi-conducting
depending on tube chirality) [4], and unique dimensions
(1–100 nm diameter, up to several centimeters length)
[5–7]. As a result of these properties, nanotubes have po-
tential applications in many fields, including composite
reinforcement [8,9], transistors and logic circuits [10],
*
Corresponding author. Tel.: +1 858 5346076; fax: +1 858 5345698.
E-mail address: kvecchio@ucsd.edu (K. Vecchio).
CNTs can be grown by a variety of means, the most
common of which are: arc discharge [13], laser ablation
[14], and chemical vapor deposition (CVD) [15–17].
In order to fully optimize the production of carbon
nanotubes, the growth mechanisms involved in their for-
mation must be completely understood, and a number
of theories have been proposed to describe this growth.
A mechanism to describe the formation of carbon nano-
tubes in the presence of a metal catalyst has been pro-
posed by Sinnott et al. [18], which is based on the
processes involved in carbon nanofiber formation as de-
scribed by Baker et al. [19–21]. In this model, carbon dif-
fuses into nanometer-scale catalytic particles. When the
solubility limit within the metal is reached, this carbon
precipitates out with a graphitic structure. Depending
on the size of the catalyst particle, graphite, carbon

0008-6223/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2005.07.023
268 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275

filaments, or carbon nanotubes can form (in order of Table 1

decreasing particle size and increasing particle curva- List of metal carbon nanotube growth catalysts studied, and the
chemical forms in which they were obtained
ture). The activation energy for nanotube and carbon fil-
ament growth has been shown to be very similar to the Metal Chemical Formula
activation energy for diffusion of carbon through the Iron Ferrocene (C5H5)2Fe
catalyst material, suggesting a relationship between Ferrous chloride FeCl2
Cobalt Cobalt chloride CoCl2
nanotube formation and carbon diffusion [22,23]. Cobaltocene (C5H5)2Co
The objective of this work is twofold. First, the Nickel Nickel chloride NiCl2
growth of carbon nanotubes was attempted using a wide Nickelocene (C5H5)2Ni
variety of metals as catalysts, and the results were ana- Chromium Chromium chloride CrCl3
lyzed to determine which catalysts worked best. Sec- Manganese Manganese chloride MnCl2
Zinc Zinc chloride ZnCl2
ondly, a comparison of the phase equilibria of both Cadmium Cadmium chloride CdCl2
the successful and unsuccessful catalysts was performed, Titanium Titanium chloride TiCl3
in particular, the carbon–catalyst binary phase diagrams Zirconium Zirconium chloride ZrCl4
were investigated to find a link between phase transfor- Zirconocene (C5H5)2Zr
mation equilibria and nanotube catalytic ability. Lanthanum Lanthanum chloride LaCl3
Copper Copper chloride CuCl2
Vanadium Vanadium chloride VCl3
Gadolinium Gadolinium chloride GdCl3
2. Experimental procedure

Carbon nanotubes were grown using spray pyrolysis
chemical vapor deposition methods modeled after that
described by Kamalakaran et al. [24]. A variety of reac-
tant solutions were used. Benzene was used as the car-
bon source, and catalysts were introduced in the form
of either metallocenes ((C5H5)2M) or metal chlorides
(MClx). Iron, cobalt, nickel, and zinc-based metalloc-
enes were directly soluble in benzene, forming solutions
of between 4 wt.% and 8 wt.% metal compound in the
benzene. The chlorides were insoluble in benzene, and
were instead dissolved in methanol in concentrations
ranging from 5 wt.% to 10 wt.%, depending on the metal
used. These solutions were then either combined with
benzene to form a single mixture or introduced simulta-
neously with a separate benzene source. A list of the
compound studied in this work is shown in Table 1.
For spray pyrolysis, this reactant mixture was stored
in a syringe and dispensed in a continuous flow at a fixed
rate through a 27 gauge needle into an argon jet ranging
between 7 · 104 sccm and 9 · 104 sccm. This high flow
rate allowed the reactant solution to be directly intro-
duced into the furnace as a liquid and at the desired con-
centration; lower flow rates allowed the benzene to
evaporate, causing the metal species to come out of solu-
tion. The gas jet sprayed the reactant solution into a
27 mm inner diameter quartz tube held inside a furnace
at 850 C; the equipment used is shown in Fig. 1. Upon
entering the growth region, the gas and reactant mixture
rapidly heats from 25 C to the reaction temperature,
where both the benzene and the metal compound are
decomposed to produce free metal atoms and smaller
carbon species, from which carbon nanotubes nucleate
and grow. For some catalysts, particularly ferrocene,
additional temperatures were studied, ranging from
800 C to 900 C. For metal chloride solutions that were
introduced separately from the benzene, the respective

Fig. 1. (a) Schematic diagram and (b) photograph of Argon jetting apparatus, reaction tube, and syringe dispensing mechanism used for CVD
growth of carbon nanotubes.
 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275
solutions were held in individual syringes, and dispensed
simultaneously into the argon flow.
The high carrier gas flow rate caused much of the
reactants to pass through the heated region (12 in. long)
without reaction; however, turbulence and boundary
layer conditions caused slower flow around the substrate
and near the tube walls. This allowed nanotube nuclei to
deposit and growth to occur, and the resulting products
were collected, transferred to scanning electron micro-
scopy (SEM) specimen holders or transmission electron
microscopy (TEM) grids, and examined using SEM, en-
ergy dispersive spectroscopy (EDS), TEM, Mossbauer
spectroscopy, and X-ray diffraction.
3. Results and discussion
Of the 13 elements studied as potential catalysts for
the growth of nanotubes (17 total compounds) only
three metals (six compounds) were successful. Iron,
cobalt, and nickel were found to successfully catalyst
the growth of carbon nanotubes in both the metallocene
and metal chloride forms, while the other elements stud-
ied either produced undesired carbon by-products (Cr,
Mn, Zn, Cd, Zr, La, V) or no products at all (Ti, Cu,
Gd).
Fig. 2. Typical aligned carbon nanotubes produced by the chemical vapor deposition of iron, nickel, and cobalt catalysts with benzene.
Fig. 3. TEM micrographs of typical carbon nanotubes produced by the decomposition of iron, cobalt, and nickel compounds, showing multi-walled
tubes of 30–40 nm diameter with multiple encapsulated catalyst particles.
269
3.1. Successful catalysts
As expected, based on previous studies in the litera-
ture, iron, cobalt, and nickel were all found to success-
fully catalyze the formation of carbon nanotubes [16].
The catalysts were mixed with the other reactants
(8 wt.% ferrocene, 10 wt.% FeCl2, 10 wt.% cobaltocene,
6 wt.% CoCl2, 10 wt.% nickelocene, 10 wt.% NiCl2) and
growth was performed as described previously.
Typical products were in the form of large mats of
well-aligned carbon nanotubes with a high purity, as
shown in the SEM micrographs of Fig. 2. By varying
the amount of reactants introduced and the total reac-
tion time, the length of the tubes in these mats could
be controlled within the range of less than 3 lm to as
long as 3 mm.
TEM imaging was also used on these samples as
shown in Fig. 3. Tube diameters varied between 20 nm
and 60 nm, and numerous, elongated encapsulated par-
ticles were observed within the tube cavities. Few amor-
phous carbon particles were observed, and most of the
catalyst in the product appears to be encapsulated.
X-ray diffraction (XRD) and energy dispersive X-ray
spectroscopy (EDS) were then used to determine the
compositions of the samples. For some runs it was diffi-
cult to obtain the required sample quantity to use this
270 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275

Fig. 4. X-ray diffraction spectra for Fe-catalyzed carbon nanotubes (top) and Co-catalyzed carbon nanotubes (bottom), with peaks labeled.

technique, so XRD was only performed on samples cat- Table 3

alyzed with ferrocene and cobalt chloride; the resulting Iron compounds present in a ferrocene catalyzed sample, obtained
using Mossbauer spectroscopy
spectra are shown in Fig. 4. A comparison between
the measured peaks and data from the literature Compound Percent in sample
[17,25–29] and the JCPDS database [30] allows the com- c-Fe (FCC) iron 21
pounds in each sample to be identified; the presence of a-Fe (BCC) iron 11
Fe3C (iron carbide) 68
graphite, a-Fe, and Fe3C is observed in the ferrocene
sample and graphite, Co, and both Co2C and Co3C
are found in the cobalt chloride sample. Nanotube walls
contribute the graphite peaks and the metal and carbide to determining exactly what iron-containing structures a
peaks are generated from the carbon-saturated catalyst particular sample contains, a Mossbauer spectroscopic
particles encapsulated within and at the tips of nano- analysis can also provide the relative amount of each
tubes. Very good agreement is found between the litera- compound present. This analysis was performed on
ture values and measured values of the peak locations. nanotubes catalyzed with ferrocene; the results are listed
Energy dispersive X-ray spectroscopy (EDS) was per- in Table 3 and show that the majority of iron in the sam-
formed to provide information on which elements are ple is in carbide form.
present and relative quantities of each element. Spectra
were gathered from multiple locations in each sample; 3.2. Unsuccessful catalysts
the averaged results are listed in Table 2.
For those carbon nanotube samples grown with an Under the growth conditions used in these experi-
iron catalyst, Mossbauer spectroscopy was also used to ments, none of the other compounds studied (except
more precisely identify the structures present. In addition for the Fe-, Ni-, and Co-based materials) were able to
catalyze the growth of carbon nanotubes. In all but
Table 2 three of the tests, black, carbonaceous soot was depos-
Relative composition of nanotube samples catalyzed by iron, nickel, ited on the quartz substrates; no deposits of any form
and cobalt compounds were found in runs with Ti, Cu, or Gd as catalysts.
Catalyst Carbon (at.%) Iron Nickel Cobalt Due to the lack of product, no further tests could be per-
Ferrocene 98.86 1.14 at.% N/A N/A formed on these samples; however, SEM observations
FeCl2 98.25 1.75 at.% N/A N/A and EDS analyses were performed on the other results.
Nickelocene 99.51 N/A 0.49 at.% N/A The soot produced in these tests was found as small (sev-
NiCl2 95.92 N/A 4.08 at.% N/A eral hundred nanometers) particles, or in larger, spheri-
Cobaltocene 98.95 N/A N/A 1.05 at.%
CoCl2 96.61 N/A N/A 3.39 at.%
cal clusters with diameters ranging from a few to the
tens of micrometers; these results are illustrated in
Averages 98.0 1.45 at.% 2.29 at.% 2.22 at.%
Fig. 5.
 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275 271

Fig. 5. Typical soot produced by unsuccessful nanotube catalysts, showing small powder (zirconocene) and larger clusters (vanadium chloride).

Table 4 scale catalyst particles are used, this graphite will be

Relative Compositions of carbonaceous soot produced using Cr, Mn, produced with a nanotube structure. Molecular dynamic
Zn, Cd, Zr, La, and V catalysts, values listed are in atomic percent
simulation results using a potential energy surface meth-
Catalyst Metal Carbon Oxygen Chlorine Sodium od have been published by Ding et al. [31] showing that
(%) (%)
these iron clusters must reach supersaturated carbon lev-
CrCl3 0.25% Cr 82.68 14.88 1.06% 1.14% els before nanotube formation begins; this saturation
MnCl2 3.03% Mn 78.93 18.04 N/A N/A
ZnCl2 3.83% Zn 69.03 18.82 8.31% N/A
has also been described by Kuznetsov with the use of
CdCl2 0.94% Cd 82.74 13.37 2.95% N/A phase diagrams [32]. The rapid diffusion of carbon in
ZrCl4 1.66% Zr 79.08 17.18 1.18% 0.90% iron allows for rapid carbide formation and quick
(C5H5)2Zr 0.16% Zr, 76.13 17.35 1.19% 1.63% graphite precipitation. With cobalt and nickel, meta-sta-
3.54% Fe ble carbides (Co3C, Co2C, and Ni3C [33]) form immedi-
LaCl3 4.30% La 76.36 14.10 5.24% N/A
ately following saturation of carbon in the solid
VCl3 15.54% Va 52.21 32.24 N/A N/A
solution, and as additional carbon diffuses into the cat-
alyst, graphite precipitates out, forming a nanotube. In
the reactant solutions used, there is a large excess of car-
The EDS spectra results for these tests are summa- bon present, pushing the systems toward graphite pre-
rized in Table 4; peaks for silicon (due to the SiO2 quartz cipitation (6–10 wt.% metal chloride or metallocene
substrates) have not been included. solutions in benzene were used, which corresponds to
In addition to the expected metal and carbon, oxygen an atomic ratios of between 90:1 and 170:1, carbon
(from the methanol used as a solvent) and chlorine atoms per metal atom). The binary phase diagrams for
(from the chloride compound) are present in almost all these systems are shown in Fig. 6 (the meta-stable car-
samples. There is a wide range of metal content ob- bide phases formed in the nickel and cobalt systems
served, as well as iron contamination in the zirconocene are not indicated).
sample (due to residual iron on the reaction tube). Sig- This type of carbon–metal phase behavior is not ob-
nificant sodium was also detected, and the source of this served in any of the other metals studied within the tem-
element could not be specifically determined, however, it perature ranges used. Unsuccessful catalysts typically
is likely that NaCl salt was present in some of the metal- fell into two categories: either there is no significant sol-
chloride compounds used. ubility of carbon in the metal or numerous stable car-
bides formed at higher carbon concentrations. In the
3.3. Carbon–metal binary phase diagram analysis carbon–copper, carbon–zinc, carbon–gadolinium, and
carbon–cadmium systems studied, the solubility limit
The binary carbon phase diagrams of nickel, iron, of carbon in the metals is extremely low (for example,
and cobalt, all of which were found to be effective in cat- only 0.0001 wt.% C in Cu at 1100 C, which is above
alyzing the growth of carbon nanotubes, were found to the melting point of Cu) [35]. Carbon cannot diffuse in
have distinct similarities not found with other elements. significant quantities into the nanoscale catalyst parti-
All exhibited some carbon solubility (0.5–1.0 wt.% car- cles, and therefore, these particles cannot act as nucle-
bon) in the solid solution within the temperature ranges ation sites for the formation of carbon nanotubes; an
studied (800–900 C). At the solid solution solubility example of this phase equilibria is shown in Fig. 7.
limit with iron, a stable carbide (Fe3C) is produced. With other potential metal catalysts, sufficient carbon
Once the Fe3C phase is completely saturated with car- solubility is observed in the solid solution; however,
bon (at 6.67 wt.% C), graphite forms and, when nano- multiple carbides readily form. Carbides are typically
272 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275
Fig. 6. Cobalt–carbon, nickel–carbon, and iron–carbon binary phase
diagrams [34].
Fig. 7. Copper–carbon binary phase diagram [34].
formed at compositions of M23C6, M5C2, M7C3, and
M3C2. Graphite precipitation does not occur until the
formation of all these carbides has occurred, and re-
quires a much higher carbon concentration in the sys-
tem. The time required for the kinetics of this carbon
diffusion and carbide formation could delay or inhibit
the graphite precipitation to an extent which would pre-
vent the formation of carbon nanotubes given the
growth conditions used in these experiments. These car-
bides are observed in the chromium and manganese sys-
tems, illustrated in Fig. 8, as well as in the vanadium
(VC, V3C2, V2C) titanium (TiC), zirconium (ZrC), and
lanthanum (La2C3 and LaC2) systems [33,35].
These findings suggest the following criteria describ-
ing the ability of a pure metal to successfully catalyze
the growth of carbon nanotubes.
1. There should be sufficient carbon solubility in the
metal solid solution (1 at.%) within the temperature
range used during growth.
2. Following saturation of the solid solution, the precip-
itation of graphite should begin without the forma-
tion of any intermediate carbides.
3. If carbides do form, diffusion of carbon through the
solid solution and the carbides should be rapid and
reach the carbon concentration needed for graphite
precipitation quickly.
3.4. Prediction of alternate catalysts
Carbon nanotubes can be formed in certain situations
without the presence of a catalyst [36,37]. However, in
order to produce nanotubes more efficiently and in a
wider range of conditions, an appropriate catalyst must
be introduced. Using the criteria found to indicate po-
tential catalytic ability for the growth of carbon nano-
tubes, a search was performed through carbon–metal
binary phase diagrams for over 70 elements in an at-
tempt to identify any other potential catalysts. Phase
diagrams of all the transition metals, as well as the lan-
thanides and actinides were examined. A large number
of these systems show negligible carbon solubility in
the solid solution, and would not be expected to provide
any catalytic action towards the formation of carbon
nanotubes.
However, a number of other metals could serve as
catalysts of nanotube growth under the proper condi-
tions. Although a number of the elements tested in this
work showed sufficient carbon solubility, the tendency
to form carbides prior to graphite precipitation inhibited
any potential catalytic ability to the point that nano-
tubes were not formed in these studies. Carbon diffusion
rates could be too slow to reach the concentrations
needed to precipitate graphite, or catalyst particles could
grow too large prior to graphite formation (due to the
continuous introduction of catalyst material) to success-
fully grow nanotubes. In appropriate conditions, such as
with arc-discharge or laser ablation growth, when using
patterned films of nanometer-scale catalyst particles, or
at elevated temperature for faster diffusion, these previ-
ously unsuccessful catalysts could produce carbon nano-
tubes [38,39]. In particular, catalytic ability has been
demonstrated in elements in the transition metal [40],
lanthanide [39,41], and platinum groups [38,40] using
 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275 273

Fig. 8. Chromium–carbon and manganese–carbon binary phase diagrams [34].

arc discharge growth processes and with growth occur-

ring from carbide phases.
For optimal growth in typical chemical vapor deposi-
tion procedures, metal catalysts need to exhibit sufficient
carbon solubility, rapid carbon diffusion, and limited
carbide formation. With the exception of iron, cobalt,
and nickel, none of the elements studied appeared to
have the required carbon-phase behavior to effectively
catalyst nanotubes with the vapor phase growth process
used in this work. For some metals, carbon is soluble
within a small temperature range, and catalytic ability
could be exhibited in this region. For other metals,
where carbide formation inhibits nanotube growth from
the pure metal, carbides could be used as potential cat-
alysts to encourage graphite precipitation, provided the
carbide particles were appropriately sized and carbon
diffusion was sufficiently fast. The use of carbides as cat-
alysts was investigated by placing titanium carbide (TiC)
particles of 50–120 nm diameter in a flow of 300 sccm
argon at 800 C, with either an acetylene or benzene car-
bon source. While no growth was achieved when using
titanium in its pure form (from decomposed TiCl4),
nanotubes were successfully catalyzed when grown from
the TiC particles. In the titanium–carbon system, graph-
ite precipitation does not occur until carbon saturation
(50 at.%) is reached in the c phase (TiC), as shown
in Fig. 9.
When using TiCl4 as a catalyst, nanotubes would not
form until titanium clusters grew from decomposed
TiCl4, diffusion of carbon formed TiC (at 35 at.%),
and then TiC saturation was reached (50 at.%); in
the conditions used in these experiments this compound
was not successful as a catalyst. With TiC, however,
graphite precipitation begins as soon as carbon satura-
tion is reached (50 at.%, starting from 35 at.% to
Fig. 9. Titanium–carbon binary phase diagram [34].
45 at.% carbon in TiC). Carbon nanotubes with diame-
ters of 20–45 nm were grown from these particles, as
shown in Fig. 10. Using this approach (nanometer-scale
carbide catalysts), nanotubes could presumably be
grown from a much more varied selection of metals;
almost any metal carbide with sufficient carbon diffusion
kinetics could work.
While this work was performed to identify the prop-
erties of certain metals which make them well suited to
catalyze the growth of carbon nanotubes, the carbon
diffusion within these metals during nanotube growth
is very similar to that occurring during carbon nanofiber
formation. The carbon nanotube growth mechanism de-
scribed by Baker et al. [19–21] and Sinnott et al. [18] ex-
plains that the role of the metal catalyst is the same
during carbon nanotube and carbon nanofiber growth,
and the type of structure formed is only dependant on
the catalyst particle size. Therefore, the results presented
in this paper for the prediction of the catalytic ability of
different metals would apply to the growth of carbon
274 C.P. Deck, K. Vecchio / Carbon 44 (2006) 267–275
Fig. 10. TEM micrographs of carbon nanotubes grown from TiC catalyst particles and the decomposition of acetylene (a), (b); and the
decomposition of benzene (c).
nanofibers as well, provided the catalyst particle dimen-
sions were in the appropriate range.
4. Conclusions
Carbon nanotube growth was attempted using a vari-
ety of different metal-containing compounds as potential
catalysts in a vapor phase CVD procedure. Nanotubes
were grown from metallocene and chloride compounds
containing iron, cobalt, and nickel. SEM imaging re-
vealed densely packed mats of well-aligned tubes and
XRD and Mossbauer analysis indicated the presence
of both pure metal and carbides in the products. None
of the other elements studied were able to catalyze nano-
tube growth under the reaction conditions used. A com-
parison was then made of the metal–carbon binary
phase diagrams for all the catalysts studied to identify
what phase equilibria is indicative of catalytic ability.
Successful elements (Fe, Co, and Ni) were found to have
some (1 at.%) carbon solubility in the solid solution,
and form few, if any, stable carbide phases. Elements
with no carbon solubility or with multiple carbide
phases did not produce nanotubes in this vapor phase
CVD process. Using these criteria, a study was made
of carbon–metal phase diagrams for over 70 elements
to identify any unknown potential catalysts. No other
elements were found to have phase equilibria and solu-
bility limits similar to Fe, Co, and Ni; however, some
elements, such as those in the lanthanide and platinum
groups, as well as some transition metals, could act as
catalysts when initially in the carbide form or at elevated
temperatures (where carbon diffusion would be more ra-
pid). The use of a metal carbide as a nanotube catalyst
was demonstrated with nanometer-scale particles of
TiC. Finally, ternary systems are now being examined
for possible new catalyst systems.
Acknowledgements
The authors thank Ralf Brunner (UC San Diego—
CMRR) and Gregg McKee (UC San Diego—MAE)
for their help and assistance throughout the course
of this work, and Fred Parker (UC San Diego—
CMRR) for his help with Mossbauer spectroscopy
and analysis.
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