JNL: JPD PIPS: 268628 TYPE: PAP TS: NEWGEN DATE: 7/2/2008 EDITOR: MM
IOP PUBLISHING JOURNAL OF PHYSICS D: APPLIED PHYSICS
J. Phys. D: Appl. Phys. 41 (2008) 000000 (6pp) doi:10.1088/0022-3727/41/1/000000
A model for catalytic growth of carbon
nanotubes
Sayangdev Naha and Ishwar K Puri
1
Department of Engineering Science and Mechanics, Virginia Polytechnic Institute and State University,
Blacksburg, VA 24061, USA
E-mail: ikpuri@vt.edu (I. K. Puri)
Received 26 December 2007, in final form 24 January 2008
Published
Online at stacks.iop.org/JPhysD/41
Abstract
Despite the utility and promise of carbon nanotubes (CNTs), their production is generally
based on empirical principles. There are only a few CNT formation models that predict the
dependence of their growth on various synthesis parameters. Typically, these do not
incorporate a detailed mechanistic consideration of the various processes that are involved
during CNT synthesis. We address this need and present a model for catalytic CNT growth
that integrates various interdependent physical and chemical processes involved in CNT
production. We validate the model by comparing its predictions with one set of experimental
measurements from a previous study for cobalt (Co) catalyzed growth. A brief parametric
study is presented subsequently. From an application perspective, the model is able to predict
the growth rate of the CNT length and its dependence on the ambient temperature and
gas-phase feedstock partial pressure.
1. Introduction
The literature pertaining to carbon nanotubes (CNTs) is mostly
experimental and there are few available models that can
predict their growth. A number of the existing models focus
on catalysis alone and do not combine all of the different
processes that contribute to CNT formation. Kuwana and
Saito [1] described nanoparticle growth from ferrocene and
provided a two-step catalytic reaction model for the formation
of Fe nanoparticles. Zavarukhin and Kuvshinov [2] proposed
a model for the production of nanofibrous carbon from
a methane–hydrogen mixture using Ni as catalyst. Scott
[3] provided a chemical model based on soot nucleation
kinetics that simulates the nucleation and growth of carbon–
nickel clusters and single-wall CNTs. Dateo et al [4]
presented a model for CNT production considering high
pressure carbon monoxide as precursor by considering the
decomposition of the catalyst precursor Fe(CO)
5
, catalyst
growth and decomposition, CNT formation and overcoating
of the catalyst. Zhang and Smith [5] provided a model
for methane decomposition and the formation of filamentous
carbon on a supported Co catalyst. They considered the
1
Author to whom any correspondence should be addressed.
effects of catalyst deactivation, metal particle size and the
carbon density profiles through the catalyst particle at different
reaction times. In a previous study [6] we discussed a model
for CNT growth on Fe catalyst substrates placed in a co-annular
ethylene/air nonpremixed flame reactors. Herein, we present
a more detailed model that predicts CNT growth in terms of
length and handles catalyst poisoning in a more representative
manner.
2. Model
The model includes a mechanism for CNT production
based on a previous diamond nucleation model [7] that
now also contains additional details about the adsorption
energies, bulk diffusion energies and sticking coefficients. The
overall mechanism considers (a) the impingement of carbon
atoms from the predominant carbon-containing species in the
ambient, (b) their adsorption and desorption at the catalyst–
gaseous hydrocarbon interface, (c) surface and bulk diffusions,
(d) nucleation and (e) separation of solid undissolved carbon
in nanostructured form. The schematic of figure 1 illustrates
the modelled processes that lead to the catalyzed formation of
CNTs. Salient features of the model are described below.
0022-3727/08/000000+06$30.00 1 © 2008 IOP Publishing Ltd Printed in the UK