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Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
 CARBON NANOTUBES:
NEW RESEARCH

No part of this digital document may be reproduced, stored in a retrieval system or transmitted in any form or
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Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
 CARBON NANOTUBES:
NEW RESEARCH

AVERY P. OTTENHOUSE
EDITOR
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

Nova Science Publishers, Inc.

New York
 Copyright © 2009 by Nova Science Publishers, Inc.

All rights reserved. No part of this book may be reproduced, stored in a retrieval system or
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LIBRARY OF CONGRESS CATALOGING-IN-PUBLICATION DATA

Ottenhouse, Avery P.
Carbon nanotubes : new research / Avery P. Ottenhouse.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

p. cm.
Includes bibliographical references and index.
ISBN 978-1-60876-700-7 (E-Book)
1. Carbon. 2. Nanostructured materials. 3. Nanotubes. I. Title.

TA455.C3O88 2009
620.1'93--dc22
2008037516

Published by Nova Science Publishers, Inc. 

  New York
 CONTENTS

Preface vii
Short Communications: On the Drude Model to Explain Quantum Transport in
Carbon Nanotubes 1
M. A. Grado-Caffaro and M. Grado-Caffaro
Short Communications: Asymptotic Analysis of Coagulation–Fragmentation
Equations 7
Francisco Torrens, and Gloria Castellano
Chapter 1 Gas-Carbon Nanotubes Interactions: A Review of ultra-high
vacuum Surface Science Studies on CNTs 17
U. Burghaus
Chapter 2 On Residual Metallic Catalyst Impurities in Carbon Nanotubes 75
Martin Pumera
Chapter 3 Insight of the Kinetics Carbon Nanotubes Growth and
Funcionalization with Freestanding Silicon Nanocrystals 81
Vladimir Švrček
Chapter 4 Carbon Nanotube Array Thermal Interfaces 101
Baratunde A. Cola, Timothy S. Fisher, and Xianfan Xu
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

Chapter 5 Computational Analysis of the Interfacial Bonding Characteristics

of Carbon Nanotube/Polymer Composites 119
Qingzhong Xue and Qingbin Zheng
Chapter 6 Mechanical Properties of Carbon Nanotubes 157
Q. Wang and K. M. Liew
Chapter 7 Electrical Properties of a Carbon Nanotube/Polymer
Nanocomposite and its Application as Highly Sensitive Strain
Sensors 175
Ning Hu, Zen Masuda and Hisao Fukunaga
 vi Contents

Chapter 8 The Ferrochemistry of Carbon Nanotubes, Diamond, Nucleic Acids

and Proteins: The Magnetic Synergism of Macromolecules And
Life’s Chemical Patterns 223
Reginald B. Little
Chapter 9 Biocompatibility Differences between Dispersed and Vertically-
Aligned Carbon Nanotubes: An In Vitro Assays Review 281
A.O. Lobo, E.F. Antunes; M.B.S. Palma; C. Pacheco-Soares,
M.A.F. Corat, V.J. Trava-Airoldi and E.J. Corat
Chapter 10 Engineered Electrical and Mechanical Properties of Carbon
Nanotube Added Si3N4 Nanocomposites 317
Csaba Balázsi, Orsolya Koszor, Balázs Fényi and
Katalin Balázsi
Chapter 11 Fluorinated Carbon Nanotubes: State of the Art, Trends and
Advanced Concepts 341
Daniel Claves
Chapter 12 Carbon Nanotubes: Applications of this Nanostructured Material for
the Development of Analytical Methods 371
César Ricardo Teixeira Tarley, Gustavo Silveira,
Bruno Eduardo Lobo Baêta, Vivian Silva Santos,
Lucas Rossi Sartori, Alexandre Kisner,
Arnaldo César Pereira and Lauro Tatsuo Kubota
Chapter 13 Physical Characteristics of Carbon Nanotubes: Experiments and
Analysis 407
Te-Hua Fang, Ruo-Ping Chang and Win-Jin Chang
Chapter 14 Dispersion and Field Emission Properties of Carbon Nanotubes 433
Hyun-Tae Kim and Dang-Hyok Yoon
Chapter 15 Application of C-Nanotubes in Ceramics 463
Guenter Motz and Sylvia Kokott-Wenderoth
Index 473
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
 PREFACE

This new and important book presents significant research on carbon nanotubes (CNTs)
which are allotropes of carbon with a nanostructure that can have a length-to-diameter ratio
greater than 1,000,000. These cylindrical carbon molecules have novel properties that make
them potentially useful in many applications in nanotechnology, electronics, optics and other
fields of materials science, as well as extensive use in arcology and other architectural fields.
They exhibit extraordinary strength and unique electrical properties, and are efficient
conductors of heat. Inorganic nanotubes have also been synthesized. Nanotubes are members
of the fullerene structural family, which also includes the spherical buckyballs. The
cylindrical nanotube usually has at least one end capped with a hemisphere of the buckyball
structure. Their name is derived from their size, since the diameter of a nanotube is in the
order of a few nanometers (approximately 1/50,000th of the width of a human hair), while
they can be up to several millimeters in length (as of 2008). Nanotubes are categorized as
single-walled nanotubes (SWNTs) and multi-walled nanotubes (MWNTs).
Short Communications - The Drude model relative to carrier drift mobility and
conductivity is discussed in relation to its applicability to explain quantum transport through
both single-walled and multiwalled carbon nanotubes. The authors show that the Drude
model, suitable to describe electrical conductivity in solids as, for instance, semiconductors, is
certainly adequate to discuss key aspects of quantum transport in multiwalled carbon
nanotubes. In this respect, conductance quantization is treated in relation to the model in
question by calculating carrier mobility and conductivity under ballistic regime. As a
consequence, an expression for the quantized conductance of a multiwalled carbon nanotube
is derived.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

The existence of single-wall carbon nanotubes (SWNTs) in organic solvents in the form
of clusters is discussed. A theory is developed based on a bundlet model for clusters
describing the distribution function of clusters by size. The phenomena have a unified
explanation in the bundlet model of a cluster, in accordance with which the free energy of an
SWNT involved in a cluster is combined from two components: a volume one proportional to
the number of molecules n in a cluster, and a surface one proportional to n1/2. A comparative
study of the droplet and bundlet models is carried out. The model yields an activation barrier
and predicts that pores with a radius below a certain critical value are unstable, while those
above this radius will grow indefinitely until the membrane ruptures. During the latter stage
of the fusion process, the dynamics were governed by the displacement of the volume of
liquid around the fusion site. Based on a simple kinetic model, micellization of rod-like
 viii Avery P. Ottenhouse

aggregates occurs in three separated stages. A convenient relation is obtained for <n> at
transient stage; at equilibrium another relation determines binding energy. A relation with
surface dilatational viscosity is obtained. The model predicts that pores with a radius below a
certain critical value are unstable.
Chapter 1 - While numerous studies concerning the synthesis and materials science
applications of carbon nanotubes have been conducted, the data obtained at well-defined
ultra-high vacuum conditions by means of surface science techniques is still scarce. The
author presents specific examples of recent ultra-high vacuum surface science projects from
the authors laboratory conducted on clean carbon nanotubes with an emphasis on applications
in heterogeneous catalysis. In addition the related surface science literature is summarized
and future directions are outlined.
In particular, kinetics and molecular beam scattering (dynamics) results for alkanes,
alcohols, and thiophene are described. Alkanes perfectly allow for characterization of
different adsorption sites on carbon nanotube bundles, while alcohols are related to fuel cell
applications, i.e., to renewable energy production and a green (environmentally friendly)
chemistry approach. Thiophene is the probe molecule of choice to characterize
desulfurization catalysts which are important for the petroleum industry. Kinetics experiments
quantify the binding strength of these probe molecules on carbon nanotubes and provide
evidence for capture effects, which are one of the main advantages of nanotubes in catalysis.
Molecular beam scattering has characterized gas-surface energy transfer processes and, again
capture effects, i.e., the adsorption of the probe molecules in carbon nanotubes.
In addition, a brief review of the related literature is included. The literature survey
(conducted early in 2008) focuses on experimental research conducted at high vacuum (< 10-
6
torr) where common surface science techniques have been applied. A number of theoretical
studies addressing a structure activity relationship (SAR) are included too. However,
electrochemistry or pure catalysis studies (conducted at high pressure and high temperatures)
are mostly omitted.
Finally, an outline of future directions in surface science on CNTs is kindly proposed.
Chapter 2 - The aim of this chapter is to discuss the problematic of residual metallic
catalyst impurities in carbon nanotubes.
Chapter 3 - In this chapter the growth kinetics of most common carbon nanotubes (CNTs)
synthesis at industrial scale by catalyst assisted chemical vapor deposition (CVD) is
discussed. It is shown that the monitoring of CNTs growth at initial stages by using a Tapered
Element Oscillating Microbalance (TEOM) brings new insights into synthesis and
controllability of the CNTs properties. The high sensitivity of the TEOM technique allows
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

precisely determinates the crucial synthesis parameters. We argue that precise TEOM control
of the reaction temperature and the partial pressure allows evaluate the order of the reaction
kinetics and absolute reaction rate. Furthermore, CNTs solve some challenges linked with
connection and manipulation of silicon nanocrystals (Si-ncs) at nanoscale level. Particularly,
direct growth of CNTs on Si-ncs in the TEOM is performed in order to connect single Si-nc.
Compared to porous catalyst supports substantial differences in CNTs growth kinetics are
observed when the synthesis is performed on flat Si-ncs surface. A model taking into
accounts an associative and competitive adsorption of ethane is used to interpret obtained
results. The diameter of the CNTs depends on the size of the Si-ncs, which remains connected
on the tip of the CNTs. The wired Si-ncs keep room temperature photoluminescence
properties. It is shown that the CNT cavity, in additionally, can serve as nano-reservoir for
 Preface ix

freestanding Si-ncs. Colloidal dispersion of freestanding Si-ncs allows entering into CNT
cavity by induced capillary force. Alternatively, the shock waves generated during Si-ncs
formation in transparent polymer by nanosecond laser processing assure the filling as well.
The authors believe that the present findings might open new opportunities and situations in a
development of new class of nanodevices for the environmental friendly applications.
Chapter 4 - Because of their excellent thermal and mechanical properties, the efficacy of
carbon nanotubes (CNTs) as a thermal interface material has recently been studied. Vertically
oriented arrays of CNTs directly synthesized on substrates form dry and separable interfaces
that have been demonstrated to achieve thermal resistances that compare favorably to state-
of-the-art thermal interface materials. A transient photoacoustic (PA) technique is used to
measure the total thermal resistances of different interface structures that comprise CNT
arrays directly synthesized on various substrates, and on one and both sides of the interface
and on thin metal foils inserted into the interface. The PA technique is also employed to
measure the CNT-substrate (growth substrate and opposing substrate) resistances and the
intrinsic resistance of the CNT arrays that sum to produce the total thermal resistance of the
CNT array interface structures. The measurements reveal that CNT-substrate resistances are
the largest local resistances in CNT array interfaces, and that the resistances at the CNT free
ends are significantly larger than the resistances at the CNT-growth substrate interfaces.
Chapter 5 - Since the discovery of carbon nanotubes (CNTs) by Iijima in 1991, CNTs
have attracted great research interest due to their unique properties such as high electrical and
thermal conductivity, excellent stiffness against bending, and high tensile strength. Using
carbon nanotubes (CNTs) as nanofibers to enhance the mechanical, electrical, thermal, and
optical properties of composite materials has been pursued extensively. Molecular mechanics
(MM) and molecular dynamics (MD) simulations have become increasingly popular in the
theoretical investigations of reinforcement mechanisms in CNT-polymer composite systems.
This paper is dedicated to conduct theoretical study on the interfacial characteristics of CNT
reinforced polymer composites.
Firstly, force-field-based MD simulations are performed to study the interaction between
polymers and SWNTs. The “wrapping” of nanotubes by polymer chains was computed. The
influence of temperature, nanotube radius and chirality on polymer adhesion was
investigated. Furthermore, the “filling” of nanotubes by polymer chains was examined. The
results show that the interaction between the SWNT and the polymer is strongly influenced
by the specific monomer structure such as aromatic rings, which affect polymers’ affinities
for SWNTs significantly. The attractive interaction between the simulated polymers and the
SWNTs monotonically increases when the SWNT radius is increased. The temperature
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

influence is neglectable for PE and PP but strong for PS and PANI.

Secondly, the authors simulations indicate that the adhesion energy between the SWNT
and the polymer strongly depends on the chirality. For SWNTs with similar molecular
weights, diameters and lengths, the armchair nanotube may be the best nanotube type for
reinforcement. The simulations of filling reveal that molecules of PE, PP and PS can fill into
a (10, 10) SWNT cavity due to the attractive van der Waals interactions. The possible
extension of polymers into SWNT cavities can be used to structurally bridge the SWNTs and
polymers to significantly improve the load transfer between them when SWNTs are used to
produce nanocomposites.
Finally, the influence of chemical functionalization on the interfacial bonding
characteristics of SWNTs reinforced polymer composites was investigated using MM and
 x Avery P. Ottenhouse

MD simulations. The simulations show that functionalization of nanotubes at low densities of

functionalized carbon atoms drastically increase their interfacial bonding and shear stress
between the nanotubes and the polymer matrix. This indicates that increasing the load transfer
between SWNTs and a polymer matrix in a composite via chemisorption may be an effective
way and chemical attachment of nanotubes during processing may be in part responsible for
the enhanced stress transfer observed in some systems of the nanotube-polymer composites.
Furthermore, this suggests the possibility to use functionalized nanotubes to effectively
reinforce other kinds of polymer-based materials as well.
The simulation results would be of important in the production of CNTs reinforced
polymer composites.
Chapter 6 - Molecular mechanics calculations for the in-place stiffness, shear modulus,
and bending rigidity of both single- and double-walled carbon nanotubes are reported by
calculating the strain energy of carbon nanotubes and graphite sheets subject to various types
of loading. Elastic rod and plate theories are employed to link the material properties of
carbon nanotubes directly to the molecular mechanics calculations. The length dependence of
these material properties is reported and investigated via nonlocal elasticity theory. In
addition, the van der Waals effect on the differences between the material properties of
double- and single-walled carbon nanotubes is also examined. The diminishment of such
differences in large sizes of carbon nanotubes is revealed from the simulations.
Molecular mechanics calculations for the in-place stiffness, shear modulus, and bending
rigidity of both single- and double-walled carbon nanotubes are reported by calculating the
strain energy of carbon nanotubes and graphite sheets subject to various types of loading.
Elastic rod and plate theories are employed to link the material properties of carbon nanotubes
directly to the molecular mechanics calculations. The length dependence of these material
properties is reported and investigated via nonlocal elasticity theory. In addition, the van der
Waals effect on the differences between the material properties of double- and single-walled
carbon nanotubes is also examined. The diminishment of such differences in large sizes of
carbon nanotubes is revealed from the simulations.
Chapter 7 - Carbon nanotubes (CNTs) of high aspect ratio possess excellent electrical
conductivity. Therefore, with a little amount of CNTs, which are dispersed into insulating
polymers, it is possible to manufacture CNT/polymer nanocomposites with very high
electrical conductivity. This kind of conductive nanocomposites can be employed in various
applications, such as highly sensitive strain sensors and electromagnetic interference
materials.
In this Chapter, the authors will mainly describe the research outcomes about the
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

electrical properties of CNT/polymer nanocomposites from experimental and theoretical

studies. First, in this work, based on the statistical percolation theory, the authors proposed a
three dimensional (3D) numerical model to predict the electrical properties of a
nanocomposite made from an insulating polymer with filled CNTs. In this model, with the
assumption of randomly distributed CNTs in the polymer, the percolation threshold was
estimated at the volume fraction of CNTs when the first complete electrically- conductive
path connected by some CNTs is formed. Furthermore, to predict the electrical conductivity
of the nanocomposite after the percolation threshold, a 3D resistor network model was
constructed, in which Kirchhoff’s current law was adopted to set up the system algebraic
equations at different nodes in the network formed by CNTs. The macroscopic current of the
nanocomposite under the applied external voltage was calculated by solving these equations,
 Preface xi

and then Ohm’s law was employed to predict the macroscopic electrical conductivity of the
nanocomposite. The influences of curved shapes of CNTs, aggregates of CNTs and tunnel
effect among CNTs on the percolation threshold and the electrical conductivity have been
investigated in detail.
To verify the above numerical model, a lot of experiments have also been performed by
the authors. The effects of various factors in the in situ polymerization fabrication process on
the electrical performances of the nanocomposite were explored. The present experimental
results plus some previous experimental results by other researchers were found to agree with
the present numerical results very well. Moreover, a simple yet reliable empirical percolation
theory has been obtained based on the detailed numerical investigations.
For the application of this nanocomposite as highly sensitive strain sensors, by
considering the tunnel effect among CNTs and the rigid-body movement of CNTs in the
polymer caused by the prescribed strain, the above numerical model was further extended for
modeling the electrical resistance change of the nanocomposite due to the strain. The relation
between the applied strain and the electrical resistance change was estimated numerically and
measured experimentally. Both numerical and experimental results, which are in very good
agreement, demonstrate that the CNT/polymer sensors possess much higher sensitivity or
gauge ratio compared with the traditional strain gauge. The tunnel effect was found to be a
key factor to control the performance of this new-type strain sensor.
Chapter 8 - Magnetic and electric phenomena have been known in matter for over 2
millennia. The existence of magnetism and electricity in both living and nonliving materials
and the intrinsic relationship between electricity and magnetism suggest intrinsic magnetic
effects on the chemistry and chemical dynamics of both inorganic and organic substances.
Such a magnetic role in matter is supported by the different types of bonds: ionic, covalent,
metallic and hydrogen bonding. The internal charges and charge motions for atomic structure
further support the magnetic role in the structure and dynamics of matter. In this perspective,
an electromagnetic interpretation by cooperative self-interactions is given for the quantum
and wave descriptions of internal charges of the atoms of matter. By considering such
magnetic effects, the nature of valence, covalent bond, and catalysis is explained. The
photophysics of organic molecules and transition metal complexes are given more meaning
by this magnetic perspective. Such a magnetic consideration allows the chemical reaction
dynamics to be explained in a more general manner for organic, organometallic, nonmetal,
ionic, transition metal and complexes substances thereof. New chemistry by the
nonpreservation of orbital symmetry becomes meaningful. The ferrochemistry (the Little
Effect) is discovered wherein the bond rearrangements and bonds of many atoms between
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

reacting substances are transformed by many polarized spins during the interactions. Such
ferrochemistry was discovered while determining the mechanism of carbon nanotube
formation. Ferrochemistry has resolved the two hundred year old diamond synthesis problem.
Unconventional nuclear phenomena have been understood by ferrochemical effects. In this
perspective, ferrochemistry is further developed among the branches of chemistry. By
correlated and exchanged fermions during macromolecular reactions, a quantum/wave
consideration of ferrochemical reactions in plasma, liquids and solids is presented. Such a
quantum/wave nature of ferrochemical dynamics determines the basis of resonance and
tautomerism. On the basis of the uniqueness of compositions of biomacromolecules and their
aqueous environments, the quantum/wave natures of many, varied, nano-arrayed,
ferrochemically reacting functional groups of proteins and nucleic acids and complexes
 xii Avery P. Ottenhouse

thereof are considered to determine emerging structures, dynamics and properties of proteins
and nucleic acids. The magnetism, magnetic order and ferrochemistry arise within and
between the biomacromolecules due to the many coupled varied weak acid - weak base
reactions by p+ transfers among the many functional groups and the continual shift and
magnetic p+ currents for their dis-equilibriums by the quantum/wave internal motions and
interactions.
Chapter 9 - An overview about carbon nanotube (CNT) production and quality
parameters will be presented, as well a review of current literature about “in vitro” assays
commonly used to evaluate the biocompatibility of CNT. The limits of colorimetric assays for
CNTs evaluation will be discussed, using comparisons between dispersed CNT and CNT
arrays. The influence of nanotopography and wettability of CNT scaffolds for cell adhesion
will be shown. Studies carried out in the authors laboratories with vertically-aligned carbon
nanotubes (VACNT) will also be presented. The authors have shown the interaction among
CNT (VACNT) and four cell lines: mouse fibroblasts (L-929), mouse embryo fibroblast
(C57/BL6) with or without green fluorescent protein (GFP) and human osteoblast (SaOS-2).
The biocompatibility tests were performed with in vitro tests on raw-VACNT and after
superficial modification by O2 plasma, which changes its hydrophobic character. The non-
toxicity, cell viability, proliferation and cell adhesion were evaluated by: (i) 2-(4,5-dimethyl-
2-thioazoly)-3,5-diphenyl-2H-tetrazolium bromide (MTT) assay; (ii) Lactate dehydrogenase
(LDH) assay; (iii) neutral red (NR) assay; (iv) Scanning electron microscopy (SEM); and
fluorescence microscopy. The influence of catalyst type, VACNT density and superficial
modification were evaluated by morphological, structural and superficial techniques: SEM,
Transmission electron microscopy (TEM), Raman spectroscopy, contact angle (CA) and X-
Ray Photoelectron Spectroscopy (XPS). High cell viability, exceptional cell adhesion and
preference were achieved.
Chapter 10 - This research explores the use of a variety of nanoparticles to impart
conductivity to ceramic matrices. The authors have chosen some highly promising families of
carbon materials: multiwall carbon nanotubes (MWCNTs), singlewall carbon nanotubes
(SWCNTs), carbon black nanograins and graphite micrograins for use as fillers. In this book
chapter, the authors report the results about two types of carbon nanotubes. The MWCNTs
and SWCNTs were dispersed in silicon nitride matrix in different percentages high as 1-
5wt%. A high efficient attritor mill has also been applied for proper dispersion of MWCNTs
in the matrix. In order to get the full use of the benefits provided by carbon nanotubes (CNT)
it is crucial to retain CNT un-attacked in the composites and to optimize the interfacial
bonding between CNT and matrix. By conventional sintering techniques, which are
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

characterized by the requirement of extended holding at very high temperatures, the

destruction of CNT has been reported. In the present work the development of sintering
processes have been performed to consolidate and tailor the microstructure of MWCNTs
reinforced silicon nitride-based ceramic composites. The silicon nitride nanocomposites
systems retained the mechanical robustness of the original systems. Bending strength high as
700 MPa was maintained and an electrical conductivity of 10 S/m was achieved in the case of
3 wt% MWCNT addition. Electrically conductive silicon nitride ceramics have also been
realized by carbon black (in order of 1000 S/m) and graphite additions in comparison.
Examples of these systems, methods of fabrications, electrical percolation, mechanical
properties and potential uses will be discussed.
 Preface xiii

This research explores the use of a variety of nanoparticles to impart conductivity to

ceramic matrices. The authors have chosen some highly promising families of carbon
materials: multiwall carbon nanotubes (MWCNTs), singlewall carbon nanotubes (SWCNTs),
carbon black nanograins and graphite micrograins for use as fillers. In this book chapter, the
authors report the results about two types of carbon nanotubes. The MWCNTs and SWCNTs
were dispersed in silicon nitride matrix in different percentages high as 1-5wt%. A high
efficient attritor mill has also been applied for proper dispersion of MWCNTs in the matrix.
In order to get the full use of the benefits provided by carbon nanotubes (CNT) it is crucial to
retain CNT un-attacked in the composites and to optimize the interfacial bonding between
CNT and matrix. By conventional sintering techniques, which are characterized by the
requirement of extended holding at very high temperatures, the destruction of CNT has been
reported. In the present work the development of sintering processes have been performed to
consolidate and tailor the microstructure of MWCNTs reinforced silicon nitride-based
ceramic composites. The silicon nitride nanocomposites systems retained the mechanical
robustness of the original systems. Bending strength high as 700 MPa was maintained and an
electrical conductivity of 10 S/m was achieved in the case of 3 wt% MWCNT addition.
Electrically conductive silicon nitride ceramics have also been realized by carbon black (in
order of 1000 S/m) and graphite additions in comparison. Examples of these systems,
methods of fabrications, electrical percolation, mechanical properties and potential uses will
be discussed.
Chapter 11 - The present contribution details, in an as exhaustive as possible way, the
fundamental knowledge acquired on fluorinated carbon nanotubes (CNT), also termed
fluorotubes. Since the discrete pioneering articles published in the field a bit more than 10
years ago, around 70 additional references have now appeared which bear witness to the
dynamism of this emergent part of the chemistry of nanotubes. As a matter of fact,
fluorination stands as the starting point for a great part of the modifications performed on
CNT, rendering fluorotubes fundamental intermediates for the integration of CNT in the
nanotechnology processes. Many synthesis routes use fluorotubes as precursors in view of the
subsequent chemical derivatization of CNT, for instance. In parallel, several attempts of
practical developments based on fluorotubes have also lately appeared throughout the
literature, covering the tribology, nanocomposites, or electrochemistry sectors, which outline
the potential interest of such fluorinated nanostructures. The first part of this chapter compiles
the main knowledge reported to date on the subject throughout a still reasonable but
increasingly abundant body of literature. The physicochemical properties and special
characteristics of the C-F chemical bond in fluorotubes are critically analyzed in a second
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

part, and the last section is devoted to some recent tentative applications and future concepts
relating to the fluorination of carbon nanotubes. The present review is essentially depicted
from the chemistry of materials standpoint. Some of the concepts illustrated throughout the
text are enriched by a few works of unpublished data from the authors group.
Chapter 12 - The use of carbon nanotubes as an analytical tool in filters and membranes,
as solid sorbent material, in electrochemical systems involving the building of sensors,
biosensors or carbon nanotube paste electrodes for stripping techniques and in separation
methods including chromatography and electrophoresis can be found in the literature. In this
chapter the authors will present a brief review of the application of CNTs in the analytical
sciences. Finally, the authors will demonstrate new analytical data (a case study) obtained in
the authors research groups involving the development of a solid phase extraction system for
 xiv Avery P. Ottenhouse

cobalt determination using CNT as well as a new potentiommetry stripping method for
antimony determination using CNT as the electrode.
Chapter 13 - This chapter studies the physical characteristics of carbon nanotubes (CNTs)
films and Co-filled CNTs by using an electron cyclotron resonance chemical vapor deposition
(ECR-CVD) method. The results show that the optimum relative intensity ratio of the D band
to G band (i.e., I D / I G ) is 2 for the cases considered in this study. The effects of different
plasma powers of 200W, 300W, 400W and 500W, on the morphology, structure and
electrical properties of the CNTs film, are also studied. The surface density of the vertical
nanotubes decreases when the plasma power is higher than 200W. The Co-filled CNTs grown
at 300W and 400W have a current discharge at the applied voltages of 30 V and 40 V,
respectively. In addition, this chapter also develops a model that analyzes the resonant
frequency of the chiral single-walled carbon nanotubes (SWCNTs) subjected to a thermal
vibration by using Timoshenko beam model, including the effect of rotary inertia and shear
deformation. The frequency obtained by Timoshenko beam model is lower than that
calculated by Euler beam model. As the nanotube aspect ratio of length to diameter decreases,
the discrepancy is more obvious. As the effect of thermal vibration increases, the frequency
for chiral SWCNTs decreases. Furthermore, the oxidation characteristics of TiN thin
films by atomic force microscopy (AFM) electrochemical nanolithography with carbon
nanotube tip are investigated.
Chapter 14 - Since carbon nanotubes (CNTs) show strong tendency to form aggregates
due to their high van der Waals interactions, their dispersion is a prerequisite for practical
applications. In order to enhance the dispersion of multi-walled carbon nanotubes (MWNTs)
in texanol, optimum type of dispersant and its concentration for six commercial dispersants
were evaluated based on the rheological results. Moreover, the cutting and dispersion
efficiencies of MWNTs were compared using conventional ball milling and high energy
milling, whereby the latter was found to be more effective. High energy milling for two hours
produced a large portion of MWNT agglomerates smaller than 150 nm, showing a drastic
increase in slurry viscosity due to the dispersion into individual CNTs. On the other hand,
120-hour ball milling was required to achieve the agglomerate size of 300 nm with less
viscosity increase upon milling. Decrease in the degree of MWNT crystallinity was observed
by both milling, even though 2-hour high energy milling showed slightly less damage than
120-hour ball milling based on XRD and Raman spectroscopy results. The field emission
properties of MWNTs were examined using a screen-printed thick film prepared by 3-roll
milling of MWNTs and UV-sensitive binder solution, with a diode-type configuration in a
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

vacuum for field emission display (FED) application. The effects of MWNT milling, and
various types of ceramic and metal fillers on the emission current density and turn-on field
were evaluated by design of experiment (DOE), whereby the emission properties were shown
to be dependent significantly on both factors. Considerably enhanced emission properties
were obtained with the paste containing 5 – 10 wt. % of either ITO or the glass frit compared
with those without a filler. The paste containing 10 wt. % ITO represented an emission
current density of 176.4 μA/cm2 at 5V/μA, a turn-on field of 1.87 V/μA for an emission
current density of 1 μA/cm2 and a field enhancement factor of 7,580. The paste formulation
was also found to be suitable for fine patterning using UV-lithography techniques. A long-
term stability test for 110 hours of a paste containing 10 wt. % ITO revealed a half-life of
approximately 30,000 hours, which is appropriate for commercial applications.
 Preface xv

Chapter 15 - Due to their molecular configuration, carbon nanotubes (CNT´s) have the
greatest tensile strength and stiffness of all known fiber-like materials combined with an
unusual flexibility and stretchability. Additionally, CNT´s exhibit an excellent electrical as
well as thermal conductivity depending on the modification. On the basis of these properties
and owing to the high aspect ratio, carbon nanotubes offer interesting possibilities for
improving the mechanical stability of plastics provided that the load can be transferred from
the polymer matrix on the CNT´s. But it is also possible to incorporate some functional
properties to use the CNT/polymer-composites as antistatic, electrostatic dissipative materials
as well as for electromagnetic shielding and absorbing.
Beside the polymer applications, research activities have also focused on the
incorporation of CNT´s into a crystalline ceramic matrix. In the case of non-conductive
ceramics, the modification with carbon nanotubes leads to an adjustable electrical
conductivity. The results from experiments to reinforce ceramics with CNT´s and to reduce
the brittleness vary according to the processing method used and the kind of nanotubes.
Especially powder ceramic/CNT-composites produced via the Spark-Plasma-Sintering (SPS)
process exhibit higher tensile strength and strain to failure values. In contrast, the traditional
hot pressing techniques do not lead to an improvement of the mechanical properties because
of the necessary higher processing temperatures and the longer manufacturing time.
A new approach to improve ceramic materials by the incorporation of C-nanotubes is
seen in polymer derived ceramic (PDC) technology, which combines both classes of
materials, polymers and ceramics. Main applications for preceramic polymers (precursors) are
in ceramic fibers, ceramic matrices and polymers as well as ceramic-like coatings. During the
last years a special polycarbosilazane (ABSE) was developed at the University of Bayreuth
for the processing of ceramic SiCN-fibers. The optimized, sequenced manufacturing consists
of four steps: polymer tailoring, fiber spinning, fiber curing and subsequent transformation of
the cured polymer fibers into ceramic fibers by pyrolysis at elevated temperatures. Because of
the low molecular weight of the crude ABSE-polymer, which results in a Newtonian melt
behavior, it was not possible to establish a stable melt-spinning process. Therefore, multi-wall
carbon nanotubes (MWCNT´s) were added to use the strong interaction between the surface
of the nanotubes with the ABSE-polymer to influence the rheology of the polymer melt with
regard to viscoelasticity. The MWCNT content also led to a remarkable increase in tensile
strength of 50 % of the polymer as well as of the resulting ceramic C/SiCN fibers.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.
 In: Carbon Nanotubes: New Research ISBN 978-1-60692-236-1
Editor: Avery P. Ottenhouse © 2009 Nova Science Publishers, Inc.

Short Communications

ON THE DRUDE MODEL TO EXPLAIN QUANTUM

TRANSPORT IN CARBON NANOTUBES

M. A. Grado-Caffaro and M. Grado-Caffaro

Permanent address: SAPIENZA-Scientific Consultants,
C / Julio Palacios 11, 9-B, 28029-Madrid (Spain)

ABSTRACT
The Drude model relative to carrier drift mobility and conductivity is discussed in
relation to its applicability to explain quantum transport through both single-walled and
multiwalled carbon nanotubes. We show that the Drude model, suitable to describe
electrical conductivity in solids as, for instance, semiconductors, is certainly adequate to
discuss key aspects of quantum transport in multiwalled carbon nanotubes. In this
respect, conductance quantization is treated in relation to the model in question by
calculating carrier mobility and conductivity under ballistic regime. As a consequence, an
expression for the quantized conductance of a multiwalled carbon nanotube is derived.

Keywords: Drude model; carbon nanotubes; electrical conductivity; drift mobility;

ballistic regime.
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

1. INTRODUCTION
The well-known Drude model relative to electron transport in macroscopic systems is
extrapolable, under certain conditions, to nanoscopic structures [1-6]. In fact, by means of this
model, analytical approaches have been made to determine electron conductance through both
single-walled and multiwalled carbon nanotubes [3-5]. In this respect, we wish to remark the
significant importance of the theoretical determination of the electrical conductance in carbon
nanotubes. This conductance was found to be quantized [3-5, 7, 8] which constitutes a
relevant fact. Conductance quantization will be treated in the following in relation to ballistic
transport; at this point, let us remember that ballistic transport is a necessary condition (but
 2 M. A. Grado-Caffaro and M. Grado-Caffaro

not sufficient) for conductance quantization (see, for example, ref.[7]). In other words,
conductance quantization implies ballistic regime but the reciprocal assertion is not true in
general. Therefore, if the carrier transport is diffusive, conductance is not quantized. Ballistic
transport through a nanotube, that is, when the electronic mean free path is much longer than
the tube length, is the regime under which, in fact, carbon nanotubes behave (see previous
references) so that scattering in these tubes should consist of elastic collisions (see, for
instance, ref.[7]). This communication is devoted to examine the Drude model within the
context of carbon nanotubes by emphasizing the main aspects related to ballistic regime and
conductance quantization.

2. THEORY
Let us consider the Drude model by which one has that the electrical conductivity is
given by σ = eNμ where e is the absolute value of the electron charge, N is the spatial
carrier density, and μ denotes carrier drift mobility which, in turn, reads μ = eτ m ∗ where
τ designates relaxation time (or momentum-scattering rate) and m ∗ stands for carrier
effective mass. Then, by replacing the second formula into the first one, it follows:

e 2 Nτ
σ= (1)
m∗

Eq.(1) is standard in physics of semiconductors and constitutes a relevant element of

reference within the context of macroscopic condensed-matter systems. Under certain
conditions, this formula can be extrapolated to nanoscale systems (see, for instance, refs.[1-
6]). In particular, let us consider a multiwalled carbon nanotube (MWCNT) conceived as a
longitudinal quantum box [2, 3]; in such a tube, conductance is quantized according to the
fact that the involved quantum number coincides with the numbering of the layers of the tube
(conductance scales with the number of layers) [2-5, 7, 8]. Therefore, quantizing formula (1)
th
for a metallic MWCNT, one has for the conductivity due to the n layer (see, for instance,
refs.[3, 5, 6]):

e 2 N nτ n
Copyright © 2009. Nova Science Publishers, Incorporated. All rights reserved.

σn = (2)
m

∗
where n designates quantum number ( n = 1,2,... ) and m has been replaced by the free-
electron mass denoted by m . In addition, now τ n is transit time or motion time (note that
transport is ballistic) so that τ n = l v n where l is the length of the tube and v n stands for
the magnitude of the quantized Fermi velocity which, for n >> 1 , approaches the electron
velocity deduced from equating the quantized electron energy E n = h n
2 2
(8ml )2
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