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Collection Highlights

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Engineered Carbon Nanotubes and Nanofibrous Materials

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Mechanical Behaviors of Carbon Nanotubes. Theoretical and

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Carbon Footprint Case Studies Municipal Solid Waste

Management Sustainable Road Transport and Carbon
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 Organized
Networks of
Carbon Nanotubes
 Organized
Networks of
Carbon Nanotubes
Edited by

K.R.V. Subramanian
Aravinda C.L. Rao
Raji George
CRC Press
Taylor & Francis Group
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Contents

Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .vii
Author Biography. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix
Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xi

1. Properties of Carbon Nanotubes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

B.V. Raghu Vamshi Krishna and Sannapaneni Janardan

2. Characterization of Carbon Nanotubes. . . . . . . . . . . . . . . . . . . . . . . . . . 9

Sannapaneni Janardan and B.V. Raghu Vamshi Krishna

3. Influence of Gulliver over Lilliput: Novel Properties of Carbon

Nanotube/Liquid Crystal Composites. . . . . . . . . . . . . . . . . . . . . . . . . . 27
S. Krishna Prasad, D.S. Shankar Rao, Marlin Baral, and G.V. Varshini

4. Selective Segregation and Crystallization Induced Organization

of Carbon Nanotube Network in Polymer Nanocomposites. . . . . . . 51
Aishwarya V. Menon, Tanyaradzwa S. Muzata, and Suryasarathi Bose

5. Mechanical Properties of CNT Network-Reinforced Polymer

Composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
Sushant Sharma, Abhishek Arya, Sanjay R. Dhakate, and
Bhanu Pratap Singh

6. Modeling Multiwalled Carbon Nanotubes: From Quantum

Mechanical Calculations to Mechanical Analogues . . . . . . . . . . . . . 107
Brijesh Kumar Mishra and Balakrishnan Ashok

7. Meshes and Networks of Multiwalled Carbon Nanotubes. . . . . . . 119

K.R.V. Subramanian, B.V. Raghu Vamshi Krishna, A. Deepak,
Aravinda C.L. Rao, T. Nageswara Rao, and Raji George

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Preface

Carbon nanotubes (CNTs) are cylindrical shells made, in concept, by roll­

ing graphene sheets into a seamless cylinder. CNTs exist as either single-
walled nanotubes (SWNTs) or multiwalled nanotubes (MWNTs). Iijima’s
report in 1991 helped create awareness of CNTs to the scientific commu­
nity and triggered a deluge of interest in CNTs. A variety of methods for
the production of aligned arrays in catalytic chemical vapor deposition has
been demonstrated. Horizontally well-aligned CNT arrays on suitable
substrates are highly desired for various SWNT device applications, such
as field effect transistors, sensors, light emitters, and logic circuits.
Regularly bent CNTs are proposed for applications including mechanical
nanospring devices, high-resolution atomic force microscopy tips, and nano­
circuit interconnections in device. Self-assembly can form some novel struc­
tures. Ensembles of CNTs form networks that can be transparent and at the
same time conductive, showing great potential for replacing the currently
used indium tin oxide (ITO), whose future availability is at risk due to the
impoverishment of the world’s sources of indium. CNT networks offer not
only an alternative to ITO but also advantages such as flexibility, usability
with plastic substrates, and capability to avoid contamination from ITO of
other device materials. In this book, we expand and elucidate some novel and
state-of-the-art techniques used for alignment of CNTs and their composites,
to form organized networks. The initial chapter dwells upon properties and
characterization of CNTs, while subsequent chapters deal with the novel and
interesting alignment methodologies and their applications.
We, the editors, Subramanian, George, and Aravinda Rao, draw upon
our extensive research experience and works in the field of organized CNT
networks to infuse this book with the required bent and perspectives. We
would like to express our sincere thanks to our management, namely
Ramaiah Institute of Technology, Bangalore, India (Shri M.R. Jayaram,
Chairman, GEF; Shri M.R. Seetharam, Vice Chairman, GEF and Director,
Ramaiah Institute of Technology; Dr. N.V.R. Naidu, Principal, Ramaiah
Institute of Technology) as well as Reliance Industries Ltd., Vadodara,
India, for supporting this endeavor. We also thank the distinguished authors
who have contributed their mite. We finally thank our family members for
their support.
Professor K.R.V. Subramanian
Professor Aravinda C.L. Rao
Professor Raji George

vii
Author Biography

Professor K.R.V. Subramanian is Professor in the

Mechanical Engineering Department and also works
as Co-Research Coordinator, Ramaiah Institute of Tech­
nology, Bangalore, India. His research interests are
solar technology, nanotechnology, carbon nanotubes,
fuel cells, energy storage, and sensors. He earned his
PhD from Cambridge University in 2006 with speciali­
zation in nanotechnology. His bachelors and masters
degree in materials engineering were from NIT, Trichy
and IISc, Bangalore, respectively. He has over 20 years
of academic and industrial work experience. He has published over 100 jour­
nal and conference papers. He has also edited 2 books. He is a Marquis Who’s
Who of the World and IBC Top 100 professionals. He has been co-principal
investigator for many government funded research projects.

Dr. Aravinda C.L. Rao is working as a General

Manager at Product Application & Research Center,
Reliance Industries Ltd., Vadodara. After completing
his doctoral studies at Bangalore University in 2001,
he pursued his post-doctoral work at IISc, Bangalore,
as an Alexander Humboldt fellow at Karlsruhe Insti­
tute of Technology, Technical University of Munich,
Germany, and University of California at Riverside.
His research interests encompass nanotechnology, graphene-based advanced
materials, polymer composites, biosensors, thin films, and coatings for elec­
tronics. He has rich and varied academic as well as industrial R&D experience
of over 18 years in multinational companies. He has authored more than
25 papers in reputed journals, a book chapter, and several conference papers.
He has handled large to medium scale R&D projects successfully and has
established and managed large research labs.

ix
x Author Biography

Dr. Raji George is a Professor and Head in the

Mechanical Engineering Department of Ramaiah
Institute of Technology (RIT), Bangalore. His areas
of interests include subjects such as nanotechnology,
mechanics of materials, and design and finite element
methods. He earned his PhD from Visvesvaraya Tech­
nological University (VTU) in 2008. He has more than
33 years experience in academia and teaching. He was
awarded Scientific Award of Excellence of 2011 by
American Biographical Institute. He was conferred the Best Engineering
Teacher Gold Medal Award for the year 2009, instituted by Sir M. Visvesvar­
aya Memorial Foundation, Bangalore. He has more than 40 journal and
conference papers to his credit. He has 1 patent granted in his name and
applied for 1 patent. He is the Principal Investigator for a major research
project for Boeing Inc.
Contributors

B.V. Raghu Vamsi Krishna Aishwarya V. Menon

Department of Mechanical Center for Nano Science and
Engineering Engineering
GITAM University Indian Institute of Science
Bengaluru, India Bangalore, India

Janardan Sannapaneni Tanyaradzwa S. Muzata

Department of Chemistry Department of Materials
GITAM University Engineering
Bengaluru, India Indian Institute of Science
Bangalore, India
Sannapaneni Janardan
Department of Chemistry, Gitam Suryasarathi Bose
School of Science Department of Materials
GITAM University Engineering
Bengaluru, India Indian Institute of Science
Bangalore, India
S. Krishna Prasad
Centre for Nano and Soft Matter Sushant Sharma
Sciences CSIR-National Physical Laboratory
Bengaluru, India New Delhi, India
Academy of Scientific & Innovative
D.S. Shankar Rao Research (AcSIR)
Centre for Nano and Soft Matter Ghaziabad, Uttar Pradesh, India
Sciences
Bengaluru, India Abhishek Arya
CSIR-National Physical Laboratory
Marlin Baral New Delhi, India
Centre for Nano and Soft Matter Academy of Scientific & Innovative
Sciences Research (AcSIR)
Bengaluru, India Ghaziabad, Uttar Pradesh, India

G.V. Varshini Sanjay R. Dhakate

Centre for Nano and Soft Matter CSIR-National Physical Laboratory
Sciences New Delhi, India
Bengaluru, India Academy of Scientific & Innovative
Research (AcSIR)
Ghaziabad, Uttar Pradesh, India

xi
xii Contributors

Bhanu Pratap Singh A. Deepak

CSIR-National Physical Laboratory Department of Mechanical
New Delhi, India Engineering
Academy of Scientific & Innovative GITAM University
Research (AcSIR) Bangalore, India
Ghaziabad, Uttar Pradesh, India
Dr. Aravinda C.L. Rao
Brijesh Kumar Mishra Product Application & Research
Computational Chemistry Unit Center, Reliance Industries Ltd.
International Institute of Vadodara, India
Information Technology
Bangalore, India Dr. T. Nageswara Rao
Department of Mechanical
Balakrishnan Ashok Engineering
Centre for Complex Systems & Soft GITAM University
Matter Physics Bangalore, India
International Institute of
Information Technology Dr. Raji George
Bangalore, India Department of Mechanical
Engineering
Dr. K.R.V. Subramanian Ramaiah Institute of Technology
Department of Mechanical Bangalore, India
Engineering
Ramaiah Institute of Technology
Bangalore, India
1
Properties of Carbon Nanotubes

B.V. Raghu Vamshi Krishna

Department of Mechanical Engineering
GITAM School of Science GITAM University
Bengaluru, India

Sannapaneni Janardan
Department of Chemistry
GITAM School of Science GITAM University
Bengaluru, India

1.1 Introduction
Carbon nanotubes (CNTs) are rolled up graphene sheets, generally of
two types, namely single-walled CNTs (SWCNTs) and multiwalled
CNTs (MWCNTs). There are variations in both SWCNTs and MWCNTs.
They vary by length, purity, and practicality. CNTs are long, thin carbon
wires just a nanometer or so in diameter; however, they can be up to
several thousands of times in length. They possess exciting mechanical,
electrical, and optical properties that would make them ideal nanoscale
materials. Rolling of CNTs is described with circumferential vector
denoted by Ch that is expressed in terms of primitive vectors of graphene
sheet [1].

Ch ¼ na1 þ ma2

where a1 and a2 are primitive vectors in 2D hexagonal lattice in

Figure 1.1. Generally, CNTs are classified into three groups according
to the values of ‘m’ and ‘n’. For armchair nanotubes (n,m = n and
chiral angle = 30°), carbon–carbon bonds are perpendicular to the
axis of tube, for zig-zag nanotubes (either n or m are zero or chiral
angle = 0°), carbon–carbon bonds are parallel to the axis of tube
as shown in Figure 1.2, and for chiral tubes (n,m and chiral angle 0° <
θ < 30°) [1].

1
2 Organized Networks of Carbon Nanotubes

FIGURE 1.1
Unit vectors a1 and a2 and armchair, zig-zag, and chiral configuration [1].

FIGURE 1.2
Armchair and zig-zag CNTs [1].

1.2 Properties of CNTs

1.2.1 Electronic Properties
Electronic properties of CNTs can be altered by changing its structure (n-m
vector). If the vector is a multiple of 3 then the CNTs are metallic (conductor)
Properties of Carbon Nanotubes 3

and if the n-m vector is not a multiple of 3 then the CNTs are semiconductors
[2]. Two main properties, Fermi energy (EF) and energy gap (Eg), are calcu­
lated to investigate the properties of chiral CNT. Energy gap is the difference
between the orbitals, that is, from the lowest unoccupied orbital (LUMO) to
highest occupied orbital (HOMO), and this energy gap is caused by the
curvature of tube wall. Electrical conductivity of CNTs is determined by
energy gap; the smaller the gap, the stronger the conductivity. EF and Eg are
defined in equations 1 and 2.

EF ¼ ðELUMO þ EHOMO Þ=2 ð1Þ

Eg ¼ ELUMO EHOMO ð2Þ

If the vector (n, m) is not a multiple of 3 then the electronic density of

states of SWCNTs shows the band gap near fermi level and produces a
semiconductor. And if the vector (n,m) is a multiple of 3, both valance
band and conduction band of SWCNTs overlap each other, producing a
conductor.
From Figure 1.3, it is observed that chiral nanotube of vector (8, 4) and
(10, 5) is direct bandgap semiconductor and (4, 2) is indirect band gap
semiconductor. CNTs of vector (6,3) and (12,6) are conductors with energy
gap of 0.33 and 0.1 eV. Metallic nanotubes are highly conductive as they
can carry billions of amperes of current due to few defects and their
resistance is also very low [3].

1.2.2 Mechanical Properties

Many experiments have been conducted to investigate the properties of
CNTs. Because of sp2 hybridization of C–C bonds, it is expected to have

FIGURE 1.3
Energy band structures of chiral SWCNTs [3].
4 Organized Networks of Carbon Nanotubes

very high Young’s modulus (in terms of TPa), breaking strength, stiffness,
and tensile strength. These properties depend on chirality and size. The
Young’s modulus of CNTs for different diameters ranges from 1.28 to 1.8 TPa,
when compared to steel (0.21 TPa) it is about 10 times stronger [4].
Treacy et al. determined the mechanical properties of SWCNTs by thermal
vibration by TEM method. The Young’s modulus E = 1.77~1.37/+2.38 TPa for
do = 5.6~24.8 nm, di = 1.0~6.6 nm, t = 3.3∼18.2 nm [4,5]. Lu has determined the
mechanical properties of SWCNTs by Empirical force-constant model method.
The properties are E = 0.97∼1.11 TPa, ν = 0.269∼0.280, G = 0.436∼0.541 TPa, for
d = 0.68~27.0 nm [4,6]. Properties of CNTs determined by different methods are
given in Table 1.1
In MWCNTs, the stress transferability between layers is weak and the
maximum load is taken by the outermost layer. So at the outermost layer
of MWCNTs, the failure will start by breaking the bonds between carbon–
carbon atoms [4].
Graphene and CNTs (armchair, zig-zag, and chiral) are modeled in
analysis system (ANSYS), and Young’s modulus was determined analyti­
cally. As the diameter of the chiral nanotube increases, there is a slight
increase in Young’s modulus, and as the diameter of the zig-zag nanotube
increases, there is an increase in Young’s modulus approximately from
0.99 to 1.05 TPa. So the mechanical properties change as the diameter and
chirality of CNTs change [14].
Because of the bending of CNTs, there is a significant change in atomic
structure from sp2 to sp3 hybridization. Because of this, the electrical
conductance of SWCNTs is greatly reduced. For armchair (n, n) CNTs,
there is no change in bandgap and their electrical conductivity remains
same. But for zig-zag (n, 0) and chiral nanotubes, the bandgap increases
due to increase in tension and because of this the conductivity of CNTs
may change from conducting to semiconducting due to deformation
shown in Figure 1.4. [15].

1.2.3 Vibrational Properties

Graphene sheet consists of two translational phonons with in-plane and
out-of-plane atomic displacements. As the graphene sheet is rolled into a
cylinder, the translational phonon perpendicular to plane displacement
corresponds to a breathing mode, in which the atoms will vibrate in
radial direction and so it is called ‘radial breathing mode (RBM)’. The
frequency of RBM is linear to radius of tube R, ωðRÞ ¼ C=R, C is constant.
The diameter of the nanotube can be calculated from the RBM wavenum­
ber because the frequency of RBM is inversely proportional to the diameter
of nanotube [16].
Early research conducted on tangled SWNTs and ropes of SWNT or
MWNTs is measured by Raman Spectra. Raman spectra exhibit three
bands: the RBM band at ~200 cm−1, that is, the vibration at which the
Properties of Carbon Nanotubes 5

TABLE 1.1
Mechanical properties of CNTs, which are determined by different methods

CNT Method Properties

SWCNTs Analytical Asymptotic Homogenization E = 1.44 TPa,

Model [7] Shear modulus = 0.27 TPa,
Tube thickness = 1.29 Å
SWCNTs Numerical–structural Mechanics-based 3D E = 0.97~1.05 TPa,
Finite Element Model (FE) approach [7] Shear modulus = 0.14~0.47 TPa,
Tube thickness = 6.8 Å
Double- Numerical–structural Mechanics-based FE E = 1.32~1.39 TPa,
walled approach [7] Shear modulus = 0.37~0.62 TPa,
CNTs Tube thickness = 6.8 Å
MWCNTs Numerical–structural Mechanics-based FE E = 1.39~1.58 TPa,
approach [7] Shear modulus = 0.44~0.47 TPa,
Tube thickness = 6.8 Å
SWCNTs Modified Morse Potential [8] E ≈ 1.13 TPa, σTS = 126.2 GPa for
armchair,
σTS = 94.5 GPa for zig-zag
SWCNTs Finite Element Analysis Beam Element E = 1.005~1.04 TPa
Model [9] G = 0.155~0.455 TPa
For armchair d = 0.5~2.8 nm
E = 1.027~1.081 TPa
G = 0.32~0.48 TPa
For zig-zag, d = 0.5~2.8 nm
E = 0.965~1.031 TPa
G = 0.32~0.48 TPa
MWCNTs Atomic Force Microscopy [10] E = 350 ± 110 GPa
G = 1.4 ± 0.3 GPa
d0=20~50 nm, L > 0.8 µm
SWCNTs Molecular Mechanics Model–Modified For zig-zag
Morse Potential. σTS= 105.38 GPa, Ɛf = 0.33
Reactive Empirical Band Order Potential For armchair
[11] σTS= 134.01 GPa, Ɛf = 0.43
MWCNTs Timoshenko Beam Model [12] For MWCNTs
E= 126~937 GPa,
G= 33~785 MPa,
d0= 30~60.9 nm,
di= 7.9~12.4 nm,
L= 1.80~18.4 mm
SWCNTs Molecular Mechanics [13] For armchair E = 0.963~1.025 TPa
SWCNTs ν = 0.15~0.29
For zig-zag and chiral, d = 0.4~1.8
nm, L = 1.8130~2.8986 nm, E = 1
TPa for graphene
6 Organized Networks of Carbon Nanotubes

FIGURE 1.4
The variation of bandgap as the strain increases for CNTs.

diameter of nanotube expands and contracts, the G band at ~1600 cm−1, that
is, the in-plane vibration of graphite, and weak disorder band (D band) at
~1350 cm−1. Figure 1.5 shows the Raman Spectra for ropes of SWCNTs at
different laser excitation energies and it can be observed that there is a

FIGURE 1.5
Raman spectra for ropes of SWNTs at five different laser excitation energies.
Properties of Carbon Nanotubes 7

sudden increase in peak intensity. For samples of nanotube usually of

different chirality and radius, the Raman spectra gives information about
diameter of nanotubes and their chirality. So Raman spectra is an important
tool for structural characterization [16].

References
1. Paradise M; Goswami T. Carbon nanotubes – production and industrial appli­
cations. Materials and Design 28 (2007) 1477–1489.
2. Yanagi K. Differentiation of Carbon Nanotubes with Different Chirality. Department
of Physics, Tokyo Metropolitan University, Hachioji, Tokyo, Japan (2014).
3. Liu J; Lu J; Lin X; Tang Y; Liu Y; Wang T; Zhu HJ. The electronic properties of
chiral carbon nanotube. Computational Materials Science 129 (2017) 290–294.
4. Hu Z; Lu X. Mechanical Properties of Carbon Nanotubes and Graphene. Elsevier
(2014).
5. Treacy MMJ; Ebbesen TW; Gibson JM. Exceptionally high Young’s modulus
observed for individual carbon nanotubes. Nature 678–680 (20 June 1996) 381.
6. Lu JP. Elastic properties of carbon nanotubes and nanoropes. Physical Review
Letters 79 (7) (18 August 1997) 1297.
7. Kalamkarov AL; Georgiades AV; Rokkam SK; Veedu VP; Ghasemi-Nejhad MN.
Analytical and numerical techniques to predict carbon nanotubes properties.
International Journal of Solids and Structures 43 (2006) 6832–6854.
8. Xiao JR; Gama BA; Gillespie JW, Jr. An analytical molecular structural mechanics
model for the mechanical properties of carbon nanotubes. International Journal of
Solids and Structures 42 (2005) 3075–3092.
9. Kirtania S; Chakraborty D. Finite element based characterization of carbon
nanotubes. Journal of Reinforced Plastics and Composites 26 (15) (2007) 1557–1570.
10. Guhados G; Wan WK; Sun XL; Hutter JL. Simultaneous measurement of
Young’s and shear moduli of multiwalled carbon nanotubes using atomic
force microscopy. Journal of Applied Physics 101 (2007) 033514.
11. Duan WH; Wang Q; Liew KM; He XQ. Molecular mechanics modeling of
carbon nanotube fracture. Carbon 45 (2007) 1769–1776.
12. Wei XL; Liu Y; Chen Q; Wang MS; Peng LM. The very low shear modulus of
multi-walled carbon nanotubes determined simultaneously with the axial
Young’s modulus via in situ experiments. Advanced Functional Materials 18 (10)
(2008) 1555–1562.
13. Ávila AF; Lacerda GSR. Molecular mechanics applied to single-walled carbon
nanotubes. Materials Research 11 (3) (2008) 325–333.
14. Lu X; Hu Z. Mechanical property evaluation of single-walled carbon nanotubes
by finite element modelling. Composites: Part B 43 (2012) 1902–1913.
15. Liu B; Jiang H; Johnson HT; Huang Y. The influence of mechanical deformation
on the electrical properties of single wall carbon nanotubes. Journal of the
Mechanics and Physics of Solids 52 (2004) 1–26.
16. Popov VN. Carbon nanotubes: properties and application. Materials Science and
Engineering R 43 (2004) 61–102.
2
Characterization of Carbon Nanotubes

Sannapaneni Janardan
Department of Chemistry, Gitam School of Science
GITAM University
Bengaluru, India

B.V. Raghu Vamshi Krishna

Department of Mechanical Engineering
GITAM School of Science GITAM University
Bengaluru, India

2.1 Introduction
The innovation of CNTs occurred conceptually in early 1950s and 1970s.
However, their significance was highlighted in 1990s by Iijima. Initial
investigations suggested that SWCNTs have rolled up graphene as a
single sheet, whereas the MWCNTs have similar structure as SWCNTs
but with more concentric tubes in multiple numbers [1–3]. Among the
three types of CNTs (zig-zag, armchair, and chiral), chiral form is having
significant optical, mechanical, and electrical properties [4, 5].
The CNTs usually possess ballistic electron transport throughout the
nanotubes due to their 1D structure at room temperature. In addition,
they possess high thermal conductivity (>3000 W/m K) than diamond
and basal plane of graphite [6]. Moreover, because of their high Young’s
modulus, they possess high mechanical properties over other steel
materials [7]. CNTs have shown significant applications in the fields of
physics and mechanics [8], hence they are involved in manufacturing of
devices such as nanomanipulation, hydrogen storage, and nanoporous
membranes [9]. There are several unexplored fields that have potential
application in aerospace, automobile, composite reinforcements, catalyst
supports, probes, sensors, and nanoreactors [10]. In addition, character­
ization techniques are highly significant in measuring the defects
occurred during purification process [11]. In this chapter we address
the significant characterization techniques that are used to determine the
complex CNTs – both quantitative and qualitative analysis. To identify

9
10 Organized Networks of Carbon Nanotubes

the large number of problems that have occurred with respect to con­
trolled production and to elucidate the morphology and structure of
CNTs, in Table 2.1 various kinds of characterization techniques and
their usages are described.

TABLE 2.1
Different analytical techniques used for the characterization of CNTs [12]

Characterization
Technique Used for Studying

Microscopy and Diffraction Techniques

AFM Morphological analysis of internal structure (diameter, number of
layers, and distance between them)
TEM Morphological analysis of internal structure
(diameter, number of layers, and distance between them)
SEM Morphological analysis of internal structure
(diameter, number of layers, and distance between them)
ND Morphological analysis of bulk samples
XRD Morphological analysis of bulk samples
Spectroscopic Techniques
RS Purity and presence of by-products, diameter distribution (n, m), and
chirality
IR and FTIR Purity, functionalization by attaching functional groups to
the sidewalls
UV–Vis and NIR Dispersion efficiency, diameter and length distribution, and purity
FS Size, dispersion efficiency (n, m), and chirality
XPS and EDS Elemental composition and functionalization (covalent and
noncovalent)
Thermal Techniques
TGA Purity and presence of by-products, quality control of synthesis and
manufacture process
Separation Techniques
SEC Purification and separation by size (length)
Capillary Purification, separation by size (length, diameter, and cross-section)
electrophoresis
Field flow Functionalization by size (length)
fractionation
Ultracentrifugation Separation by chirality, electronic type, length, and enantiometric
identity
Characterization of Carbon Nanotubes 11

Among the above characterization techniques, the significant techniques

are listed below.

2.2 Characterization Techniques for CNTs

2.2.1 X-Ray Photoelectron Spectroscopy
It is one of the significant techniques used for the identification of chemical
structure of the CNTs. Generally, the SWCNTs that are free from the
dopants consist of three peaks: (i) sp3 carbon peak at 285 eV, (ii) sp2 carbon
peak at 284.3 eV, and (iii) sp3 carboxyl group (C–O) peak at about 288.5 eV
[13]. In case of MWCNTs, the sp3 carbon energy position is about 284.6 eV,
and 0.3 eV negative shift occurred between SWCNTs and MWCNTs clearly
reveals the information about the weaker C–C bond binding energy and the
interlayer spacing. The shifts in the binding energy always vary with the
diameter of the nanotubes in MWCNTs, and for 30 nm diameter aligned
MWCNTs, binding energy is about 50 meV between the sidewalls and tips.

2.2.2 Electron Microscopy

To observe the size, shape, and structure of the CNTs, electron microscopy
(SEM, TEM) is one of the essential techniques. These techniques usually
work based on the Lamberts law and analyze the CNTs’ cross-section
intensity. TEM is used to determine the linear adsorption coefficient and
inner and outer diameter of MWCNTs [14]. MWCNTs intershell spacing,
which is generally varying with diameter of CNT (0.34–0.39 nm), was
identified by TEM. STM is a technique used to experimentally find out
the energy band models and density of states, and it will give a clear
picture about the electron densities with its structure [15]. To identify any
kind of CNT structure, always coat the CNT on the conducting substrate
and perceive the structure at low temperatures (4.2 K) [16]. Chirality and
its influence on electronic properties of CNTs are generally determined by
STM. In addition, it is also used to determine the properties of intramole­
cular junction and for measuring the electronic contacts, doping, defects
and symmetry. Atomic vacancies (lateral size 0.5–0.8 Å, height 0.1 nm) of
the metallic and semiconducting CNTs are also identified effectively by
Computer simulation coupled STM [17].

2.2.3 X-Ray Diffraction

The statistical characteristics of CNTs such as diameter, distribution of
chirality, number of layers, internal spacing, impurities, and structural
strain were efficiently identified by XRD from Table 2.2, and the
12 Organized Networks of Carbon Nanotubes

TABLE 2.2
Characterization of pure, OH, and COOH functionalized MWCNTs

2θ Characteristic Interlayer Spacing Crystalline Size

Type of CNTs (°) Peaks (d002) (m) (D) (m) [Ref]

Pure 25.6 002 3.47 × 10−10 5.2 × 10−9 [20,21]

MWCNTs 40.0
59.0
71.0
(-OH) 26.2 002 3.47 × 10−10 3.3 × 10−9 [21]
MWCNTs
(-COOH) 26.1 002 3.44 × 10−10 3.5 × 10−9 [21]
MWCNTs

pattern of CNTs resembles the pattern of graphite, in which MWCNTs

show peak at (002) clearly identified from Figure 2.1, which is also
present in the XRD pattern of graphite, and the intensity of the peak
always depends upon the alignment of the CNTs, that is, the reduction
of the intensity of the peak (002) represents that the CNTs are properly

FIGURE 2.1
XRD spectra of MWCNTs.
Source: Evaluating the characteristics of multiwall carbon nanotubes, J. H. Lehman et al.,
Carbon, 49(8) (2011).
Characterization of Carbon Nanotubes 13

aligned [18]. However, this technique is not useful in differentiating

the CNTs and graphite [19].

2.2.4 Raman Spectroscopy

This technique efficiently determines the tube alignment, defects, and purity as
well as distinction of the MWCNTs relative to other carbon allotropes. In
addition, it significantly describes the structure of SWCNTs. It is a nondestruc­
tive technique used to detect the purity of the CNTs and determine the
properties of CNTs through its vibration modes resulting from the scattered
photons released from the sample that is bombarded with intense light beam.
It generally produces two kinds of bands: (i) graphitic band (G band) observed
at around 1500–1600 cm−1, which originates from the graphene sheets’ vibra­
tion planes. (ii) Defect band (D band) observed at around 1300–1350 cm−1,
which originates from the sidewall of CNTs with defects. In addition, the ratio
of defect band and graphitic band (D/G) will clearly give idea about the
quality of the nanotubes, that is, if the D/G ratio is small then the CNTs are
having minimum defects in their structure [22–26]. However, aggregation of
CNTs will influence the D, G band signals, so in order to overcome the
interferences of the aggregation of CNTs, treating with surfactants such as
Triton X-100 is useful [27]. The diameter and chiral angle integers, n and m
determine the structure and size of the CNTs. Based on different n,m values,
the structure of the CNTs also varies from zig-zag, chiral, and armchair [28].
The characteristic peaks of SWCNTs in the Raman spectrum have lots of
features, which include a frequency peak at <200 cm−1, which is absent in
graphite. The peaks that are obtained at 1340 cm−1 represent the disorder in
the graphite material, which is known as D band having chirality due to
double resonance conditions [29]. Moreover, in individual SWCNTs, D band
generally splits into two bands and the separation always depends upon the
incident light [30]. The multiple peaks obtained in 1550–1600 cm−1 range
generally correspond to G band. For graphite, a single peak is obtained at
1582 cm−1, which represents the graphitization of the sample and is classi­
fied into G+ and G− bands. G+ band represents the atomic displacement in
the direction of axis of CNT, but in G− band, displacement is done in the
circumferential direction and it will vary for metallic and semiconducting
systems. The line obtained at 2600 cm−1 is the overtone of the D band, which
is also called as GI band and represents the long-range order in the sample.
G band is the significant characteristic feature in distinguishing both
SWCNTs and MWCNTs, which is decomposed into two bands in SWCNTs
and it is asymmetric in MWCNTs [31].

2.2.4.1 Raman Spectra of CNT

From Figure 2.2, it is clearly possible to distinguish the MWCNTs (S0)
and their functionalized forms (S1, S2, S3) through chemical oxidation
14 Organized Networks of Carbon Nanotubes

FIGURE 2.2
Raman spectra of pristine MWCNTs (S0) and their oxidized forms (S1, S2, S3).
Source: Characterization of multi-walled carbon nanotubes functionalized by a mixture of
HNO3/H2SO4, Le Thi Mai Hoa, Diamond and Related Materials, 89 (2018) 43.

by using HNO3 and H2SO4 at various reaction parameters, which

revealed that the peaks of D band for pristine MWCNTs, that is, S0,
and oxidized MWCNTs, that are, S1, S2, S3 are at 1328, 1331, 1330, 1332
cm−1, respectively. The G band for pristine MWCNTs (S0) and their
oxidized forms (S1, S2, S3) was obtained at 1580, 1582, 1581, 1583 cm−1,
respectively in Table 2.3. The significant higher frequency shifts of
oxidized samples over normal pristine MWCNTs were mainly due to

TABLE 2.3
Raman spectral data of pristine MWCNTs and their oxidized forms [24].

HNO3 and H2SO4 Treatment D Band Location G Band Location Id/Ig

Sample Ratio Time (h) (cm−1) (cm−1) Ratio

S0 No treatment No treatment 1328 1580 1.15

S1 1:3 6 1331 1582 1.20
S2 1:3 12 1330 1581 1.29
S3 1:3 18 1332 1583 1.40
Characterization of Carbon Nanotubes 15

doping through oxidation. The basic peaks of MWCNTs are retained

even after oxidation, which indicates the presence of graphite structure
as such after oxidation. The structural defect that is measured by the
ratio of D and G bands (Id/Ig) is determining the presence of larger
proportion of sp3 carbon, which in turn is proportional to the defects
and degree of disorder in the MWCNTs. The percentage of defects is
increased with increase in the treated time, which can be easily
observed through Table 2.3.

2.2.5 Absorption Spectroscopy

2.2.5.1 FT-IR Spectrophotometer
This technique is used to determine the quantitative and qualitative
analysis of samples. Moreover, it is highly significant in determining
the functional groups attached to the CNTs and the intensity of the
peak increases with increase in the OH functional groups on the
CNTs [32].

2.2.5.2 FT-IR Spectrum of CNT

The FT-IR spectra of MWCNTs in Figure 2.3 has shown characteristic
peaks at 1096 cm−1, which represent C–O stretching frequency, and the
peak resonates at 1632 and 1634 cm−1 represent C=C stretching fre­
quency and peaks at 2926 and 2856 cm−1 represent CH2 asymmetric
and symmetric stretching and the absorptions at 3436 cm−1 represent
OH stretching. There is a comparative view of FT-IR spectra for CNT,
oxidized CNT, and HAP-CNT represented in Table 2.4 [33]. The peak
present with the 3000–3600 cm−1 is associated with hydroxyl group
due to CNT oxidation. The C=O group resonates at 1735cm−1 (carbonyl
acid stretching frequency), C–O–H in-plane bending at 1435 cm−1, C–
O–H out of plane bending at 995 cm−1, C–O stretching at 1232, 1139,
and 1067 cm−1, which have resemblances with Silverstein et al. [27].
The peak of C=C resonates at 1624 and 1497 cm−1 (vibrations of
aromatic nucleus), 889 and 846 cm−1 (adjacent or aromatic C–H vibra­
tion), and 660 and 560 cm−1 bands represent polar clusters attached to
the CNTs aromatic ring. The phosphate group resonates at 560, 601,
and 961 cm−1; the crystalline apatite arrangement was vibrated at 1037
and 1095 cm−1. The carbonyl absorption was shifted to 1740 cm−1,
which represents the successful bonding of COOH with HAP cation,
and oxidized CNT vibrations were completely merged with phosphate
vibrations at 958, 599, and 567cm−1.
16 Organized Networks of Carbon Nanotubes

FIGURE 2.3
IR spectra of HAP, CNT, oCNT, oCNT-HAP.
Source: Oxidized-sulfonated multi-walled carbon nanotube/hydroxyapatite hybrid parti­
cles: Synthesis and characterization, Kaio A.B. et al., Journal of Solid State Chemistry, 279
(2019) 120924.
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